Chemical Reaction Engineering:

Overview
•CRE
CRE Basics
•What are we trying to accomplish?
•What technical skills do we use?
•Basic Eq
Equations:
ations LHS
LHS=RHS
RHS
•LHS = reactor
•RHS = kinetics, transport and deactivation
•For mass, heat and momentum
•CRE as a Field
•Timeline
•ISCRE
•Key Textbooks
•Typical Outlines
•Our Outline
CRE Overview 1
Chemical Reaction Engineering
g g Basics
• Traditional View of CRE: Analysis and
Design for the Commercial Practice of
Chemistry
o Deals with issues of lab vs. p
process scale
o Mixing, heat, etc.
• CRE also very useful in the design and
analysis of laboratory experiments
• A “chemical process” is usually at the
h
heart off the
h CRE application
li i
 A Schematic Chemical Process

Raw
Separation
p Reaction Separation
p Product
Material

• A chemical reactor is at the heart of the

Chemical Process
• Reactor
R t may constitute
tit t only
l 10-25%
10 25% off
process cost, but it can affect the cost of
the rest of the process significantly:
• Selectivity: Separations
• Activity: Conditions, materials of construction, pumps,
valves, compressors, etc.
 Additional Observations
• Most Commercial Reactions
E l aC
Employ Catalyst
t l t
• Many Sophisticated Reactors
o FCC, Shell-and-Tube, Fluidized Bed,
MicroReactor
•E
Energy/Heat
/H t Management
M t is
i
Crucial
• Safety
• Selectivity
• Catalyst Properties
 Basic Equations
q in CRE

n+2 Equations:

n Mass Balances
Energy Balance
Momentum Balance

LHS = RHS

LHS = Reactor Type, Reflects Mixing

RHS = φηr
φ = catalyst
t l t activity/d
ti it /deactivatio
ti ti n index
i d
η = catalyst effectiveness/utilization factor
r = intrinsic
t s c rate
ate
 Conventional Reactor Material Balances

Reactor Material Balance

Batch dA
= − rA
dt

PFR (Constant Volume) dA

= − rA
dτ

PFR (Molar Expansion) dF A

= − rA
dV

CSTR ( A − A0 )
= − rA
τ

Axial Dispersion
p Reactor ((with first order dC 1 d 2C
− = − kτ C
reaction) dz Pe L dz 2

Simplified Riser Reactor dFA

= −(1 − ε ) ρ cat rA
dV

Mechanism and Reactor Balance Solved Sequentially

CRE Overview 6
 Conventional: Analytical Rate Laws Derived
f
from Mechanism
M h i BEFORE U Use IIn Reactor
R Model
M d l
A Heterogeneous Chemistry (A Æ B) Example

A + l ⇔ Al
Al ⇔ Bl
Bl ⇔ B + l

l0 ( A − B / K )
rA =
⎛ 1 1 1 ⎞ ⎛ 1 1 + K sr ⎞ ⎛ 1 1 + K sr ⎞
⎜ + + ⎟ +⎜ + ⎟ KAA + ⎜ + ⎟K B
⎝ K A ksr k A Kk B ⎠ ⎝ K A k sr Kk B ⎠ ⎝ K A ksr Kk A ⎠ B

surface rxn control adsorption control

desorption control

l0 k A ( A − B / K )
l k K (A− B / K) l k K( A − B / K ) rA =
rA = 0 sr A rA = 0 B K
1 + K A A + KBB 1 + K A A + KK B A 1 + A B + KBB
K

CRE Overview 7
 Basic Governing Equations
Illustrate MRT Appeal

Consider A → B
dA / dτ = −ko exp(− E * / RT ) A (1)
ρC P dT / dτ = kA(−ΔH ) − U ( S / V )(T − TC ) (2)
• Eq. 1 provides the effect of T
Eq
• Eq. 2 provides the heat generation and heat removal terms
• MRT technology provides unusual control over U(S/V)
• MRT: limiting-
limiting case approximation, U(S/V) large ((->isothermal)
isothermal)
• CRT: limiting- case approximation, U(S/V) small (-> adiabatic)

CRE Overview 8
ISCRE: The International Symposia on
Chemical Reaction Engineering
Co‐Sponsoring
Name Place Country Year Organizations
ESCRE 1 Amsterdam Netherlands 1957 EFChE
ESCRE 2 Amsterdam Netherlands 1960 EFChE
ESCRE 3 Amsterdam Netherlands 1964 EFChE
ESCRE 4 Brussels Belgium 1968 EFChE
ISCRE 1 Washington USA 1970 ACS/AIChE
ISCRE 2 Amsterdam Netherlands 1972 EFChE
ISCRE 3 Evanston USA 1974 ACS/AIChE
ISCRE 4 Heidelberg Germany 1976 EFChE
ISCRE 5 Houston USA 1978 ACS/AIChE
ISCRE 6 Nice France 1980 EFChE
ISCRE 7 Boston USA 1982 ACS/AIChE
ISCRE 8 Edinburgh Great Britain 1984 EFChE
ISCRE 9 Philadelphia USA 1986 ACS/AIChE
ISCRE 10 Basel Switzerland 1988 EFChE
ISCRE 11 Toronto Canada 1990 ACS/AIChE/CSCE
ISCRE 12 Torino Italy 1992 EFChE
ISCRE 13 Baltimore USA 1994 ACS/AIChE
ISCRE 14 Brugge Belgium 1996 EFChE
ISCRE 15 Newport USA 1998 ACS/AIChE
ISCRE 16 Cracow Poland 2000 EFChE
ISCRE 17 Hong Kong China 2002 Asia Pacific CRE
ISCRE 18 Chicago USA 2004 ACS/AIChE
ISCRE 19 Potsdam/Berlin Germany 2006 EFChE
ISCRE: The International Symposia on
Chemical Reaction Engineering
The Discipline: Typical Text Structure
1. Homogeneous Kinetics
2. Heterogeneous Kinetics
3. Transport
a) Internal
b) External
4. Isothermal Reactors
a) Batch
b) CSTR
c) PFR
5. Non‐Isothermal Reactors
a) Energy Balance
b) Multiplicity, Stability
6. Fixed Bed Reactors
7. Fluid Bed Reactors
8 Catalyst
8. C t l tDDeactivation
ti ti
9. Optimization
10. Gas‐Liquid Reactions
11. Lab Issues
12. Modeling
Basic Kinetics and Reactors

1. Rate Laws
2. Basic
i Ideal
d l Reactors
3. Performance and Combinations
4
4. Lab Reactors
5. Laboratory Experiments
 Rate Laws at the Core of
Reaction Engineering
Mechanism Interpretation ↔ rA = f(C A , C B , T, P, ε , cat, ...) ↔ Process Chemistry

Examples

rA = kC A
rA = kC 2A
kC 3A / 2
rA =
1 + kC A
kC AC B
rA =
(1 + K AC A + K B C B ) 2
 A Biochemical Example
Substrate (S) ⎯Enzyme
⎯ ⎯⎯ (E)
→ Products (P)

Analysis : S + E ←⎯→
1, 2
ES ←⎯→
3, 4
P+E
Rate Eo = E + ES
k 3 Eo ( S − P / K )
rate =
k
Km + S + 4 P
k1

CS
 Amorphous Silicon Fabrication
Mechanism :
SiH 4 ←
⎯→
1
SiH 2 + H 2
SiH 2 ←
⎯→2
Si + H 2

k1k 2 SiH 4
Rate Law : r =
k −1 H 2 + k 2
Analysis
a ys s :
d ( SiH 2 )
= 0 = k1SiH 4 − (k −1 H 2 + k 2 ) SiH 2
dt
Rate SiH 2 = 1
k SiH 4
k 2 + k −1 H 2
k1k 2 SiH 4
r = k 2 SiH 2 =
k 2 + k −1 H 2

H2
 Hydrolysis in Supercritical Water
Mechanism : H 2O + R − L ⎯
⎯→
k
R − OH + HL

ε
r = ko f ( μ ≠ , μ H O , μ RL )C H 2O C RL
2

2ε + 1

k Tr = 1.1

CH2O
Increases in CH2O increases density which increases ε
 Epoxy‐Amine Kinetics
NH 2 − R − NH 2 + EO − R'− EO → NH 2 − R − NH − CH 2OH − CO − R'− EO

r = kAE (1 + k ' x) = kAE (1 + k " OH )

Autocatalysis by product OH groups

Rate Tr = 1.1

Conversion
 Catalytic HDN
1st
Mechanism : RN + 2 H 2 ⎯k⎯→ RH + NH 3

Increasing RNo

lnRN/RNo

Strong competitive adsorption

kK ( RN − RH • NH 3 / K )
Rate Law : r =
1 + K ( RN + NH 3 )

time
Underlying
y g Mechanism
Thermal Cracking
A → 2β
1 st
β + A→μ+B A ⎯k⎯→ B + C
μ →C+β
2 β → TP
2 μ → TP
β + μ → TP

n = 1/ 2 n = −1 / 2
n=0

logk1st
kA3 / 2 kA3 / 2
Rate Law : r = =
1 + KA (1 + 2 KA + KA2 )1/ 2

logAo
Strong UD Presence in Chemical Reaction Engineering

R.H. Wilhelm Award in Chemical Reaction Engineering

R. H. Wilhelm 1966 M. Dudukovic 1994
D. L. Katz 1967 J. Villermaux 1995
N. R. Amundson 1973 M. R. Feinberg 1996
M. Boudart 1974 J. A. Dumesic 1997
R. Aris 1975 D. Ramkrishna 1998
J. J. Carberry 1976 S. Sundaresan 1999
J. M. Smith 1977 K. F. Jensen 2000
P. B. Weisz 1978 G. N. Stephanopoulos 2001
O. Levenspiel 1979 Bruce C. Gates 2002
C. N. Satterfield 1980 Enrique Iglesia 2003
R. A. Schmitz 1981 Teh C. Ho 2004
V. W. Weekman, Jr 1982 Massimo Morbidelli 2005
G. R. Gavalas 1983 Christopher Bowman 2006
G. F. Froment 1984 Matthew Neurock 2007
E. E. Petersen 1985 Michael T. Klein 2008
D. Luss 1986 Raymond J. Gorte 2009
K. B. Bischoff 1987 Ioannis G. Kevrekidis 2010
L. L. Hegedus 1988 Dionisios G. Vlachos 2011
V. Hlavacek 1989 Nicholas Delgass 2012
L. K. Doraiswamy 1990 Liang-Shih Fan 2013
J. L. Hudson 1991 Manos Mavrikakis 2014
A. T. Bell 1992 Harold H. Kung 2015
A. Varma 1993 Israel Wachs 2016