Unit 3 Reactor Models based on the Reaction Kinetics

Mapping Reactor Performance

Decisive Factors
• Flow pattern and mixing of the reacting
phases
• Rates of the chemical reactions
fast:
→ Performance determined by local
equilibria or transport processes
slow:
→ Performance controlled by chemical
reactions

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 Unit 3 General Basis of Reactor Modelling

Conservation Equations
• Material Balance (total mass, atoms)
• Energy Balance (Enthalpy)
• Momentum Balance

accumulation  input through  output through  generation  consumption 

 within the  =  system − system  +  within the  −  within the 
 system   boundaries   boundaries   system   system 

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Unit 3 General Basis of Reactor Modelling

Input/output through system boundary Real Situation

occurs via:
• Convective flow
• Dispersive flux
- diffusion
- turbulence (fluctuations of the flow velocity)
• Transport to or from another phase

Pseudohomogeneous Model
Momentum Balance:
often reduced to empirical pressure loss formula:
dP ρ
= −f (ε, Re) ⋅ ⋅ u 2
dz 2

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Unit 3 Basic Equations

Material Balance:

∂ci m
= − div(uc i ) + div(Di grad c i ) + βa∆ci + ∑ν ij rj
e

∂t j =1

Energy (Enthalpy) Balance:

∂ (ρcp T) m
= − div(ρcp Tu) + div(λ grad T) + ha∆T + ∑ rj (−∆H R ) j
e
∂t j=1

Region over which the balance is invoked:

• Differential Control Volume (if gradients exist in the reactor)
→ Differential Equations (ODE, PDE)
• Reactor Volume (if gradients are absent)
→ Algebraic equations (AE)

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Unit 3 Reactor Models based on the Reaction Kinetics

Reactor Models Available in Aspen Plus

Material and Equilibrium Kinetics

Energy Balance

RSTOIC REQUIL RCSTR

RYIELD RGIBBS RPLUG
RBATCH

• RSTOIC, RYIELD, RGIBBS and RCSTR may have any number of feed streams.
• REQUIL is limited to 2-Phase calculations and needs the reaction stoichiometry.
• RGIBBS performs multiphase equilibria and is non-stoichiometric.
• Heats of reaction are not required. Aspen Plus calculates heats of reaction using heats
of formation
• Kinetics: built-in power law model
built-in generalised Langmuir-Hinshelwood-Watson model
user-written Fortran subroutine
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Unit 3 Ideal Reactors

Continuous Stirred Tank Reactor (CSTR)

Batch Reactor

Continuous Tube Reactor (Pflug Flow Reactor, PFR)

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Unit 3 Continuous Stirred Tank Reactor

Industrial Relevance
• Liquid Phase Reactions

Pro‘s:
Simplifying Assumptions
• High capacity and constant product
• Ideally mixed quality
• Stationary
Con‘s:
• Low reaction rate
cA0 cA0 • Broad residence time distribution
• More complex system (compared to
cA cA batch)
t x

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Unit 3 Continuous Stirred Tank Reactor

Material Balance (Single Phase, Reactant i)

0 = n
i0 − n
i − R i VR

Enthalpy Balance (Single Phase)

0 = q 0ρ0cp0T0 − qρcp T + ha(TW − T) + VR ∑ (−∆H R )rj

j

Example: single phase, single reaction, isothermal

V V c c X
τ = R = R A0 = A0 A rA
Reaktions-
q0 n
A0 rA geschwindigkeit
CSTR-
Stoffbilanz
for constant VR:
Steigung
V c −c
τ = R = A0 A = -1/ττ
q0 rA

CA5CA4CA3 CA2 CA1 CA0 8

Unit 3 Continuous Stirred Tank Reactor

Residence Time Behaviour:

Inlet Exit

Tracer
marking

Switch
marking

t=0 t=0

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Unit 3 Continuous Tube Reactor (PFR)

Industrial Relevance
• Mainly for gas phase reactions

Simplifying Assumptions Pro‘s:

• 1-dimensional, i.e. only axial flow • Very simple (no moving parts)
(independent of r and ϕ)
• Narrow residence time distribution
• No backmixing (plug flow)
• Stationary
Con‘s:
• Difficult to operate at high viscosity
cA0 x=0 cA0 (liquids) and low flow velocity
• Limited heat transfer
x=l
cA cA
t x

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Unit 3 Continuous Tube Reactor (PFR)

Material Balance (Single Phase, Reactant i)

0 = n
i − (n
i + dn
i ) − R i dVR

Enthalpy Balance (Single Phase)

d(qρc pR T) dA
0=− + h(TW − T) + VR ∑ (−∆H R ) j rj
dV dV j

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Unit 3 Continuous Tube Reactor (PFR)

Residence Time Behaviour:

Inlet Exit

Tracer
marking

Step
marking

t=0 t=τ

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