CHAPTER FIVE

MULTIPLE REACTIONS
1

Multiple reactions
Usually, there are more than one reaction occur in
a chemical reactor.
One of the key factors in the economic success of
a chemical plant is the minimization of undesired
side reactions that occur along with the desired
reaction.
2

Types of multiple reactions
Parallel reaction (competing reactions)
A

B

k1
k2

2CO2  2 H 2O

Example

O

CH 2  CH 2  O2

C

CH 2  CH 2

Series reactions (consecutive reactions)
A

k1

Example

B

k2

C

Desired product

O

E .O .
E .O .
CH 2  CH 2  NH 3  HOCH 2 NH 2    ( HOCH 2CH 2 ) 2 NH    ( HOCH 2CH 2 )3 N

Independent reactions
A

k1

B

C

k2

D

Example
3
The cracking of crude oil to form gasoline
(Feed stocks containing many reactants)

Contacting Patterns .Batch 4 .

Contacting Patterns 5 .

S S DU rD k D  1 2   CA rU kU 6 We want this value as large as possible! .Parallel reactions Purpose: maximizing the desired product in parallel reactions A kD A kU D (desired) U (undesired) 1 rD  k D C A rate law 2 rU  kU C A 1 2 The rate of disappearance of A:  rA  rD  rU  k D C A  kU C A Define a rate selectivity parameter.

Maximizing the rate selectivity parameter1/2 S DU k D  1 2  CA kU 1 > 2 C  1 2 A 0 keep the concentration of A as high as possible in the gas phase: without inerts and at high pressure in the liquid phase: minimize the use of diluents a batch or a plug-flow reactor is preferred • because CA starts at a high value and drops progressively • cf: CA in a perfectly mixed CSTR is always at its lowest value. NOT recommended.e. 7 . (i. the outlet concentration).

Maximizing the rate selectivity parameter2/2 S DU   1 < 2 kD  1 2 CA kU – keep the concentration of A as low as possible • diluting the feed with inerts • a CSTR reactor is preferred • a recycle reactor in which the product stream acts as a dilutent could be used to maintain the entering concentrations of A at a low value. . S DU kD  1 2  CA kU What about this bit? 8 This is actually affected by the reaction temperature.

Temperature effects 1/2 S DU kD  1 2  CA kU Arrhenius Equation Recall  ( E D  EU )   RT   k D AD  e kU AU differences between the activation energy  ratio of fequency factor 9 .

– Not so low that the desired reaction does not proceed to any significant extent. 10 .Temperature effects 2/2  ( E D  EU )   RT  • ED > EU k D AD    e kU AU – The reaction should be operated at the highest possible temperature to maximize SDU. • ED < EU – The reaction should be operated at a low temperature to maximize SDU.

5   CA       CA   AQ   1  1 rQ   0. together with their corresponding rate laws.00452 exp  5000    300 T        CA   0. Q and U.0018 exp  25000    300 T    A D   1  1 rD   0. and two that are undesired.0012 exp  26000    300 T      1.5 How and under what conditions should the reactions above be carried out 11 to minimize the concentrations of the unwanted products U and Q? . are A U   1  1 rU   0. D. These gas-phase reactions.Parallel reactions example 1/2 Reactant A decomposes by three simultaneously reactions to form three products: one that is desired.

00452 exp  5000    300 T        CA   0 .66e   0. which may be accomplished by a. using low pressures (if gas phase) c.0018 exp  25000    300 T      high temperature 1. High temperatures.0012 exp  26000    300 T     1 1    300 T  1000      CA   S D / UQ rD 0.Parallel reactions example 2/2 1. the rate of formation of Q will be negligible with repect to the rates of formation of D and U at high temperature. using a CSTR or a recycle reactor low concentration of A A D   1  1 rD   0. AQ   1  1 rQ   0. adding inerts b.5   CA   Due to its low activation energy.5 S D / UQ rD  rU  rQ 12 . Low concentration of A. 2.5 rU CA A U   1  1 rU   0.

What about two reactants? A+B kD A+B kU D (desired) U (undesired) S DU rate law 1/3 1 1 2 2 rD  k D C A C B rU  kU C A C B rD k D  1 2  1  2   CA CB rU kU 13 .

3 Different reactors and schemes for minimizing unwanted product 14 .Figure 6.

1 > 2 2/3 rD k D  1 2  1  2   CA CB rU kU  Maintain both CA and CB as high as possible  A tubular reactor or a batch reactor  High pressures (if gas phase)  When 1 > 2. 15 .What about two reactants? S DU  When 1 > 2. In this way. 1 < 2  Make CA high and CB low  A semibatch reactor in which B is fed slowly into a large amount of A  A tubular reactor with side streams of B continuously fed to the reactor  A series of small CSTRs with A fed only to the first reactor and small amounts of B fed to each reactor. B is mostly consumed before the CSTR exit stream flows into the next reactor.

1 < 2 3/3 rD k D  1 2  1  2   CA CB rU kU  Maintain both CA and CB as low as possible  A CSTR. or a tubular reactor in which there is a large recycle ratio  A feed dilute with inerts  Low pressures (if gas phase)  When 1 < 2.What about two reactants? S DU  When 1 < 2. 16 . 1 > 2  Make CA low and CB high  A semibatch reactor in which A is fed slowly into a large amount of B  A tubular reactor with side streams of A continuously fed to the reactor  A series of small CSTRs with B fed only to the first reactor and small amounts of A fed to each reactor.

If the first reaction is fast and the second reaction is slow. a large yield of D can be obtain.Series reactions Purpose: maximizing the desired product in series reactions A k1 D k2 U When to stop? Time is the key factor here!!! (desired) (undesired) If the first reaction is slow and the second reaction is fast. the desired product D will be converted to U. . or if the tubular flow 17 reactor is too long. it will be extremely difficult to produce D. If the reaction is allowed to proceed for a long time in a batch reactor.

0.Example 6-4 1/4 Muximizing the Yield of the Intermediate Product The oxidation of ethanol to form acetaldehyde is carried out on a catalyst of 4 wt% Cu 2 wt% Cr on Al2O3. and 98. respectively.9% N2). acetaldehyde is also oxidized on this catalyst to form carbon dioxide. 18 . 1  O2 2 5  O2 2 CH 3CH 2OH ( g )  -H   O  CH 3CHO  -2H   O 2CO2 2 2 The reactions are irreversible and first-order in ethanol and acetaldehyde. Unfortunately. The reaction is carried out in a threefold excess of oxygen and in dilute concentrations (ca. Consequently. Determine the concentration of acetaldehyde as a function of space-time.1% ethanol. 1% O2. the volume change with the reaction can be neglected.

Example 6-4 2/4 A Mole balance on A: Rate law for A: k1 B k2 C dFA  rA dW rA   k1C A Stoichiometry ( change of volume is neglected): dC A v0  k1C A dW FA  C Av0 W = 0. CA = CA0 C A  C A0 e  k1 W v0  W v C A  C A0 e  k1  0 19 .

Example 6-4 3/4 A Mole balance on B: Rate law for B: k1 B k2 dFB  rB dW dC B v0   k1C A  k 2C B dW rB  k1C A  k 2C B Stoichiometry ( change of volume is neglected): C FB  C B v0  W v 0 C A  C A0 e  k1  dC B  k 2C B  k1C A0 e  k1  d  Integral factor. CB = 0 d (C B e k2  ) ( k 2  k1 )   k1C A0 e d  20 . ek2’  e  k1   e  k 2    C B  k1C A0  k 2  k1   ’ = 0.

To find the optimum reactor length.Example 6-4 4/4  e  k1   e  k 2    C B  k1C A0  k 2  k1   Optimum Yield The concentration of B goes through a maximum at a point along the reactor. we differentiate the above equation: dC B  k1C A0    k1e  k1   k 2 e  k 2   0   d   k 2  k1     optimum   1 k ln 1 k1  k 2 k 2 Woptimum  v0 k ln 1 k1  k 2 k 2 21 .

Complex reactions  Complex reactions consist of combinations of parallel and series reactions.  It is usually easier to solve the problems using moles Nj or mole flow rate Fj rather than conversion.  relate the rate of reaction of each species to the species with known rate laws (based on stoichiometry)  determine the net rate of formation of each species  combine all of the above and solve the resulting set of coupled differential or algebraic equaitons 22 .  Procedure:  number each reaction  mole balances for each species  determine the rate laws for each species in each reaction.

If q reactions are taking place A  B   k1 A  3C  D A  2C  k 2 A  3E 2 B  3E  k 3 B  4 F ...Net rates of reaction Sum up the rates of formation for each reaction in order to obtain the net rate of formation..  rqB   riB i 1 q rj   rij i 1 species reaction number 23 . 1 k qA A  B   G 2 q rA  r1 A  r2 A  r3 A ...  rqA   riA i 1 q rB  r1B  r2 B  r3 B ..

Rate laws The rate laws for each of the individual reactions are expressed in terms of concentrations. Example : 2 rij   kij Ck C j 3 24 . C j. of the reacting species.

aA  bB  cC  dD  rA  rB rC rD    a b c d r r r r iA iB iC Example    iD :  ai  bi ci di for the ith reaction 25 .Stoichiometry: relative rates of reaction Relate the rate law for a particular reaction and species to other species participating in that reaction.

5 r2 N 2  k 2 N 2 C NO 2  r3O2  k3O2 C N 2 CO2 2 Write the rate law for each species in each reaction and then write the net rates of formation of NO. and N2. O2. 26 Write the mole balances on a PFR in terms of molar flow rates for each species .Example 6.6 1/4 Complex reactions in PFR Consider the following set of reactions: 4 NH 3  6 NO   k1  5 N 2  6 H 2O 2 NO   k2  N 2  O2 N 2  2O2   k3  2 NO2  r1NO  k1NO C NH 3 C NO 1.

Example 6.5  ( r1NO )  k1NO C NH 3 C NO 6 6 r1H 2O  r1NO  k1NO C NH 3 C NO 1.5  ( r1NO )  k1NO C NH 3 C NO 3 3 5 5 1.5 r1NO r1NH 3 r1N 2 r1H 2O    5 1  2 1 3 6  r1NH 3 r1N 2 2 2 1.5 27 .5 r2 N 2  k 2 N 2 C NO 2  r3O2  k3O2 C N 2 CO2 2 1.6 2/4 2 5 k1 NO  NH 3    N 2  H 2O 3 6  r1NO  k1NO C NH 3 C NO 2 NO   k2  N 2  O2 1 O2  N 2   k3  NO2 2 Reaction 1:  r1NO  k1NO C NH 3 C NO 1.

we have For reaction 3. we have O2  r3 N 2 r3 NO2 r3O 2   1 1/ 2 1 1 N 2   k3  NO2 2 r3 NO2   r3O2  k3O2 C N 2 CO2 2  r3 N 2  q rj   rij  r2 NO  2r2 N 2  2k 2 N 2 C NO 1 1 2 (r3O2 )  k3O2 C N 2 CO2 2 2 i 1 3 rNO   riNO  r1NO  r2 NO  0  k1NO C NH 3 C NO i 1 3 rN 2   riN 2  r1N 2  r2 N 2  r3 N 2 i 1 3 1.Example 6.5 2 2  k1NO C NH 3 C NO  k 2 N 2 C NO  k3O2 C N 2 CO2 6 2 rO2   riO2  r1O2  r2O2  r3O2  k 2 N 2 C NO  k3O2 C N 2 CO2 i 1 2 2 2 28 2 .6 3/4 2 NO   k 2  N 2  O2 r2 NO r2 N 2 r2O2   2 1 1 Similary.5  2k 2 N 2 C NO 5 1 1. for reaction 2.

the using the fact FT   F j j 1 determined..6 4/4 For gas-phase reactions.5 2 2  rN 2  k1NO C NH 3 C NO  k 2 N 2 C NO  k3O2 C N 2 CO2 dV 6 2 5 2.5  FNH 3  k1NO CT 0  6  FT   FNO       FT  1 .5  FNH 3  k1NO CT 0   FT Mole balance on N2 ….5  2 F  2k 2 N 2 CT 0  NO   FT  2 dFN 2 5 1 1. the system can be . Fj F j P T0 FT P0 T FT Mole balances on all the species Mole balance on NO dFNO 1.5 2  rNO  k1NO C NH 3 C NO  2k 2 N 2 C NO dV 2. 29 .   FNO     F  T  1 ..Example 6. the concentration of species j is : C j  CT 0 C j  CT 0 For no pressure drop and isothermal operation.5 2  1 2 F 3  FN 2    k 2 N 2 CT 0  NO   k3O2 CT 0  2  FT   FT   FO2   FT 2    n If all the mole balance equations are obtained.

30 . We therefore want to maximize the production of m-xylene.Example 6-7 1/4 HydrodeaIkylation of Mesitylene in a PFR The production of m-xylene by the hydrodealkylation of mesitylene over a Houdry Detrol catalyst involves the following reactions: Desired product m-Xylene can also undergo hydrodealkylation to form toluene: Undesired product The second reaction in undesirable. because m-xylene sells for a higher price than toluene.

7 mol% hydrogen and 33. mesitylene.2( ft 3 / lb mol ) 0.  r1M  k1C M C H 0. The rate laws for reactions 1 and 2 are. At 1500 ºR. T = toluene. 31 .Example 6-7 2/4 The hydrodealkylation of mesitylene is to be carried out isothermally at 1500 ºR and 35 atm in a packed-bed reactor in which the feed is 66.2( ft 3 / lb mol ) 0. the specific reaction rates are: k1  55. respectively.5 r2T  k 2C X C H 0. and H = hydrogen.5 / h k 2  30.3 mol% mesitylene.5 / h The bulk density of the catalyst has been included in the specific reaction rate. The volumetric feed rate is 476 ft3/h and the reactor volume is 238 ft3. X = m-xylene. Determine the concentrations of hydrogen. Me = methane. and xylene as a function of space time.5 where the subscripts are: M = mesitylene.

5 0. Rate laws for each species: (PFR) 3.5 0.5 0 .Example 6-7 3/4 Reaction 1: M  H  X  Me Reaction 2: X  H  T  Me r1M r1H r1 X r1Me    1 1 1 1 r2 X r2 H r2T r2 Me    1 1 1 1 1. Convert F to C : (PFR) H dFH  rH dV rH  r1H  r2 H  k1C H C M  k 2C H C X M dFM  rM dV rM  r1M  k1C H C M X dFX  rX dV rX  r1 X  r2 X  k1C H C M  k 2C H C X T dFT  rT dV rT  r2T  k 2C H C X 0.5 0.5 rMe  r1Me  r2 Me  k1C H CM  k 2C H C X Left as intermediate product FMe  ( FH 0  FH )  v0 (C H 0  C H32) .5 0. Mole balances: 2.5 0.5 FH  v0C H reactant FM  v0C M reactant FX  v0C X FT  FM 0  FM  FX  v0 (CM 0 C M C X ) Originally from M Me dFMe  rMe dV intermediate product 0.

D.5 0.5  k1C H CM d dC X 0.E.5 0.5  k1C H C M  k 2C H C X dV dC H 0.5  k1C H C M  k 2C H C X dV space time dCM 0.5   k1C H C M dV V  v0 d (v0C X ) 0.5 0.Example 6-7 4/4 d (v0C H ) 0. solver CX 33 .5  k1C H CM  k 2C H C X d d (v0CM ) 0.5  k 2C H C X dV d (v0C H 0  v0C H ) dV 0 .5  k1C H CM  k 2C H C X d d (v0CM 0  v0CM  v0C X ) 0 .5  k1C H C M  k 2C H C X Optimum CH CM O.5 0.5 0.

5 0.5 0 .5C X V FH  v0C H reactant M FM 0  FM   rM rM  r1M  k1C H 0.5C M V FM  v0C M reactant X FX  rX V rX  r1 X  r2 X  k1C H C M  k 2C H C X T FT  rT V rT  r2T  k 2C H C X 0.5 FX  v0C X FT  FM 0  FM  FX  v0 (CM 0 C M C X ) Originally from M Me FMe  rMe V intermediate product 0. Rate laws for each species: (CSTR) 3. Convert F to C : (CSTR) H FH 0  FH  rH rH  r1H  r2 H  k1C H 0. but now in CSTR 1.5 rMe  r1Me  r2 Me  k1C H CM  k 2C H C X Left as intermediate product FMe  ( FH 0  FH )  v0 (C H 0  C H ) 34 .5C M  k 2C H 0.Example 6-8 1/2 Complex reactions in CSTR The same reactions as the previous example.5 0. Mole balances: 2.

35 .Example 6-8 2/2  V v0 space time CH 0  CH 0.5  k1C H C M  CX 0.5 0. We are going to solve the problems WITH volume change and we should be using “molar flow rate” as the dependent variable.5  k1C H C M  k 2C H C X  CH Optimum CM CX We have dealt with problems WITHOUT volume change and we used “concentration” as the dependent variable.5  k1C H C M  k 2C H C X  CM 0  CM 0.5 0 .