Classification of chemical reactions useful in reactor modeling

Non-catalytic Catalytic

Most gas-phase reactions Most liquid-phase reactions

Homo-
Reactions in colloidal systems
geneous Fast reactions such as burning
of a flame Enzyme and microbial reactions
Burning of coal Ammonia synthesis
Roasting of ores Oxidation of ammonia to produce
Attack of solids by acids nitric acid
Hetero-
geneous Gas-liquid absorption with
Cracking of crude oil
reaction
Reduction of iron ore to Oxidation of SO2 to SO3
iron and steel

June 5, 2008 FILS – Chemical Reactors 1

Homogeneous Chemical Reactors – Revisited Notions
 Classification of polymerization systems

June 5, 2008 FILS – Chemical Reactors 2

Homogeneous Chemical Reactors – Revisited Notions
 Classification of chemical reactions by stoichiometry
S
• single 
j 1
j Aj  0
• multiple
 A  0   rank   
R  S 
• series
   ij Aj  0
• parallel
i 1  j 1 

• competitive

• side – by – side

• mixed

• polymerization

June 5, 2008 FILS – Chemical Reactors 3

Homogeneous Chemical Reactors – Revisited Notions
 The moment generating function (MGF) is the tool to compute the moments
which serve to characterize the polymer distribution;
  y, t  is the generic function; y is the ordering parameter and t is the
independent variable (time)

  y, t   yP1  t   y 2 P2  t   L   y x Px  t  ; y 1
x 1

Px  t  the concentration of the polymer having

x-mers in its chain at time t ≡ x-mer

r
  
 y    y, t 
permits the computation of some remarkable
moments of the distribution
 y 

June 5, 2008 FILS – Chemical Reactors 4

Homogeneous Chemical Reactors – Revisited Notions
 First order moment → mean of the distribution


P  t    xPx  t 
x 1

Second order moment → dispersion of the distribution


 2
P  t    x 2 Px  t 
x 1

Useful particular form of Γ (y,t)

 
1    1, t    Px  t  10    1, 0    Px  0 
x 1 x 1

June 5, 2008 FILS – Chemical Reactors 5

Homogeneous Chemical Reactors – Revisited Notions
 The conversion
Single reaction chemical process
S

 j Aj  0
j 1
  k d   q Q  s S K
a A  b BK 
kr

The degree of transformation for each reactant species is given by

the fractional conversions

N  NA N  NB b N A0
X A  A0 ; X B  B0 XB  XA
N A0 N B0 a N B0

 q 
N A  N A0  1  X A  N Q  N A0  M QA  X A 
 a 
N Aj 0
M jA 
 b   s  N A0
N B  N A0  M BA  X A  N S  N A0  M SA  X A 
 a   a 
June 5, 2008 FILS – Chemical Reactors 6
Homogeneous Chemical Reactors – Revisited Notions
 The degree of advancement / The extent
S

Single reaction chemical process  A

j 1
j j 0

N Aj  N Aj 0
 ; j  1, 2,K , S N A j  N A j 0   j
j
R  S 
Multiple reaction chemical process    ij Aj  0
i 1  j 1 

i 
 N Aj  N Aj 0  i
; i  1, 2,K , R N Aj  N Aj 0   ij  i
R

 ij i 1

S R
NT  N 0   ij  i
j 1 i 1

June 5, 2008 FILS – Chemical Reactors 7

Homogeneous Chemical Reactors – Revisited Notions
 Definition of the reaction rate
1 dN A j moles of Aj which modify during chemical process
rAj  
V dt  volume of fluid   time 
V can be replaced by A (aria), W (mass of catalyst),
Vw (volume of catalyst), Vr (volume of \reactor)

 volume   mass of   surface   volume   volume 

 rAj   
rAj   
rAj   
rAj   rAj
 of fluid   solid   of solid   of solid   of reactor 

For complex reactions - the equivalent reaction rate for every reaction

1 1  dN Aj  1 d i
ri     , i  1, 2,K , R
V  ij  dt   V dt
 i
June 5, 2008 FILS – Chemical Reactors 8
Homogeneous Chemical Reactors – Revisited Notions
 Perfect CA0, XA = 0
Fv0, FM0

mixing CAf , XAf

V, XA, CA, -rA Fvf , FMf
Ideal
Flat velocity profile
Plug
flow
Flow

Bypasses
Real Shortcuts/Channeling
Stagnant zones
Local recycling

June 5, 2008 FILS – Chemical Reactors 9

Homogeneous Chemical Reactors – Revisited Notions
 Residence Time Distribution of Fluid in Vessels

t1
 E  t  dt
0
E
RTD, or E curve

Fraction of exit stream

Total area = 1 older than t 1

0
0 t1 t


 E  t  dt  1
0

 t1
E  t  dt  1   E  t  dt
t1 0

June 5, 2008 FILS – Chemical Reactors 10

Homogeneous Chemical Reactors – Revisited Notions
 F Step input signal
The F curve 1

FV c  t   FV c0 F  t  Tracer output signal

of F curve

c t c  ti 
F  t  F  ti   0
c0 c0 0 t t

E
The E curve Ideal pulse input

FV c  t  dt  m E  t  dt Area 1 Tracer output or E curve

c t c  ti 
E t  
E  ti   
0
 c  t  dt
0
 c  t  dt
0
0 t t

June 5, 2008 FILS – Chemical Reactors 11

Homogeneous Chemical Reactors – Revisited Notions
 Computing the performance of a chemical reactor

A) Macrofluid – use the flow distribution information directly to

compute the performance of the chemical reactor

B) Microfluid – 1) use the flow distribution information to identify a flow

model, best suited for the particular reactor
– 2) use the flow model to aggregate a mathematical
model which will give the performance of the chemical
reactor

June 5, 2008 FILS – Chemical Reactors 12

Homogeneous Chemical Reactors – Revisited Notions
 The main problem of reactor design is how best to include the factors
affecting the chemical process in a mathematical model which has to be
as complicate as needed. Maybe the best approach is “start by trying the
simplest model and then only add complexity to the extent needed”,

b)

Feed
Product
a) Steady-state same
composition at any
Three general types point
c) Product
• the batch Feed

• the steady-state flow Composition at any

Composition
point is unchanged
• the unsteady-state flow (fed- changes with time
with time
batch/semi-continuous reactor) B A B B
Product
d)
A A
Volume and
composition Only volume Only composi-
change changes tion changes

June 5, 2008 FILS – Chemical Reactors 13

Homogeneous Chemical Reactors – Revisited Notions
 A discontinuous or batch reactor has no fluid
streams flowing through. Perfect mixed
V(t) medium
The total feed is introduced before start, and no
withdrawal is made until the reaction has reached X A (t) C A (t)
the degree of completion desired.

The mathematical model results from mass balances for all species
 Input of mass to   Output of mass from   Accumulation of mass 
     
 the system during    the system during    within the system 
 the time period t   the time period t   during the time period t 
     

 amount of mass   amount of mass 

   
 in the system    in the system 
 at time t  t   at time t 
 n   n 

June 5, 2008 FILS – Chemical Reactors 14

Homogeneous Chemical Reactors – Revisited Notions
 S

Single Reaction Chemical Process 

j 1
j Aj  0

The Characteristic Equation

1
X Af dX A rA ⋅ V
t  N A0 
0 rA V
Operating conditions
0
Performance XA
Initial conditions t
Reaction time Area =
N A0
R S

Multiple reactions chemical processes  i 1 j 1

ij Aj  0

1 d i
 ri    , i  1, 2,K , R
V dt
The vector of extents of all reactions, kmol

The extent of reaction “i”, kmol

June 5, 2008 FILS – Chemical Reactors 15
Homogeneous Chemical Reactors – Revisited Notions
The Characteristic Equation and the Volume of Reaction

A) The volume of reaction is constant during the chemical process

1) Single reaction chemical process

XA C
dX A A
dC A
t  C A0 
0
rA  X A 
 
CA0 A 
r CA 
p
1 A
dp A
t 
Rgas pA 0 rA  p A  T

2) Multiple reactions chemical process

d V i
 ri  V  , i  1, 2,K , R
dt
The vector of volumic extents of all reactions, kmol∙m-3

The volumic extent of reaction “i”, kmol ∙m-3

June 5, 2008 FILS – Chemical Reactors 16

Homogeneous Chemical Reactors – Revisited Notions
The Characteristic Equation and the Volume of Reaction

B) The volume of reaction is variable during the chemical process

1) Single reaction chemical process

V  V0  1   X A 

XA dX A
t  C A0 
0
 1   X A  rA  X A ,  
2) Multiple reactions chemical process

 d i 1 d i 1 d mi 1
 ri      ri      ri   m  , i  1, 2,K , R
V dt m dt  dt 
The vector of mass
The mass extent of extents of all
reaction “i”, kmol ∙kg-1 reactions, kmol∙kg-1

June 5, 2008 FILS – Chemical Reactors 17

Homogeneous Chemical Reactors – Revisited Notions
 A continuous reactor has a stream of fluid flowing through.

Plug flow

Flow Ideal

Perfect mixing

Steady-state means that there is no accumulation of any property,

whatsoever.

Homogeneous means that there is a single phase flowing through the

reactor.

June 5, 2008 FILS – Chemical Reactors 18

Homogeneous Chemical Reactors – Revisited Notions
The plug flow reactor – distributed parameter system (the composition
of the fluid varies from point to point along a flow path).

Single reaction chemical processes

Differential form

dX A rA  X A  rA  X A 
 
dV FMA0 FV 0 C A0

equivalent
dz

Integral form dφ


X Af
V dX A

FMA0 C A0
 
0
rA  X A  C A0, XA = 0 FMA FMA + dFMA C Af , X Af
Dv0, F MA0 XA X A + dX A Dvf , FMAf

June 5, 2008 FILS – Chemical Reactors 19

Homogeneous Chemical Reactors – Revisited Notions
 Single reaction chemical processes

Constant volume
PFR’s characteristic equations DCR’s characteristic equations
X Af X Af
V0 dX A dX A
FV 0
  D  C A0 
0
rA  X A 
t  C A0 
0
rA  X A 
Formally, for the constant volume case, the equations are the same,
so the integrated form of the DCR could be used directly for the PFR

Variable volume
PFR’s characteristic equations DC’s characteristic equations
X Af
V dX A
X Af
dX A
FV 0
 t  C A0 
0
rA  X A ,  
t  C A0   1   X A  rA  X A ,  
0

June 5, 2008 FILS – Chemical Reactors 20

Homogeneous Chemical Reactors – Revisited Notions
 Multiple reactions chemical processes

d  m ,i ri   m 
 , i   1, 2,K , R
dz  u
Vector of reactions’ mass extents
i
 m ,i 
Fm
Mass extent Local fluid velocity
of reaction “i”

Average density

June 5, 2008 FILS – Chemical Reactors 21

Homogeneous Chemical Reactors – Revisited Notions
 Space-time, Space-velocity and Mean Residence Time

Space-time A space-time of 2 min means that

 time required to process one  every two minutes one reactor
1 
 D    reactor volume of feed measured     time  volume of feed at specified
s   conditions is being treated by the
 at specified conditions  reactor
Space-velocity
 number of reactor volumes of  A space-velocity of 5 hr-1 means
1  
s   feed at specified conditions which    time1  that five reactor volumes of feed at
D   specified conditions are being fed
 can be treated in unit time  into the reactor per hour
Mean Residence Time

t   t E  t  dt
0

June 5, 2008 FILS – Chemical Reactors 22

Homogeneous Chemical Reactors – Revisited Notions
 The perfectly mixed reactor – concentrated parameter system
(there are no property gradients in the volume of reaction).

Single reaction chemical processes

The characteristic equation relates in a simple way the four terms XA, rA, V,
FMA0; thus, knowing any three allows the fourth to be found directly.

V XA

FMA0 rA  X A 
The driving force responsible for the
accomplishment of the chemical
process is at its minimum.
Conditions within
reactor and at exit

1
rA

Area=V/FMA0
0
XA
June 5, 2008 FILS – Chemical Reactors 23
Homogeneous Chemical Reactors – Revisited Notions
 Multiple reactions chemical processes

ri   m 
 m ,i  , i   1, 2,K , R

Vector of reactions’ mass extents
i
 m ,i 
Fm
Mass extent
of reaction “i”

Mean density

June 5, 2008 FILS – Chemical Reactors 24

Homogeneous Chemical Reactors – Revisited Notions
 Polymerization processes and reactors
The properties of a polymer depend not only on its gross chemical
composition but also on its molecular weight distribution, copolymer
composition distribution, branch length distribution, and so on. The
same monomer(s) can be converted to widely differing polymers
depending on the polymerization mechanism and reactor type. This is
an example of product by process, and no single product is best for all
applications. Thus, there are several commercial varieties each of
polyethylene, polystyrene, and polyvinyl chloride that are made by
distinctly different processes.

The most important – whether the continuous phase contains a

significant concentration of high-molecular weight polymer. When it
does, the reactor design must accommodate the high viscosities and
low diffusivities typical of concentrated polymer solutions. The design
of reactors for operation with a continuous polymer phase has distinct
elements, accordingly. When the polymer-rich phase is dispersed, the
chemical kinetics and mass transfer steps may be very complex

June 5, 2008 FILS – Chemical Reactors 25

Homogeneous Chemical Reactors – Revisited Notions
A polymerization reactor will be heterogeneous whenever the polymer
is insoluble in the mixture from which it was formed. This gives rise to
the precipitation, slurry, and gas-phase polymerizations. If the polymer
is soluble in its own monomers, a dispersed-phase polymerization
requires the addition of a nonsolvent (typically water) together with
appropriate interfacial agents. These extraneous materials need
additional downstream purification and separation and may
compromise product quality. Bulk polymerizations from pure, undiluted
monomer are nominally preferred, although the use of a solvent to ease
processing problems is quite common. For high-volume polymers, like
high-volume chemicals, continuous operation is generally preferred
over batch.

June 5, 2008 FILS – Chemical Reactors 26

Homogeneous Chemical Reactors – Revisited Notions
Polymerization reactors have several characteristics that are different
from most of the chemical reactors:
1. The viscosity of the fluid is a strong function of conversion.
2. Polymerization reactions are strongly exothermic.
3. Most polymerization reactions are strongly influenced by trace
impurities, which strongly affect properties.
4. They frequently involve multiple phases.
5. They frequently use catalysts.
6. Condensation polymerization produces a side product such as H20,
which must be removed from the product and which can cause
complications with reversibility.
7. It is frequently desired to produce a blend of several components,
and reactors must be designed to accomplish this.
8. Solvents are frequently used to control rates and flow characteristics.

June 5, 2008 FILS – Chemical Reactors 27

Homogeneous Chemical Reactors – Revisited Notions
CSTRs are widely used for free-radical polymerizations.
• main advantages
•the solvent or monomer can be boiled to remove the heat of
polymerization;
•fairly narrow molecular weight and copolymer composition
distributions can be achieved.
• principal disadvantages
• high conversions are difficult to achieve (they suffer from the
usual problem of low average reaction rate)
• at high conversion the viscosity can be several orders of
magnitude higher than the design limit for stirred tanks.
Stirred tanks or functionally equivalent loop reactors are also used for
the transition metal polymerization of olefins and dienes when the
catalyst is homogeneous. CSTRs are used for the low-molecular-
weight portions of condensation polymerizations when the
stoichiometry requirements are not severe. Some practical designs use
stirred tanks up to about 75% conversion, with further polymerization
carried out in a tubular reactor.

June 5, 2008 FILS – Chemical Reactors 28

Homogeneous Chemical Reactors – Revisited Notions
The CSTRs produce the narrowest possible MWD for fast chain
growth, short chain lifetime polymerizations like free-radical and
coordination metal catalysis. The mean residence time in the CSTR
will be minutes to hours, and the chain lifetimes are fractions of a
second. Any chain that initiates in the CSTR will finish its growth there.
All the polymer molecules are formed under identical, well-mixed
conditions and will have as narrow a molecular weight distribution as is
possible for the given kinetic scheme.

Condensation polymers and living addition polymers continue to grow

throughout their stay in the reactor. All the chains in a CSTR grow in
the same reaction environment and, subject to the equal reactivity
assumption, grow at the same rate. The chain lengths will have an
exponential distribution, whenever the residence time is reasonably
long. The living polymer will emerge from a CSTR dramatically
different from the narrow molecular weight distribution possible in a
batch reactor. CSTRs cannot be used to produce block copolymers or
homopolymers with narrow molecular weight distributions.

June 5, 2008 FILS – Chemical Reactors 29

Homogeneous Chemical Reactors – Revisited Notions
The uniform chemical environment of a CSTR makes it ideally suited for
the production of copolymers. If the assumption of perfect mixing is
justified, there will be no macroscopic composition distribution due to
monomer drift, but the mixing time must remain short upon scale-up.
Laminar flow is almost inevitable in a polymer reactor when the polymer
is soluble in the continuous phase. Molecular diffusivities are also low.
This combination suggests that segregation is a possibility in a stirred
tank reactor. A segregated stirred tank gives broader molecular weight
distributions, higher conversions, and broader copolymer composition
distributions than a CSTR that has good internal mixing. Given the
appropriate rate expressions, calculations are quite feasible for the
limiting cases of complete segregation and perfect mixing.

June 5, 2008 FILS – Chemical Reactors 30

Homogeneous Chemical Reactors – Revisited Notions
 PFRs are seldom used polymerization processes.

Web-coating polymerizations (for photographic film and coated

abrasives) literally achieve a piston flow reaction environment.
Mechanically driven screw devices used as finishing reactors
for PET closely approximate piston flow. Motionless mixers can
do this as well. However, polymer reactors that closely
approximate piston flow are the exception.

Tubular reactors are occasionally used for bulk, continuous

polymerizations. A monomer or monomer mixture is introduced
at one end of the tube and, if all goes well, a high-molecular-
weight polymer emerges at the other. The classic example is
the high-pressure polymerization of ethylene in a single tube
approximately 1.75 inches in diameter and several miles long.
Scale-up is done by adding another mile to the tube length.

June 5, 2008 FILS – Chemical Reactors 31

Homogeneous Chemical Reactors – Revisited Notions