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ENGS 157

Chapter 7
Reactor Design

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ENGS 157 Outline

Intro to process design

Process creation
Simulation to assist in process creation
Heuristics for process synthesis
REACTOR DESIGN
Synthesis of separation trains
Second law analysis
Heat and power integration
Heat exchanger design
Capital cost estimation
Profitability analysis

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Overview of Ch. 7: Reactor Design

Be familiar with types of reactor models available in
simulators and their use in process simulation.
Be able to design a system for heat transfer in association
with the reactor, to sustain an exothermic or endothermic
reaction at the desired temperature, and study the design
using simulation.

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Reactor Models
Chemical reactors are typically custom designed to involve:
Multiple phases (e.g. vapor, liquid, reacting solid, solid catalyst)
Different geometries (e.g. stirred tanks, tubular, nozzles,
membranes)
Various regimes of momentum, heat, and mass transfer (e.g.
viscous flow, turbulent flow, conduction, radiation, diffusion,
dispersion)

Attempts to develop generalized reactor models have had

limited success
Simulators provide ideal reactor models appropriate for
early stages of process synthesisgive effluents and heat
duties.

When details become important in later design stages,

replace ideal models with custom-made modelscan insert
into simulators

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Ideal Reactor Models

Most simulators provide four kinds of reactor models:
1. Stoichiometric
2. Equilibrium

Good for very early stages when conducting

mass & energy balances; do not take kinetics into
account!

3. Continuous-stirred-tank reactor (CSTR)

4. Plug-flow tubular reactor (PFR)

Kinetic models
useful for sizing
reactors

Aspen has 2 additional models:

1. Yieldmodels reactor by specifying reaction yields of each

component. Useful when: a) stoichiometry and kinetics
unknown, b) yield distribution data (or correlations)
available
2. Batchkinetic batch (or semi-batch) kinetic model; uses holding
tanks to interface with steady-state operations

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Stoichiometric Reactor Models

Reaction stoichiometry:
C

v A 0,i 1,..., R
ij

j1

2H2 + CO CH3OH

Aj = chemical formula for species j

vij = stoichiometric coefficient for species j in rxn i

vij =

-2
-1
1

How far a reaction has proceeded:

Xk

moles of k reacted nk, in nk, out

moles of k fed
nk, in

0 Xk 1
(fractional conversion)
Relative (dimensionless) value

moles of k reacted
nk, in nk, out
k

stoichiometric coefficient of k
vk
6

Units = moles/time
(molar extent)
Absolute value

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Aspen RStoich Block

Performs mass balance calculations based on reaction
stoichiometry
Used when reaction kinetics are unknown or unimportant
Can use to calculate Hrxn, adiabatic temperature rise

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Equilibrium Reactor Models

For equilibrium reactions: aA + bB + rR + sS +
Two methods can be used to calculate equilibrium:
1) Calculate equilibrium constants from Gibbs energy
of reaction combined with material balance equations

Grxn
aRr aSs ...
a b
K (T ) exp
RT a A aB ...

rxn

K
ai

= equilibrium constant
= component activity

Gi

= Gibbs energy of formation

Grxn
= Gibbs energy of reaction

rG sG ... aG bG ...

Requires stoichiometry for all reactions

2) Determine minimum Gibbs energy for the reacting

system Only requires list of all possible products

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Gibbs Energy, G

Minimum Gibbs Energy

Grxn= (G/ )T,P
Grxn < 0

Grxn > 0

Grxn < 0 forward rxn spontaneous

Grxn > 0 reverse rxn spontaneous

Grxn = 0

Grxn = 0 equilibrium

Molar Extent,

Minimum Gibbs energy model:

G
0
N

where

G NiG i
i 1

Ni = mole number of component i

Gi = partial molar Gibbs energy of i

Components = feed + possible products

Mole number constrained by atom balance
9

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Aspen REquil Block

Calculates equilibrium constants from Gibbs energy
Can restrict equilibrium by specifying one of:
Molar extent of the reaction
A temperature approach to chemical equilibrium

Temperature approach is the number of degrees above

the reactor temperature at which chemical equilibrium is
determined:
TEquil=TR + T

10

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Aspen RGibbs Block

Handles simultaneous phase and chemical equilibrium by
minimizing the Gibbs free energy with phase splitting
Does not require reaction stoichiometry
Can also restrict equilibrium
Only Aspen Plus unit operation that calculates solid-liquidvapor equilibrium

11

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REquil vs. RGibbs

Two advantages of RGibbs:
1) Dont need to specify stoichiometry, only possible
products
2) Can handle multiple phases and simultaneous
phase equilibrium
Why not always use RGibbs instead of REquil?
Chemical reactions are usually known by the time
the reactor is to be designed, thus can use REquil
RGibbs useful for preliminary exploration of
thermodynamic possibilities
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Ideal Kinetic Reactor Models

Mole Balance:

Systemvolume

Fjo

Gj

rateofflowjin + rateofformation
jbyreaction

Fjo

Gj

Fj

rateofflowjout

Fj

Fj

Fjo

13

moles
time

r dV
j

moles
volume time * volume

rateofaccumulation
ofjwithinsystem
dNj
dt

dNj
dt

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CSTRs
Molebalanceequation:
V

Fjo

r dV

Fj

dNj
dt

r dV r V
j

Steadystate

perfectmixingnospatialvariationinrate

CSTRdesignequation:
V

FjoFj+Vrj=0

Fjo - Fj
- rj

mole/time
mole/(time * volume)

14

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CSTRs
Intermsofconcentration:
voCjo - vCj
V
- rj

wherev=volume/time

AnimportantcharacteristicofCSTRs:
Cj|tank=Cj|exitstream

Cjo

Cj

Concentrationinexitstreamis
sameasthatinthetank

Truefortemperatureandconversion,too
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PFRs
Now,considerplugflowreactor(PFR)
Alsoreferredtoastubularreactors
Assumptions:
Perfectradialmixing;dC/dr=0
Noaxialmixing(plugflow)

Perfectradialmixing

Noaxialmixing
Plugflow

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PFRs
Toderivedesignequation,applymolebalancetoadifferential
slice:
Fj

y y+y

Fj|yFj|y+y+rjV=0

Intermsofconcentration:

17

Intermsofreactor
volume:

Assume:
Vwellmixed,butadjacentVnot
Steadystate

Fj | y y - Fj | y
rj
V
d(vCj)
rj
dV
Fj

dFj
Fjo rj

lim

V 0

dFj
rj
dV

wherev=volumetricflowrate

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Design Equations as f(X)

CSTR:
Recall:

FA=FAo(1X)

MolebalanceforconstantV:

FAoX=rAV

DesignequationintermsofX:

FAoX
(-rA)exit

PFR:
Recalldifferentialmolebalance:

dFA
rA
dV

Molebalanceforentirereactor:

FA=FAo(1X)

d[FAo(1 - X)]
rA
dV
18

dX
FAo
rA
dV

(note:forAasreactant,
dFA,rAbothnegative)

dX
- rA
0

V FAo

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Comparing CSTR and PFR Volumes

ConsiderreactionAproductswithfollowingconversiondata:
Recalldesignequations:
30
25

FA0
rA
(L)

20

FAoX
(-rA)exit

CSTR

dX PFR
- rA
0

CSTR

V FAo

15
10
5

19

LevenspielPlot

PFR

Q:WhatCSTRvolumeis
requiredtoachieve80%
conversion?
V20L

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Q:HowaboutPFRvolume?
Willitbegreaterorless
X
thanforCSTR?

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CSTRs in Series
Consider2CSTRsinseries:the1stachieving40%conversion,
andthe2ndachieving80%
X1=0.4
30
25

FA0
rA
(L)

X2=0.4

20
15

V13.6L

10

V210L13.6Ltotal
CSTRsinseriesrequire
lessvolumethansingle
CSTR!

5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
20

As#CSTRsinseries,
thetotalvolume
approachesthatofPFR

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Aspen RCSTR and RPlug Blocks

RCSTR performs a mass and energy balance around
an ideal continuous stirred tank reactor with known
reaction kinetics
Assumes perfect mixing on both macroscopic and
microscopic levels
RPlug Performs a mass and energy balance around an
ideal plug flow reactor
Assumes perfect mixing in the radial direction and no
mixing occurs in the axial direction
Optional coolant stream can also be specified
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Specifying Reactions for CSTRs and PFRs

Rate-controlled and non-electrolyte equilibrium reactions are specified as
Reaction IDs that can be referenced in kinetic reactors, columns, and pressure
relief calculations. These reactions can be used by:
RBatch, RCSTR, and RPlug, the kinetics-based reactor models
RadFrac for reactive distillation
Pressure Relief model for pressure relief calculations in reactive
systems
The reaction kinetics of rate-based reactions can be represented using
any of the following expressions:
Power Law kinetic model
Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model (not
applicable to reactive distillation systems)
User-defined kinetic model written in Fortran or Aspen Custom
Modeler
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Aspen Reactor Model Summary

23

Model

Description

RStoich

Non-kinetic model; performs balances based on reaction

stoichiometry

REquil

Non-kinetic model; calculates equilibrium composition using known

stoichiometry

RGibbs

Non-kinetic model; calculates equilibrium composition by

minimizing Gibbs energy

RCSTR

Kinetic model for ideal CSTR

RPlug

Kinetic model for ideal PFR

RBatch

Kinetic model for ideal batch or semi-batch reactor

RYield

Non-kinetic model; performs balances based on product yields

USER

Allows user-defined, non-conventional kinetics

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Aspen Reactor Model Demo

Model ethyl acetate formation from ethanol and acetic
acid:
C2 H 5OH CH3COOH CH3COOCH 2CH3 H 2O

RCSTR: adiabatic temperature rise and Hrxn

REQUIL: equilibrium, known stoichiometry
REGIBBS: equilibrium, unknown stoichiometry
RCSTR: kinetic CSTR reactor
RPLUG: kinetic PFR reactor
RBATCH: kinetic batch reactor
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Aspen Reactor Model Demo

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Aspen Reactor Model Demo

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Batch vs. Flow and Tank vs. Tube

For producing high-volume chemicals, flow reactors are usually preferred. Recall
that an ideal PFR exactly duplicates the kinetic behavior of an ideal batch reactor.
Reasons for preferring one over the other involve secondary considerations such as
heat and mass transfer, ease of scale-up, and materials handling logistics.
Flow reactors favored for large scale commodity chemicals.
Tube reactors (i.e. PFRs) are typically preferred over tank reactors; exceptions
occur when plug flow is not possible and/or superior product results from the special
reaction environment in stirred tanks.
Tubular reactors are generally used for gaseous reactions, but are also suitable for
some liquid phase reactions.
Selectivity is often better in tube reactors than in stirred tanks (depends upon
kinetics)
If high heat transfer rates are required small diameter tubes are used to increase
the surface area to volume ratio. Several tubes may be arranged in parallel,
connected to a manifold or fitted into a tube sheet in a similar arrangement to a shell
27 and tube heat exchangers.

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Selectivity
Can have multiple reactions in which desired product, D,
is formed and undesired product, U, is also formed
A

Parallel reactions:

D
k
A U U

Series reactions:

A k D D k U U

kD

Want to minimize U and maximize D

Instantaneous selectivity:
SD/U
28

rD rate of formation of D

rU rate of formation of U

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Selectivity
Overall selectivity:

ND
Final moles of desired product

NU Final moles of undesired product

continuous

batch

Trade-off: reactor costs vs. separation costs

Total cost

Reactor cost

Cost

Reaction Selectivity
29

Separator cost

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Parallel Reaction Selectivity

Competing parallel reactions:

Product rate laws:

kD

kU

rD kDCA1
rU kU CA2

Reactant rate law:

rA rD rU

Instantaneous selectivity:

30

SD/U

rA kDCA1 kU CA2

rD kD 12
CA
rU kU

Want to maximize SD/U

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Selectivity: Effect of Relative Reaction Orders

Case 1: 1 > 2

Let a 1 2 SD/U

rD kD a
CA
rU kU

To maximize SD/U should keep CA as high as possible during reaction

Run gas-phase reactions w/o inerts at high P; run liquid-phase reactions with
minimal diluents

Use batch or PFR reactor, NOT CSTRin batch and PFR, CA starts high and
drops progressively; in CSTR, CA always at lowest value (i.e. outlet concentration)

Case 2: 2 > 1

Let b 2 1 SD/U

31

rD
kD
kD

rU kU CA 2 1 kU CAb

To maximize SD/U should keep CA as low as possible during reaction

CSTR preferred to keep CA at low value

Could use diluent and/or product recycle to dilute CA

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Selectivity: Effect of Temperature

Sensitivity of SD/U to temperature:

SD/U

ED EU
kD AD
~

exp

kU AU
RT

Case 3: ED > EU kD increases more rapidly

with increasing T than does kU maximize
SD/U by operating at highest possible T

Case 4: EU > ED kD increases less rapidly

with increasing T than does kU maximize
SD/U by operating at low T, but not so low that
reaction rate becomes extremely slow
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Non-Isothermal Reactor Design

Adiabatic reactor always considered first: simple, leastexpensive option
For highly exothermic or endothermic reactions, need
temperature control:
Excess reactant
Inert diluent
Cold/hot shots
External heating/cooling
Inter-stage cooling/heating

Want design to maximize rate and conversion, and be

safe!!
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Excess Reactant B
Product
A
Reactor

Separator

B
B
CW, cold stream
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Excess Inert Diluent S

Product

A
B

Reactor

Separator

S
S

35

CW, cold stream

Disadvantage: Introduce new component S to
separate from product and recycle

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Cold/Hot Shots
B (cold feed)

Reactor

Reactor

More A

36

Reactor

More A

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External Heating/Cooling
Feed

Coolant
Reactor

Cooler
External heat
exchanger,
jacket, or
internal coils
Product

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Intercoolers
B
A

38

Reactor

Reactor

Reactor

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Example: Exothermic, Reversible Reaction in PFR

Isothermal trajectory

39

Optimum temperature decreases as fractional conversion increases

Heat duty profile through PFR must be tailored to achieve optimal
trajectory

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Reactor Design Summary

Become familiar with Aspen Plus reactor models:
Stoichiometric (RSTOICH)
Equilibrium (REQUIL, RGIBBS)
Kinetic (RCSTR, RPLUG, RBATCH)
Black box (RYIELD)

Recall ideal kinetic reactor design equations (CSTR, PFR)

Know rules of thumb for selecting batch vs. flow reactors,
and tank vs. tube reactors
Design strategies for dealing with heat of reaction

40