Lecture 17

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
 Web Lecture 17
Class Lecture 22–Thursday 4/4/2013
Introduction to Catalysts and Catalysis
 Interstage cooling
 Noble Prize 2007
 Catalytic steps

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 Catalysts and Catalysis
 A Catalyst is a substance that affects the rate of
chemical reaction but emerges from the process
unchanged.
 Catalysis is the occurrence, study, and use of
catalysts and catalytic processes.

Approximately 1/3 of the GNP of materials

produced in the U.S. involves a catalytic process.

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 Catalysts and Catalysis
Catalysts affect both selectivity and yield

Different reaction paths

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 Catalysts and Catalysis

Different shapes and sizes of catalyst.

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 Catalysts and Catalysis

Catalytic packed-bed reactor, schematic.

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 Steps in a Catalytic Reaction

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 Active Sites
 Reactions are not catalyzed over the entire
surface but only at certain active sites or centers
that result from unsaturated atoms in the surface.

 An active site is a point on the surface that can

form strong chemical bonds with an adsorbed
atom or molecule.

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Active Sites – Ethylidyne on Platinum
 The Adsorption Step

Vacant and occupied sites

For the system shown, the total concentration of sites is

Ct = Cv + CA.S + CB.S

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 The Adsorption Step
A  S  A S
rAD  k A PACv - k -AC AS  k A PACV  C AS / K A 
K A  k A / k A [atm-1 ]

@ equilibriu m : rAD  0 C AS  k A PACV

rAD / k A  0 C AS  k A PACV

Ct  CV  C AS  CV  K A PACV  CV (1  K A PA )
𝐶
𝐶 =
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1+𝐾 𝑃
 Langmuir Adsorption Isotherm
𝐶
𝐶 =
1+𝐾 𝑃

𝐶 ∙ =𝐾 𝑃 𝐶

𝐶 ∙ = 𝐶

𝐶∙ 𝐾 𝑃
=
𝐶 1+𝐾 𝑃
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 Langmuir Adsorption Isotherm
C AS C AS K A PA

CT
Increasing T Ct 1  K A PA

Slope=kA
Langmuir Adsorption
Isotherm

PA

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 The Surface Reaction Step

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 The Surface Reaction Step

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 The Surface Reaction Step

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 The Surface Reaction Step

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 The Surface Reaction Step

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 Steps in a Catalytic Reaction

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Desorption from the Surface for the Reaction

A 
 B C


C S 
 CS

 PC C  
rDC  k D CCS   (10-20)
 K DC 

rDC  rADC
1
K DC 
KC
rDC  k D CCS  KC PC C   (10-21)
 Steps in a Single-Site Catalytic Reactor
 C AS 
Adsorption A  S  A S  rA  rAd  k Ad  PACv  
 k A 

 C B S 
Surface Reaction A  S  B  S  rA  rS  k S C AS  
 k C 

Desorption BS  B S  rA  rD  k D CBS  k B PBCB 

Which step is the Rate Limiting Step (RLS)?

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 The Rate Limiting Step:
Which step has the largest resistance?

Electrical analog to heterogeneous reactions

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 Collecting and Analyzing Data

Collecting information for catalytic reactor design

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 Collecting and Analyzing Data

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 Catalytic Reformers
 Normal Pentane Octane Number = 62
 Iso-Pentane Octane Number = 95

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 Catalytic Reformers
0.75 wt% Pt
n-pentane i-pentane
Al2O3

-H2 Al2O3 +H2

n-pentane n-pentene i-pentene i-pentane
Pt Pt

Al2O3
n-pentene i-pentene

N I

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 Catalytic Reformers
Isomerization of n-pentene (N) to i-pentene (I) over alumina
Al2O3
N I

1. Select a mechanism (Mechanism Single Site)

Adsorption on Surface: N S  N S
Surface Reaction: N S  I S
Desorption: I S  I S
Treat each reaction step as an elementary reaction when writing rate laws.
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 Catalytic Reformers
2. Assume a rate-limiting step.
Choose the surface reaction first, since more than 75%
of all heterogenous reactions that are not diffusion-
limited are surface-reaction-limited. The rate law for the
surface reaction step is:
N SS  I SS

 C 
 rN   r  rS  k S  C NS 
I
' I S

 KS 

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 Catalytic Reformers
3. Find the expression for the concentrations of
the adsorbed species
CN.S and CI.S. Use the other steps that are not limiting to
solve for CN.S and CI.S. For this reaction:

N S  N S
rAD
From  0: C NS  PN K N C
kA
I S  I  S
rD PI C 
From  0: C IS   K I PI C
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kD KD
 Catalytic Reformers
4. Write a Site Balance.

Ct  C  C NS  CIS

5. Derive the rate law. Combine steps 2, 3 and 4 to

arrive at the rate law :
k
 

 k s Ct K N PN  PI K P 
 rN  rS 
1  K N PN  K I PI 
k PN  PI K P 
 rN   rS 
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1  K N PN  K I PI 
Catalytic Conversion of Exhaust Gas

1994 2004 2008

HC 0.41 0.125 0.10
CO 3.4 3.4 3.4
NO 0.4 0.4 0.14

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CO  NO  CO 2  N 2
2


 Catalytic Conversion of Exhaust Gas

  C 
NO  S NO • S rANO  k NO PNO C V  NO•S  C NO•S  K NO PNO C V
  K NO 

  C 
CO • S CO • S rACO  k CO PCO C V  CO•S  C CO•S  K CO PCO C V
  K CO 

CO • S  NO • S  CO 2  N • S  S rS  k S C CO•S C NO•S 


N •S N •S

N 2 g   2S 
rD  k D C 2N•S  K N 2 PN 2 C 2V  C N•S  C V K N PN 2

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 Catalytic Conversion of Exhaust Gas

rS  k S C NO•SCCO•S 

rS  k SK NOKCO PNOPCO C 2V

C T  C V  C NO•S  CCO•S  C N•S

 C V  C V K NOPNO  C V KCO PCO  C V K N 2 PN 2

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 Catalytic Conversion of Exhaust Gas
Ct
CV 
1  K NO PNO  K CO PCO  K N 2 PN 2
k
  
k S K NO K CO C 2t PNO PCO
  rS 
 rNO
1  K NO PNO  K CO PCO  K N 2 PN 2 
2

kPNO PCO
 
 rNO
1  K NO PNO  K CO PCO  K N 2 PN 2 
2

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 Catalytic Conversion of Exhaust Gas
kPNOPCO
 
rNO
1 K NOPNO  KCOPCO  
2
K N 2 PN 2

Neglect K N 2 PN 2
kPNOPCO
  
rNO 2
1 K NOPNO  KCOPCO 



Catalytic Conversion of Exhaust Gas
kPNOPCO
 
rNO 2
1 K NOPNO  KCO PCO 
Find optimum partial pressure of CO
drNO 
0
dPCO
1 K NOPNO
PCO 
KCO


 End of Web Lecture 17

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