Chemical Reaction Engineering

Lecture 6: Complex Reactions

Jayant M. Modak Department of Chemical Engineering Indian Institute of Science, Bangalore

Topic 3: Complex systems

! Analysis

of Simple complex systems ! Kinetics of complex systems

" " "

Chain reaction Catalysis Polyermization

! Lumping

analysis

Complex systems - Examples

! Large

number of reactions and reactants

Thermal cracking of alkanes C3 H 8 ! C3 H 6 + H 2 C3 H 8 ! C2 H 4 + CH 4 C3 H 8 + C2 H 4 ! C2 H 6 + C3 H 6 Cracking of crude to petrol Metabolic network inside cell

Complex systems - Examples

! Chain

reactions

Thermal decomposition CH 3CHO ! CH 4 + CO Auto " oxidation R " H + O2 ! ROOH Polymerization styrene ! poly ( styrene)

Complex systems - Examples

! Catalytic

reactions

Thermal decomposition C12 H 22O11 + H 2O !acid! C6 H12O6 + C6 H12O6 !" Ammonia synthesis 1 3 N 2 + H 2 !Fe" NH 3 ! 2 2

Yield conversion diagram

Polymer weight distribution

Catalytic reaction kinetics

3.0 2.5 2.0

pO2
0.061 0.132 0.263 0.526 0.789

rate

1.5 1.0 0.5 0.0 0.0 0.2 0.4 0.6 0.8 1.0

1.2

1.4

pEthylene

Complex reactor behavior

Cracking of ethane to ethylene

CC 2 H 4 H H 2! 6 2+
2! C 3+ H8 H H C 2 6C 4
C 2H H+ C 2 2 ! 4 2
! New
" " "

questions

Are all products useful? How to monitor the reaction? Is conversion of ethane the only criteria for design?

Parallel reactions

C !4 2 H C + HH 2 6 2 2H C + 4 C !8 C H H 2 6 3

" A1 !

A2 A3

Series reactions

C6 C 4 H H ! +2 H 2 2 C4 2 22 H C H !+ 2

A1 ! A2 ! A3

Complex (Series-parallel) reactions

C 6! 4 H H C +2 H 2 2 22 6! 8 C C H C +H H 3 4 C 8 C 4! 8 C H 2 + H C +H H 3 4 4

A1 " !

A2 A3

A2 + A3 ! A4

Independent Reactions

C6 C 4 H H ! +2 H 2 2 C8 C6 H H 3 +2 ! H 3

A1 ! A2 A3 ! A4

Desired and Undesired Reactions

CC 2 H 4 H HA 2! 6 2+
1

! A2 A3

2! C 3+ A ! H8 H H C 2 6C 4

A1 ! A2 ! A3

Yield

Desired reaction Undesired reaction

Overall Yield Y2 =

A1 ! A2 A1 ! A3

r1 r2

Exit molar flowrate of desired product Inlet molar flowrate of reactant

Selectivity

Desired reaction Undesired reaction

Instantenous Selectivity
Overall Selectivity

A1 ! A2 A1 ! A3

r1 r2

r1 s2 = r1 + r2

Exit molar flowrate of desired product ! S2 = Exit molar flowrate of all products

Selection of reactor type and conditions

Desired reaction Undesired reaction

CSTR C2 r1 = C10 ! C1 r1 + r2
PFR

A1 ! A2 A1 ! A3
C10

r1 r2
r1 dC1 r1 + r2

C2 1 = C10 ! C1 C10 ! C1

C1

"

Complex systems - selectivity

q2-q1

selectivity (C1)

1 0 -1

C10-C1

Complex systems series reactions

A1 ! A2 A2 ! A3
!=0.1
1.0

r1 = k1C1 r1 = k2C2
A1 A2 A3

" = k2 / k1

Concentration

0.8 0.6 0.4 0.2 0.0 0

10

Time

Concept of yield-conversion diagram

A1 ! A2 A2 ! A3 r1 = k1C1 r1 = k2C2

" = k2 / k1

Concept of rate determining step

A1 ! A2 A2 ! A3
!=0.1
1.0

r1 = k1C1 r1 = k2C2
A1 A2 A3

" = k2 / k1

Concentration

0.8 0.6 0.4 0.2 0.0 0

10

Time

Concept of rate determining step

A1 ! A2 A2 ! A3
!=5
1.0

r1 = k1C1 r1 = k2C2
A1 A2 A3

" = k2 / k1

Concentration

0.8 0.6 0.4 0.2 0.0 0

10

Time

Concept of quasi-equilibrium approximation

A1 ! A2 A2 ! A3
1.0 0.8

r1 = k1C1 ! k!1C2 r1 = k2C2 ! k!2C3

k1=1, k-1=0.5, k2=k-2=1
C1 C2 C3

concentration

0.6 0.4 0.2 0.0 0 1 2 3 4 5

time

Concept of quasi-equilibrium approximation

A1 ! A2 A2 ! A3
1.0 0.8

r1 = k1C1 ! k!1C2 r1 = k2C2 ! k!2C3

k1=1, k-1=0.5, k2=k-2=10
C1 C2 C3

conntration

0.6 0.4 0.2 0.0 0 1 2 3 4 5

time

Concept of quasi-equilibrium approximation

A1 ! A2 A2 ! A3
1.0 0.8

r1 = k1C1 ! k!1C2 r1 = k2C2 ! k!2C3

k1=1, k-1=0.5, k2=k-2=10
C1 C2 C3 C1 (e) C2 (e)

conntration

0.6 0.4 0.2 0.0 0 1 2 3

time

Concept of quasi-steady state approximation

A1 ! A2 A2 ! A3
!=5
1.0

r1 = k1C1 r1 = k2C2
A1 A2 A3

" = k2 / k1

Concentration

0.8 0.6 0.4 0.2 0.0 0

10

Time

Concept of quasi-steady state approximation

A1 ! A2 A2 ! A3
1.0 0.8

r1 = k1C1 r1 = k2C2

" = k2 / k1

C3/C10

0.6 0.4 0.2 0.0 0 1 2 3 4

k2 1 10 50
!

k1t

Chemical Reaction Engineering

Lecture 6: Complex Reactions

Jayant M. Modak Department of Chemical Engineering Indian Institute of Science, Bangalore

Chain reactions
! Combustion

reactions ! Decomposition reactions ! Autooxidation! ! Polymerization!

Chain reactions decomposition of acetaldehyde

CH 3CHO ! CH 4 + CO
CH 3CHO ! CH 3 + CHO CH 3 + CH 3CHO ! CH 3CO + CH 4 CH 3CO ! CH 3 + CO 2CH 3 ! C2 H 6

3/2 r = kCCH 3CHO

Polymerization
! Chain
" "

CH polymerization of 2 = CHX

( RX )

Ethylene (X=H), vinyl chloride (X=Cl) Styrene (X=C6H5) etc

! Initiator

I (!-!)!
C6 H 5COO ! OOCC6 H 5 " 2C6 H 5COO # + RX " # ! RX # ! RX + RX " # ! ( R) ! RX # ! ( R) j !1 ! RX + RX " # ! ( R) j ! RX # ! ( R) j !1 ! RX + XR ! ( R)i !1 ! # " # ! ( R) j !1 ! RX ! XR ! ( R)i !1 ! #

Initiation Propogation

Termination

Polymerization
Initiation
0 I !! 2# " i # + M !! R1 "

k0 = 10$4 $ 10$6 k p = 102 $ 104

Propogation

R1 + M !! R2 "
p R j $1 + M !! R j "

kp

Termination

a R j + Ri !! Pi + j "

ka = 106 $ 108

Polymerization
Species I ! R1 Rj Pj r0 = 2 fk0 I ri k P MR j ka 2 Appearance disappearance k0 I ri = ki !M k p MR1 + ka R1 " R j

k p MR j + ka R j " Ri
j#i

"R

Ri

Polymerization
Initiation rate Total radicals Monomer consumption Radical concn polymer generation ri = 2 fk0 I # ri & !R j = " 0 = % ( $ ka ' rM = k p M " 0 # ri & # & 1 Rj = % (% ( $ k P M ' $ 1 + ri / rM ' rP = R j
j

1/ 2

ka # ri & j )1 2 % kP M ( $ '

Polymerization
1.4

time (min)

weight fraction

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 500

360 180 60

1.4

Initiator

weight fraction

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 500

1000 1500 2000 2500 3000

0.04 0.02 0.08

number of monomers

1000 1500 2000 2500 3000

number of monomers

Polymer weight distribution

Chemical Reaction Engineering

Catalytic reactions

Jayant M. Modak Department of Chemical Engineering Indian Institute of Science, Bangalore

Catalytic reactions
Heterogeneous catalysis
Gas (2nd Liquid) Solid

Catalyst

Liquid

Catalytic reactions
Example: Hydrogen peroxide decomposition 2H2O2 2H2O + O2

H2O2 soluti on 25C stable over months

>320C uncontrolled, thermal decomposition in seconds

25C controlled, catalytic or enzymatic decomposition in seconds

Catalytic reactions

Efficiency of Phthalic Acid Anhydride Production

Catalytic Oxidation of o-Xylene in the gas phase on V2O5-catalyst

Non-catalytic Oxidation of naphthalene in fluid phase with MnO2+HCl (1872), Chromic acid (1881), Oleum (1891)

Yield: 5-15%

Yield: 75-87%

Catalytic reactions
Efficiency of nitrogen fixation

catalytic processes

Catalytic reactions
substrates

Product spectrum from partial oxidation of propene

catalysts products acrolein acrylic acid propene + oxygen acetone propylene oxide acetic acid 1,5-hexadiene benzene

Catalytic reactions
reaction: substrate A Boundary layer product P

Steps during the course of the reaction " External diffusion # Internal diffusion $ Adsorption on the active ' sites Surface reaction ! forming the products Desorption of the & products % Internal diffusion External diffusion

fixed bed reactor

Lumping analysis
1.0 0.8 0.6 0.4 0.2 0.0 0.0 0.1 0.2 0.3 0.4 0.5

A10=1, A20=0, A30=0

A1

1.0

A10=1, A20=0, A30=0

A1+A2 A3
1 2

Concentrations

A3

Concentrations

A2

0.8 0.6 0.4 0.2 0.0 0.0 0.1 0.2 0.3

0.4

0.5

Time
1.0

Time
1.0 0.8

A10=0.5, A20=0.5, A30=0

Concentration
B

A10=0.5, A20=0.5, A30=0

A1+A2 A3
1 2

Concentrations

0.8 0.6 0.4 0.2 0.0 0.0 0.1

0.6 0.4 0.2 0.0 0.0 0.1 0.2 0.3

0.2

0.3

0.4

0.5

0.4

0.5

Time

Time

Lumping analysis
1.0

1=A1+A3, 2=A2
Initial A1,A2,A3

Concentration

0.8

1,0,0 0,0,1

0.6 0.0 0.1 0.2 0.3 0.4 0.5

Time