Reactor Exercises - 2013 PDF
Reactor Exercises - 2013 PDF
Reactor Exercises - 2013 PDF
2
Example 3: Isothermal, second-order reaction
The reaction A+BC+D is carried out at 80 C in an isothermal, perfectly stirred tank reactor. The
reaction rate can be described as second-order, where k 0,058 m3 /(kmol min) .
At 80 C, 240 kg of material A (MA=60 g/mol) and 400 kg of material B (MB=90 g/mol) is measured
into the stirred tank. At this point, the volume of the (liquid) reaction mixture is 900 dm3. The reaction
does not change the volume. How much time is required to reach 95% conversion?
Solution
t 9,96 min
In aqueous solution, the reaction is reversible and second-order. A series of isothermal experiments
with 2.7 mol/dm3 initial concentration were performed in a laboratory-scale batch reactor to determine
the reaction rate coefficient. A sample was taken from the reactor every 10 minutes, and the
conversion of sodium propanoate was determined:
time (min) 0 10 20 30 50
Conversion (%) 0 39 55 64 72,5 80
Based on the data in the table, design an isothermal batch reactor do produce 1360 kg/h propanoic
acid. Servicing time (loading, heating, cooling and emptying) is 45 minutes per batch. Since the
equilibrium conversion of sodium propanoate is 80%, use an operating conversion of 75%. Initial
concentrations in the industrial reactor are 323 kg/m3 sodium propanoate and 123.4 kg/m3
hydrochloric acid (100% HCl). The density of the reaction mixture is constant, 1200 kg/m3.
V 11,8 m 3
4
Example problems: continuous stirred tank reactors
reactor. The desired conversion is 75 %. Feed streams are equal and contain only one component each.
Stream A contains 2.8 mol/dm3 of component A, stream B contains 1.6 mol/dm3 of component B. The
value of k1 is 7 dm3/(molmin), the value of k-1 is 3 dm3/(molmin). What is the required feed rate?
Solution
5
V dm 3
VA VB 4
2 min
m3
V V t 0,1 5 min 0,5 m3
min
Example 18: Isothermal tubular reactor, gas phase reaction, no change in the number of moles
Mehtane and sulphur react in gas phase at 600 C and atmospheric pressure, yielding carbon
disulphide and hydrogen sulfide. The reaction is carried out in an isothermal tubular reactor. The
reaction rate of sulphur can be described with the equation kcAcB (k = 119,8 m3/molh), provided that
the reaction equation is the following:
CH4+2S2CS2+2H2S i.e.
A+2BC+2D
The feed is stoichiometric, the feed rate of methane is 23,8 mol/h.
What is the required residence time to achieve an 18% conversion of methane? What is the required
size of the reactor?
Example 19: Isothermal, gas phase reaction, no change in the number of moles
The following second-order reaction is carried out in an isothermal, ideal tubular reactor.
A+BC+D k = 5.2710-3 m3mol-1s-1
The feed contains only reactants. The pressure and temperature in the reactor are 1.3 bar and 500 C.
a) The feed stream contains the component is stoichiometric ratio. What percent conversion can be
achieved with a residence time of 8 s??
b) What is the required residence time if twice the required amount of component A is added, and
40% percent conversion is desired? What percent is the flow rate of that in part a)?
7
L
v2 t t 8s
2 1 1,46
v1 L t 2 5,47 2 s
t1
kmol
n c 8,33
h
X 0,33
Example 22: Adiabatic reaction, gas phase reaction, no change in the number of moles
Carbon monoxide and water are converted into carbon dioxide and hydrogen at atmospheric pressure
in an adiabatic tubular reactor. The reaction goes to equilibrium. The feed temperature is 380 C, the
feed rate 2.5 m3/s. The ratio of CO and H2O in the feed is 1:4, the feed contains no inert gas of reaction
products. The outlet stream temperature is 500 C. The reaction enthalpy is 39,4 kJ/mol, the molar
heat capacity of the gas mixture is 34 kJ/(kmolK). Calculate the conversion and the maximal
temperature increase for the reaction!
8
Example 23: Adiabatic reaction, tube reactor, liquid phase second-order reaction
A second-order A+BC+D reaction is carried out in an ideal adiabatic tube reactor with a volume of
0.12 m3. The reaction rate constant can be calculated with the equation 6.52105e-42300/RT kmol/(m3s).
The initial concentration of both components is 1,1 kmol/m3. The feed contains no product, its
temperature is 12 C, the feed rate is 410-4 m3/s. The reaction enthalpy is 42600 kJ/kmol, the specific
heat capacity of the mixture is 2800 J/(kgK), its density is 840 kg/m3. Calculate the conversion!
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Example problem: combinations of different reactor types
Example 27: Comparison of continuous mixed tank reactor and tubular reactor. Isothermal and
adiabatic reaction.
10 dm3/s (cA = 7,5 mol/dm3) of material A and 20 dm3/h (cB = 3,75 mol/dm3) of material B is fed into a
continuous reactor. The feed temperature is 20 C and contains no reaction products. The required
conversion is 95%. The second-order reaction is of type A+B2R. The reaction rate coefficient can
be calculated by the following equation:
8100
dm 3
k 1,63 1010 e T
mol s .
The reaction enthalpy is 82 kJ/mol, the reaction mixture has a density of 1050 kg/m3 and a specific
heat capacity of 3.5 kJ/(kgK). The density and specific heat capacity can be considered to remain
constant during the reaction.
a) How much product is obtained in each hour?
b) If the reaction is to be carried out in a continuous stirred tank reactor in adiabatic mode, what is
the required volume of the reactor?
c) What is the required volume of an ideal displacement tubular reactor in adiabatic mode?
Solution
kmol
n R 540
h
b)
10
1 X
t 135,6 s
k c A0 (1 X ) 2
3
dm
V t V 135,6 s 30 4067,8 dm 3 4,1 m 3
s
c)
dm 3
V t V 17,4 s 30 522 dm 3 0,522 m3
s
Practice problems
Problem 1
An isomerisation reaction is to be carried out in an perfectly stirred, isothermal batch reactor. The
reaction is first-order. The density of the mixture can be approximated as 865 kg/m3, independent of
temperature. The preexponential factor is 45.46 h-1, the activation energy is 14742.5 J/mol. Filling the
reactor requires 20 minutes, emptying requires 10 minutes. The temperature adjustment requires 10
minutes (during which the reaction can be considered to not run). 1500 t of product must be obtained
in 6800 operational hours per year. Conversion is 99%.
What is the required volume of the stirred batch reactor for operating temperatures of 80 and 120 C?
(4 m3, 1.43 m3)
Problem 2
Design a reactor capable of synthesizing three different products. For each product, the required
design capacity, reaction type and order and the required temperature are shown in the following table.
Parameter product product product
Reaction type A+BT AT 2AT
Yearly hours of operation 2500 1000 3500
Yearly production 50 kmol 200 kmol 80 kmol
Temperature (C) 110 130 160
Reaction rate coefficient 0.1 m /(kmolh)
3
0.2 m /(kmolh)
3
0.5 1/h
Conversion 92% 99% 95%
Reactants are fed into the reactor at 20 C. The average rate at which the reactor can be heated is
5 C/min. Loading takes 10 minutes, emptying and cleaning takes 60 minutes. Assume that the
reaction starts only upon reaching the required temperature. Reacting components are available in 1
kmol/m3 concentration. Reactants are fed into the reactor in stoichiometric ratio.
What is the required volume of the stirred batch tank reactor? (V1=2.47 m3; V2=2.27 m3, V3=2.15 m3,
hence 2.5 m3).
Problem 3
An A + 2B C + 2D reaction is carried out in solution at 90 C in an isothermal, perfectly stirred
batch reactor. The reaction rate can be described as second-order, i.e. r kc AcB , where
k = 0.1 m3/(kmolmin). The solvent is fed into the tank reactor first, then 20 kg of material A
(MA = 90 g/mol) and 40 kg of material B (MB = 90 g/mol) are added. The (liquid) reaction mixture has
a volume of 900 dm3 at this point. The reaction causes no volume change. What is the attainable
conversion after 90 minutes? (X = 81.6%)
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Problem 4
An A + 2B C + 2D reaction is carried out in solution at 90 C in an isothermal, perfectly stirred
batch reactor. The reaction rate can be described as second-order, i.e. r kc AcB , where
k = 0.1 m3/(kmolmin). The solvent is fed into the tank reactor first, then 20 kg of material A
(MA = 90 g/mol) and 50 kg of material B (MB = 90 g/mol) are added. The (liquid) reaction mixture has
a volume of 900 dm3 at this point. The reaction causes no volume change. How much time is required
to reach 90% conversion? (t = 166.8 min)
Problem 5
An A + 2B C + 2D reaction is carried out in solution at 80 C in an isothermal, perfectly stirred
batch reactor. The reaction rate can be described as second-order, i.e. r kc AcB , where
k = 0.058 m3/(kmolmin). The solvent is fed into the tank reactor first, then 30 kg of material A
(MA = 90 g/mol) and 50 kg of material B (MB = 90 g/mol) are added. The (liquid) reaction mixture has
a volume of 1050 dm3 at this point. The reaction causes no volume change. How much time is
required to reach 90% conversion? (t = 298.6 min)
Problem 6
An A + B C + D reaction is carried out in solution at 80 C in an isothermal, perfectly stirred batch
reactor. The reaction rate coefficient is k = 0.058 m3/(kmolmin). The solvent is fed into the tank
reactor first, then 30.5 kg of material A (MA = 90 g/mol) and 29.5 kg of material B (MB = 90 g/mol)
are added. The (liquid) reaction mixture has a volume of 890 dm3 at this point. The reaction causes no
volume change. How much time is required to reach 90% conversion? (t = 337.4 min)
Problem 7
Acetic anhydride is hydrolyzed in a continuous stirred tank reactor at 25 C. The reaction is pseudo-
first-order. In the feed stream (0.4 m3/h) the concentration of acetic anhydride is 1 kmol/m3. The
reaction rate coefficient is 0.0806 min-1. The required conversion is 98%. Calculate the required
reactor volume! Calculate the daily consumption of acetic anhydride! (V = 4.05 m3, 9.6 kmol/day)
How will the conversion change if the feed is increased by 20%? (X=0.976)
Problem 8
A second-order, irreversible reaction (2AT) is carried out in a continuous stirred tank reactor. In the
feed stream (0.4 m3/h) component A is present in a concentration of 1 kmol/m3. The reaction rate
coefficient is 7.8 m3(kmolmin)-1. The required conversion is 98%. Calculate the necessary reactor
volume! Calculate the daily feed reactant consumption! (V = 2.1 m3, 9.6 kmol/day)
Problem 9
k1
An equilibrium reaction of the type A+B C+D is carried out in a 0.2 m3 continuous stirred tank
k 1
reactor. The feed streams have equal volumetric flow rates and contain only one component each.
Stream A contains 2.8 mol/dm3 of component A, stream B contains 1.6 mol/dm3 of component B. The
value of k1 is 7 dm3/(molmin), the value of k-1 is 3 dm3/(molmin). What is the equilibrium
conversion? (X = 75.47%)
Problem 10
k1
An equilibrium reaction of the type A+B C+D is carried out in a 0.2 m3 continuous stirred tank
k 1
reactor. The feed streams have equal volumetric flow rates and contain only one component each.
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Stream A contains 3.2 mol/dm3 of component A, stream B contains 2.1 mol/dm3 of component B. The
value of k1 is 7 dm3/(molmin), the value of k-1 is 3 dm3/(molmin)..
What is the equilibrium conversion? (X = 72.14%)
At what feed rate will the conversion be 70%? (64.5 dm3/min)
Problem 11
An A + B C + D second-order reaction is carried out in a 0.12 m3 ideal adiabatic tubular reactor.
The reaction rate coefficient can be calculated by the formula 6.52105e-42300/RT m3/(kmols). The
initial concentration of both A and B is 1.1 kmol/m3. The feed contains no product, has a temperature
of 12 C and a volumetric flow rate of 410-4 m3/s. The reaction enthalpy is -42600 kJ/kmol, the
mixture has a specific heat capacity of 2800 J/(kgK) and a density of 840 kg/m3. Calculate the
conversion! (X = 88.9%)
Problem 12
The liquid-phase first-order irreversible reaction AT is carried out in an isothermal batch reactor
having with volume V = 2 dm3. The concentration of component A at the start and end of the reaction,
the reaction time and the heat removed in order to ensure isothermal conditions were measured at
70 C and at 100 C. The results are shown in the following table:
T (C) 70 100
3
cA0 (kmol/m ) 3 3
t (min) 40 34
3
cA (kmol/m ) 2.1 0.9
Q (kJ) 302.4 705.6
What volume should an adiabatic tubular reactor have, if 17.1 kmol/h of product T must be
synthesized operating at 90% conversion? The available concentration of material A is 3 kmol/m3, fed
into the reactor at 70 C. The density can be approximated as 1000 kg/m3, the specific heat capacity is
3500 J/(kgK). (V = 2.44 m3)
Problem 13
The reaction A + B C + D is second-order. The initial mixture contains component A 2.5 kmol/m3,
component B is added in 20% excess. The feed mixture has a flow rate of 4 m3/h and enters the reactor
at 20 C. The reaction enthalpy is -42 kJ/mol, the density is 900 kg/m3, the specific heat capacity is
2.8 kJ/kgK. These parameters do not depend on the temperature.
5000
m3
The reaction rate coefficient can be calculated with the formula k = 6.5 106 e T .
kmol min
What conversion can be achieved in a 2.5 m3 continuous reactor operating at 65 C? The reactor can
be charged at most to 80%. (X = 0,8614)
In order to maintain 65 C, should the reactor be heated or cooled? What is the required heat duty?
(requires heating, 91.8 MJ/h)
What conversion can be achieved in a 0.8 m3 adiabatic tubular reactor? (X = 0,775)
Problem 14
The liquid-phase second-order irreversible reaction A + B C is carried out in an adiabatic tubular
reactor. The reaction occurs in solution, the concentration of the components in the storage tanks are:
solution A 0.2 kg/dm3 (MA = 100 g/mol); solution B 0.112 g/dm3 (MB = 80 g/mol). The solutions are
fed into the reactor from the storage tanks at the following rates: solution A at 2 dm3/min, solution B at
3 dm3/min. The value of the reaction rate coefficient is known at two temperatures: 1.7 dm3/(molh) at
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20 C, 10 dm3/(molh) at 50 C. What is the necessary volume of the adiabatic tubular reactor, if the
feed temperature is 20 C and the desired conversion is 90%? What is the hourly production of C? The
enthalpy of the reaction is -242 kJ/mol, density is 850 kg/m3, specific heat capacity is 3 kJ/(kgK).
(V = 120 dm3, 216 mol C produced every hour).
Problem 15
Materials A and B react in the irreversible second-order reaction A + B C + D. Solutions of A and
B are fed separately at 30 C into the continuous stirred tank reactor with a useful volume of 2 dm3.
Solution A is fed at a rate of 2 dm3/h and has a concentration of 2 mol/dm3, Solution B is fed at a rate
of 3 dm3/h and has a concentration of 2 mol/dm3. Operating the reactor at 30 C, the outlet
concentration of A is 0.06 mol/dm3. The folume of the reaction mixture does not change during the
reaction. If the reaction is carried out in an isothermal tubular reactor operating at the same parameters
(feed and outlet rates, concentrations, temperatures) as the tank reactor, what should be the volume of
that tubular reactor? (V = 0.3 dm3)
Problem 16
The following irreversible liquid-phase reaction is second-order: A + B C + D; MA = 50 g/mol,
MB = 120 g/mol, MC = 100 g/mol, MD = 70 g/mol. The following data are available from laboratory
experiments:
800 g of 30% pure A and 1200 g of 40% pure B are loaded into a batch reactor. Initially, products C
and D are not present in the reaction mixture. The density of the reaction mixture is 1000 kg/m3 and
does not change during the operation. Operating the reactor at 20 C, 11 minutes after the start
material C has a concentration of 180 g/dm3.
50 cm3/min of a 5 mol/dm3 solution of A at 20 C and a solution of B with the same flow rate,
concentration and temperature is fed into a continuous tank reactor having a useful volume of 2 dm3.
The outlet stream is at 60 C and contains 0.125 mol/dm3 of A. The reactor can be considered to be
perfectly isolated. The reaction mixture has a specific heat capacity of 4.18 kJ/(kgK).
What is the required volume of an adiabatic, ideal tubular reacor if the required yearly production is
1500 t at 95% conversion? Calculate with 7000 hours of operation per year. The adiabatic tubular
reactor is operated with equimolar feed at 20 C containing 3 mol/dm3 A. (V = 14.1 dm3)
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Bibliography
Bittrich, H.-J., Haberland, D., Just, G.: Kmiai kinetikai szmtsi mdszerek, Mszaki Knyvkiad,
Budapest, 1984.
Fogler, H.S.: Elements of chemical reaction engineering, Prentice Hall, Upple Saddle River, 1992.
Ghasem, N., Henda, R.: Principles of chemical engineering processes, CRC Press, Boca Raton, 2009.
Hougen, O.A., Watson, K.M., Ragatz, R.A.: Chemical Process Principles, Vols. I. and II., Wiley,
New York, 1959.
Laidler, K.J.: Chemical Kinetics, McGraw Hill, NewYork,1965.
Sawinsky J. (szerk.): Vegyipari mveleti szmtsok III. Reaktorok, Megyetemi Kiad, Budapest,
1998.
Sawinsky J., Dek A., Simndi B.: Vegyipari mveletek III. Kmiai reaktorok, Megyetemi Kiad,
Budapest, 2001.
Smith, J.M.: Chemical Engineering Kinetics, McGraw Hill, NewYork, 1970.
Szab Z.G.: Kinetic Characterization of Complex Reaction Systems, in Comprehensive Chemical
Kinetics, Vol. 2., Eds. Bamford, C.H., Tipper, C.F.H., Elsevier, Amsterdam, 1969.
Westerterp, K. R., van Swaaij, W. P. M., Beenackers, A. A. C. M.: Chemical Reactor Design and
Operation, Wiley, New York, 1984.
Winterbottom, J.M., King, M.B.: Reactor design for chemical engineers, Stanley Thornes (Publishers)
Ltd., Cheltenham, 1999.
Zrnyi M.: A fizikai kmia alapjai II., Mszaki Knyvkiad, Budapest, 2006.
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Appendix Tables
Calculations for isothermal batch reactors and isothermal tubular reactors (V = constant)
X dX
t c j0
0 j r
The jth component is always the limiting component. In the table, this is always component A. For batch reactors t denotes the reaction time, for tubular
reactors t denotes the average residence time.
Table 1. Calculations for isothermal batch tank reactors and isothermal tubular reactors. Integration aid.
Reaction type and Reaction rate equation X dX Value of t after integration X (by rearranging the
t c A0 0
order Ar previous column)
substituted
AB rk c A0 X c A0 X k t
zero-order
t
k 0
dX k c A0
AB r k c A k c A0 (1 X ) 1 X dX 1 1 e kt
first-order
t
k
0 (1 X )
k
ln(1 X )
2AP v. A+BP r k c A2 k c A2 0 (1 X ) 2 1 X dX (1 X ) 1 1 k t c A0
t 1 X
second-order k c A0 0 (1 X ) 2 k c A0 k c A0 1 X 1 k t c A0
(cA0 = cB0)
A+BP r k c A cB 1 X dX 1 c B 0 c A0 X cB 0 (e k t(cB 0 cA 0 ) 1)
second-order k c A0 (1 X ) (cB 0 c A0 X )
t
k 0 (1 X ) (cB 0 c A0 X )
k (c B 0 c A 0 )
ln
cB 0 (1 X ) cB 0 e k t( cB 0 cA0 ) c A0
(cA0 < cB0)
r k1c A k 1c B 1 X dX 1 k k 1 k1
(1 e ( k1 k1 )t )
k1
t ln(1 1 X)
A B k1c A0 (1 X ) k 1c A0 X k1 0 k k 1 k1 k 1 k1 k1 k 1
k 1 (1 1 X)
k1 k 1 k1
cB0=0 c A0 k1 (1 X)
k1
17
Calculations for isothermal, ideally stirred tank reactors
V V t
1
(c j0 c j ) j r 0 in steady state, for reactions without volume change. Substituting the conversion:
t
1 ( c j0 c j ) j r 1 j r
0 X
t c j0 c j0 t c j0
The jth component is always the limiting component. In the table, this is always component A.
AB r k c A k c A0 (1 X ) 1 X k t
first-order k 1 X 1 k t
1
X k (1 X )
t
AB r k c Am k c Am0 (1 X ) m 1 X k t c Am01
m1
m-order (m 1) k c A0 (1 X ) m 1 k t c Am01
1 k c mA0 (1 X ) m
X
t c A0
2AP v. A+BP r k c A2 k c A2 0 (1 X ) 2 1 X
2k t c A 0 1 1 4 k t c A 0
second-order k c A0 (1 X ) 2
2k t c A 0
(cA0 = cB0)
18
1 k c 2A0 (1 X ) 2
X
t c A0
19