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Chemical Reaction Engineering

Mole Balances

Prof. Zayed Al-Hamamre

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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888

Content

 Introduction
 Reaction Rate
 General Mole Balance
 Balance on Batch Reactor
 Balance on CSTR
 Balance on PFR
 Packed Bed Reactor

2
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Introduction
What is Chemical Reaction Engineering (CRE) ?

 Understanding how chemical reactors work lies at the heart of almost every
chemical processing operation.

 Design of the reactor is no routine matter, and many alternatives can be


proposed for a process.
 Reactor design uses information, knowledge and experience from a variety
of areas - thermodynamics, chemical kinetics, fluid mechanics, heat and
mass transfer, and economics.

 CRE is the synthesis of all these factors with the aim of properly designing
and understanding the chemical reactor.

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Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
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Introduction

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Modeling of Digestive System of a Hippopotamus

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How do we design a chemical reactor?

Type & size

Maximize the space-time yield of the desired product


(productivity lb/hr/ft3)

Stoichiometry
Kinetics
Basic molar balances Reactor volume
Fluid dynamics

Use a lab-scale reactor to determine the kinetics!


6
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Reactor Design

Reaction
Stoichiometry
Kinetics: elementary vs non-elementary
Single vs multiple reactions

Reactor
Isothermal vs non-isothermal
Ideal vs nonideal
Steady-state vs nonsteady-state

7
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What type of reactor(s) to use?

in
Continuously Stirred
Tank Reactor (CSTR)

out

Plug flow reactor (PFR)


Well-mixed batch reactor
8
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What size reactor(s) to use?

Answers to this questions are based on the desired


conversion, selectivity and kinetics

Kinetics
Reactor type Conversion
& &
size Material & selectivity
energy
balances

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Chemical Identity
• A chemical species is said to have reacted when it has lost its chemical identity.
• The identity of a chemical species is determined by the kind, number, and
configuration of that species’ atoms.
• A chemical species is said to have reacted when it has lost its chemical identity.

1. Decomposition CH3CH3  H2 + H2C=CH2

2. Combination N2 + O2  2 NO

3. Isomerization C2H5CH=CH2  CH2=C(CH3)2

 Two isomers display different chemical and physical properties

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Reaction Rate
 The reaction rate is the rate at which a species looses its chemical identity per unit
volume.
 The rate of a reaction (mol/dm3/s) can be expressed as either
the rate of Disappearance: -rA
or as
the rate of Formation (Generation): rA
 Consider the isomerization AB

rA = the rate of formation of species A per unit volume

-rA = the rate of a disappearance of species A per unit volume

rB = the rate of formation of species B per unit volume


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Reaction Rate
 The rate of reaction tells us how fast a number of moles of one chemical species are
being consumed to form another chemical species.
 It is assumed that the total mass is neither created nor destroyed when a chemical
reaction occurs.
EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e.,

rB = 0.2 mole/dm3/s

12
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Reaction Rate
• EXAMPLE: AB

rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s

The rate of formation (generation of A) is

rA= -0.2 mole/dm3/s

13
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Reaction Rate
EXAMPLE:

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Reaction Rate
• For a catalytic reaction, we refer to -rA',
which is the rate of disappearance of species A on a per mass of catalyst basis
(mol/gcat/s)
NOTE: dCA/dt is not the rate of reaction
 It is simply a mole balance that is only valid for a constant volume batch
system
Consider species j:
 rj is the rate of formation of species j per unit volume [e.g. mol/dm3/s]
 rj is a function of concentration, temperature, pressure, and the type of catalyst (if
any)
 rj is independent of the type of reaction system (batch, plug flow, etc.)
 rj is an algebraic equation, not a differential equation

15
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Rate Law for rj


A  B  products

1st order in A, 1st order in B, 2nd order overall r A  kC A CB

nth order in A r A  kC A n

k1C A
Michaelis-Menton: common in enzymatic reactions  rA 
1  k 2C A
rj depends on concentration and temperature:
 Ea 
 
-rA  A e RT  C A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature
16
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General Mole Balance
System
Volume, V

Fj0 Gj Fj

Molar Flow Molar Flow  Molar Rate  Molar Rate 


 Rate of    Rate of   Generation    Accumulation
       
Species j in  Species j out of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
 time   time   time   time  17
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General Mole Balance


in - out + generation = accumulation
dN j
Fj  Fj  Gj 
0 dt
 mol   mol   mol  d
      mol 
 s   s   s  dt

Nj: moles j in system at time t

If the system is uniform throughout its entire volume, then:


G j  rj V
Moles
Moles j
generated per
generated per Volume
= unit time and
unit time (m3)
volume
(mol/s)
(mol/s•m3)
18
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General Mole Balance
Non-Uniform Generation system
If rj varies with position (because the
temperature or concentration varies) then
rj1 at location 1 is surrounded by a small V
Rate is rj1
subvolume V within which the rate is within this Rate is rj2
uniform V volume within this
m V volume
G j  lim  rjV   rjdV
m→∞ i1
V→0

1 111
then G j     rj x, y, z  dx dy dz
000

1 y Plug in rj and integrate over x, y, and z


1
x 19
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General Mole Balance


Fj0 Fj
Gj

System volume

In - Out + Generation = Accumulation


dN j
Fj0  F j  G j 
dt
dN j
Fj0  F j rj V  uniform rate in V
dt
V dN j
Fj0  F j   rj dV  nonuniform rate in V
dt
Next time: Apply BME to ideal batch, CSTR, & PFR reactors 20
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Batch Reactor

21
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Batch Reactors Properties

• Reactants are placed in the reactor,


and the reaction is allowed to
proceed for some amount of time
• Closed system- no addition of
reactants or removal of products
during the reaction
• Unsteady-state conditions- the
composition changes with time
• Ideal batch reactor- vessel is
perfectly mixed
• Concentration and temperature are
spatially constant, but NOT constant
in TIME
22
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Examples of Batch Reactor
Lab-Scale
Typical Commercial Batch
Batch Reactor
Reactor

Motor for agitation

23
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Mole Balance for Batch Reactor


No flow in
In - Out + Generation = Accumulation
or out!
V dN j
X X
Fj0 F j Fj F j   rjdV 
0 dt
0 0
V dN j
  r jdV  Batch Reactor
dt Design Equation

If the reactor is perfectly mixed, the temperature, concentration, &


therefore the reaction rate are spatially constant:
dN j Ideal Batch Reactor
rj V 
dt Design Equation 24
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Chapter 1
Mole Balance for Batch Reactor

dN A
Integrating dt 
rAV

when t  0 N A  N A0
t  t NA  NA
NA
dN A
t   rAV
N A0

Time necessary to reduce the number of moles of A from NA0 to NA.

25
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Chapter 1
Mole Balance for Batch Reactor

NA
dN A
t   rAV
N A0
NA

26
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Continuous Stirred Tank Reactor (CSTR)

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(CSTR) Properties

• Continuously add reactants and


remove products (open system)
• Inlet stream instantaneously mixes with
bulk of reactor volume
• Ideal batch reactor- assume perfect
mixing occurs in vessel
• Temperature and concentration are
uniform throughout space
• Composition of the exit stream is the
same as that inside reactor (CA,outlet =
CA, tank)
• Steady-state conditions- the reaction
rate is the same at every point and
does not change with time
28
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Examples of CSTRs

Laboratory-Scale Bioreactor
29
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CSTR Mole Balance


Fj0 Fj
In - Out + Generation = Accumulation
V dN j CSTR is at steady state
Fj F j   rjdV  (SS), so no change in
0 dt
moles j with time!
0
V
 Fj F j   rjdV  0 Steady State CSTR
0 Design Equation

A perfectly mixed CSTR has no spatial variations in reaction rate


 Fj F j rj V  0 Rearrange to put in terms of V
0

rj is measured at the Fj F j Ideal Steady State


0  V CSTR Design
outlet because Cj,exit
 rj
= Cj,tank Equation 30
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CSTR Mole Balance
Fj F j
V 0
 rj
Reactor volume required to reduce the entering flow rate of species j
from Fj0 to Fj at the outlet (and in the tank)
How do we determine the molar flow rate, Fj (units = mol/time)?
Fj   C j   
moles j  moles   volume 
  
time  volume   time 
Cj: concentration of j : volumetric flow rate
Ideal SS CSTR design equation in terms of concentration:
C

C
j

0  j

V

rj

 31
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Plugged Flow Reactor (PFR)

32
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PFR Properties

• Also called a tubular reactor


• Cylindrical pipe with openings at
both ends
• Steady movement of material
down length of reactor
• Reactants are consumed as they
flow down the length of the
reactor
• Operated at steady state:
• No radial variation in
temperature, concentration,
or reaction rate
• All fluid/gas elements have
the same residence time
33
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Industrial PFRs

Polyethylene reactor:
• 16 inch inner diameter
• Operates at 35,000 psi & 600 °F
• Has a vertical orientation when in use
Courtesy of Autoclave Engineers of Snap-tite, Inc. 34
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Mole Balance – PFR
 In a plug flow reactor the composition of the fluid varies from point to point along a
flow path. Consequently, the material balance for a reaction component must be
made for a differential element of volume ΔV ΔV

FA0 FA
dNj
Fj0 - Fj + rjV =
dt
dN j Divide by V
Fj  Fj  rj V   Fj  Fj  rjV  0
V V V dt V V  V
V
0
Fj  Fj lim dFj
V V V
Fj V  V Fj V V→0  rj
  rj  0   rj dV
V V
If we assume the PFR is ideal, the degree of completion is not Ideal SS PFR
affected by PFR shape, only by PFR volume Design Eq.
35
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Plug Flow Reactor


FA FA 0
dF A dF A
The integral form is: V  
FA 0
rA
   rA
FA

This is the volume necessary to reduce the entering molar flow


rate (mol/s) from FA0 to the exit molar flow rate of FA.

Profile of the molar flow rate of reactnant and product in a PFR

36
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Packed Bed Reactors (PBR)

37
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Packed Bed Reactors (PBR)


• Cylindrical shell, vertically oriented
• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of
catalyst inside
• Reactants enter top and flow through the
packed bed of catalyst
• Concentration gradient of reactant and
product down the length of the reactor
• Reaction occurs on the surface of the catalyst
pellets
• Reaction rate is based on the mass of the
solid catalyst, W, not reactor volume V
38
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Packed Bed Reactor - Mole Balances

PBR
FAo FA

mol
Units for the rate of a catalytic rxn (rj’) :
s  kg catalyst

39
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Packed Bed Reactor - Mole Balances


W
PBR

FA FA

W W  W
dN A
FA W   FA W  W   rA W 
dt
Steady State dN A
0
dt
F A W  W  F A
lim W
 rA
W  0 W 40
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Packed Bed Reactor - Mole Balances

Rearrange:
dFA
 rA
dW
The integral form to find the catalyst weight is:
FA FA 0
dFA dFA
W  rA
 
FA
 rA
FA 0

PBR catalyst weight necessary to reduce the entering


molar flow rate FA0 to molar flow rate FA.

41
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Fluidized CSTR Containing Catalyst Particles

42
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Fluidized CSTR
Use basic molar balance to derive a reactor design equation for a fluidized CSTR
containing catalyst particles. The equation should be in terms of catalyst weight (W)
and the reaction rate for an equation that uses solid catalyst. Assume perfect mixing and
steady-state operation of the CSTR.

In - Out + Generation = Accumulation


W dN j
Fj0  F j   rj ' dW 
dt
 mol   mol   mol  d
       kg   mol 
 s   s   kgs  dt

1. Simplify this expression. Things to consider: Is there flow? Accumulation? Is


the reaction rate the same everywhere in the reactor?
W dN j
Fj0  F j   rj ' dW  At steady state
dt
43
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Fluidized CSTR

 Fj0  F j rj ' W  0 Rearrange to get in terms of W

Fj0  Fj Ideal Fluidized


 Fj0  Fj  rj ' W   W CSTR Design
rj '
Equation

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r’j vs rj
Consider a reaction that occurs on a catalyst surface (a heterogeneous
rxn).
How is the reaction rate r’j that is in terms of the weight of catalyst
related to the rate in terms of volume (rj)?

Hint: rj = x r’j What is x?

mol  mol  Rearrange to


3
 x  solve for x
sm  s  kg catalyst 
 mol  s  kg catalyst 
 
3  x
sm  mol 

45
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r’j vs rj

 kg catalyst  catalyst weight Bulk catalyst


 3
  x   b density
 m  catalyst volume
rj = b r’j

46
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Test
Use your result from the previous question to derive a reactor design equation for
a fluidized CSTR containing catalyst particles. The equation should be in terms of
catalyst weight (W) and the reaction rate for an equation that uses solid catalyst.
Assume perfect mixing and steady-state operation of the CSTR.
Fj0  Fj Need an equation that has W
CSTR design equation: V
rj instead of V and –rj’ instead
of -rj

Step 1: Come up with an equation that relates V to W (V=?W) & substitute this
equivalency into the CSTR design equation.

Fj0  Fj W Fj0  Fj
W V W Substitute W/ρb for V
V  
b  b rj
V b in design eq: rj

47
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Test Cont.
Step 2: Substitute an expression that relates –rj to –rj’ into the design eq:
mc
la
o
m
l m
o

s
k
g
t
a
l
y
s
t
s

Units for rj: Units for rj’:


 3 

From the previous question: rj = b r’j

W Fj0  Fj W Fj0  Fj Fj0  Fj Ideal Fluidized


   Simplify:  W 
b rj b b  rj '  rj ' CSTR Design
Equation

48
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Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor Differential Algebraic Integral
NA NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A
t
CSTR FA 0  FA
V
rA FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
V
FA FA
PBR dFA dFA
dW
 rA W 
FA 0
rA
W 49
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Selection of Reactors
Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production
CSTR: most homogeneous liquid-phase flow reactors
• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of the
flow reactors - very large reactors are necessary to obtain high
conversions
PFR: most homogeneous gas-phase flow reactors
• relatively easy to maintain
• usually produces the highest conversion per reactor volume (weight of
catalyst if it is a packed-bed catalyze gas reaction) of any of the flow
reactors
• difficult to control temperature within the reactor
• hot spots can occur
50
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Example 1
The reaction A→B is to be carried out isothermally in a continuous-flow reactor.
Calculate the CSTR volume to consume 99% of A (CA=0.01CA0) when the
entering molar flow rate is 5 mol A/h, the volumetric flow rate is constant at 10
dm3/h and the rate is –rA=(3dm3/mol•h)CA2.

 
Fj  C j   0 = 10 dm3/h = 
reactor
FA0=5 mol A/h FA=CA where CA = 0.01CA0

d d
N t
j
F

F
r
V
j

j
j
CSTR design eq: In - Out + Gen = Accumulation 0   
0
F FA C   C A
 V  A0  V  A0
rA rA
Substitute in:
–rA=(3dm3/mol•h)CA2 & CA=0.01CA0
51
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Example 1 Cont.

C A0  0.01C A 0 Factor CA0 1  0.01


V V
3 dm3 molh 0.012 CA02 numerator 3 dm3 molh 0.012 CA02
0.99 5 mol
 V= We know . FA 0 h =0.5 mol

  2 C C =
3 dm molh  0.01 C A0 What is CA0?
3 A0 A0
0 3
10 dm h dm3

V

0.99 10 dm3 h 
 V  66,000 dm3
3 dm 3

molh  0.01
2
0.5 mol dm  3

52
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Example 2
The reaction A→B is to be carried out isothermally in a continuous-flow reactor.
Calculate the PFR volume to consume 99% of A (CA=0.01CA0) when the entering
molar flow rate is 5 mol A/h, the volumetric flow rate is constant at 10 dm3/h and
the rate is –rA=(3dm3/mol•h)CA2.
5mol h mol
C A0 = =0.5
 
3
0 = 10 dm3/h =  10 dm h dm3
Fj  C j  
reactor
FA0=5 mol A/h FA=CA where CA = 0.01CA0

dFA dC A Substitute in: –rA=(3dm3/mol•h)CA2 but


PFR design eq:  rA   rA
dV dV not CA=0.01CA0 until after integration!

0.01C A0
dC A  dm3  2  dC A V
   3  CA     dV
dV  molh 
  3 dm3 molh   C A0 CA 2 0

53
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888

Example 2 Cont.
b a
1 n
b

n
1

n
1

n
1
b

b
x

n
1
n

 
d
x

x
d
x

    b dx 1
REVIEW:
     
      2  
n
1

n
1
x

for n≠1:  
a

     ax x a

  1 1  10 dm3 h  1 1  dm3
  0.01C  C   V     V
 3
3 dm molh  
A0 A0 
 3 
 3 dm molh  
 
0. 01 0. 5  0.5  m ol

Much smaller V required to get same conversion in a PFR than


 660 dm3  V
in a CSTR

54
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 3
The gas phase reaction A→B+C will be carried out isothermally in a 20 dm3
constant volume, well-mixed batch reactor. 20 moles of pure A is initially placed in
the reactor. If the rate is –rA=kCA and k=0.865 min-1, calculate the time needed to
reduce the number of moles of A in the reactor to 0.2 mol.

d d
N t
j
F

F
r
V
dNA Batch reactor

j
j
In - Out + Gen = Accum 0     rA V 
0 dt design eq

Need to convert to dCA/dt NA


How is dCA/dt related to dNA/dt?
CA  so NA  CA V
V

dNA d dNA dC A dV dNA dC A Plug into


   CA V   V  CA  V
dt dt dt dt dt 0 dt dt design eq

55
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888

Example 3 Cont.
dC A dCA Plug in rate dCA Rearrange
 rA V  V  rA  law  k C A 
dt dt dt & integrate
1 n
b

b a
d
x
l
n
x

l
n
b
l
n
a

REVIEW:            ln  ba 
x


a

for n=1:  

t CAdC A  kt  ln C A Convert Cj  kt  ln NA V  t  1 ln NA


 k  dt   C A0 back to Nj/V k NA0
0 C CA NA0 V
A0

min 0.2
Substitute in values for k, NA0, & NA t ln  t  5.3 min
0.865 20

56
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Industrial Reactors

Liquid-Phase Reactions

Gas-Phase Reactions

57
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888

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