Reacting System Design

Objective: Sequence the steps necessary to develop reacting

system design at different levels of detail.
Outline
Synthesize Chemistry
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 = 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

conversion (overall or per pass), selectivity, and yield

Determine Kinetics and Thermodynamic Feasibility of Reaction

Thermodynamics for Equilibrium
Kinetics (literature)
http://kinetics.nist.gov/kinetics/welcome.jsp
Pilot/Bench Scale Reaction
Determine Transport Properties
Determine the rate determining step
Kinetic, mass transfer, heat transfer limited
Choose the reactor type
Determine Operating Conditions
Size
Internals
Determine Material of Construction
Optimize
Instrument and Control
 Levels of Detail

Skeleton
Reaction Chemistry, Yield based Conversion, Equilibrium
Conversion
Can select some of the operating conditions, Phases
involved (homogenous vs. heterogeneous), temperature,
pressure, limiting reactant, mode of operation (adiabatic
vs. isothermal)
Short-Cut
Reaction Rate
Sizing
Optimization
Rigorous/Detailed
Non-ideal reactor behavior
CFD
Internals
Instrumentation and Control
Optimization
Review of Basic Types of Reactors
Configurations that Result in Plug Flow Reactor
Configurations that Result in Stirred Tank Reactor
 Heat Transfer Considerations
Indirect mode
Direct Mode
 Reaction Equilibrium

Preliminaries:
∆𝐺𝐺 𝑜𝑜 = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝐾𝐾
Related to reaction stoichiometry, ∆𝐻𝐻 𝑜𝑜 , Cp,i
Single reaction
𝐾𝐾 𝑘𝑘𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 + ⋯ ⇔𝑘𝑘𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑟𝑟𝑟𝑟 + 𝑠𝑠𝑠𝑠 + ⋯

𝑘𝑘𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝐾𝐾𝑖𝑖 =
𝑘𝑘𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟

Start with general representation

𝑥𝑥𝑅𝑅𝑟𝑟 ∙ 𝑥𝑥𝑆𝑆𝑠𝑠 … ∅ � 𝑆𝑆𝑠𝑠 …

� 𝑟𝑟𝑅𝑅 ∙ ∅
∑ 𝛼𝛼𝑖𝑖
𝐾𝐾 = 𝑎𝑎 ∙ 𝑃𝑃
𝑥𝑥𝐴𝐴 ∙ 𝑥𝑥𝐵𝐵𝑏𝑏 … �𝐴𝐴𝑎𝑎 ∙ ∅
∅ � 𝑏𝑏𝐵𝐵 …

𝑥𝑥𝑖𝑖 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑜𝑜𝑜𝑜 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑖𝑖

 � 𝑖𝑖 = 𝑓𝑓̂𝑖𝑖
𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ∅ fugacity
𝑃𝑃

� 𝛼𝛼𝑖𝑖 ← 𝑠𝑠𝑠𝑠𝑠𝑠 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠ℎ𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑒𝑒𝑛𝑛𝑛𝑛𝑛𝑛

𝑃𝑃 = 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

𝑛𝑛𝑖𝑖
𝑙𝑙𝑙𝑙𝑙𝑙 𝑥𝑥𝑖𝑖 =
𝑛𝑛𝐴𝐴 + 𝑛𝑛𝐵𝐵𝐵𝐵 + ⋯ + 𝑛𝑛𝑅𝑅 + 𝑛𝑛𝑆𝑆 + ⋯ + 𝑛𝑛𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖

𝑛𝑛𝑅𝑅𝑟𝑟 ∙ 𝑛𝑛𝑆𝑆𝑠𝑠 … 𝑃𝑃 ∑ 𝛼𝛼𝑖𝑖

𝐾𝐾 = 𝑎𝑎 𝑏𝑏 ∙ 𝐾𝐾∅�𝑖𝑖 ∙ � �
𝑛𝑛𝐴𝐴 ∙ 𝑛𝑛𝐵𝐵 … ∑ 𝑛𝑛 𝑖𝑖

Rearrange to represent conversion as dependent

variable:
 ∑ 𝛼𝛼𝑖𝑖
𝑛𝑛𝑅𝑅𝑟𝑟 ∙ 𝑛𝑛𝑆𝑆𝑠𝑠 … 𝐾𝐾 ∑ 𝑛𝑛𝑖𝑖
= ∙ � �
𝑛𝑛𝐴𝐴𝑎𝑎 ∙ 𝑛𝑛𝐵𝐵𝑏𝑏 … 𝐾𝐾∅�𝑖𝑖 𝑃𝑃

T effect:
Exothermic
𝑎𝑎𝑎𝑎 𝑇𝑇 ↑ 𝐾𝐾 ↓ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ↓

Endothermic
𝑎𝑎𝑎𝑎 𝑇𝑇 ↑ 𝐾𝐾 ↑ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ↑
P effect:
Explicit

� 𝛼𝛼𝑖𝑖 < 0 𝑃𝑃 ↑ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ↑

� 𝛼𝛼𝑖𝑖 < 0 𝑃𝑃 ↑ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 ↓

Inert effect:

Opposite of P

Multiple Reactions:
• Write each reaction separately
𝑁𝑁𝑁𝑁
𝜈𝜈
𝐾𝐾𝑗𝑗 = � 𝑎𝑎𝑖𝑖 𝑖𝑖,𝑗𝑗 𝑓𝑓𝑓𝑓𝑓𝑓 𝑗𝑗 = 1, 2, … , 𝑁𝑁
𝑖𝑖=1

o Can be simplified for gases, ideal solutions, ideal

gases
• The reactions are coupled through compositions that
are a function of extent of reaction for each reaction
(ξj)
• Multiple reactions are best solved using Gibbs free
energy minimization techniques.
What about Irreversible Reactions
 More General Reactor Selection scheme

State
Homogenous (G or L or S)
Gas Usually Plug Flow

Liquid Usually CSTR unless pressure is high

Heterogeneous (with or without Catalyst)

Gas-Solid Usually Fixed Bed for PFR

(Transport/Slurry Reactor, Hearth, Spray
reactor)
Fluidized Bed for CSTR
Gas-Liquid Bubble or Spray Column (thin film, tray)
CSTR
Liquid-Liquid Bubble Column (thin film, tray)
CSTR
Liquid-Solid Fixed Bed or Slurry reactor
CSTR
Gas-Liquid-Solid Trickle Bed
Pressure

Low State always dictates the reactor

Choice

High Plug Flow due to sealing problems

 Temperature

Low Previous Factors dictate

Medium Use Heating Medium
High (773K) Use Furnace or Kiln

Type of Mixing

PFR Heat Removal more difficult

Prefer Endothermic rxns
RTD narrow prefer for
polymerization

CSTR Heat Removal Easier

Better for exothermic rxns
Broad RTD
Concentration low and
Uniform
 Temperature Control

Adiabatic Easy to build

Preferable for Endothermic rxns
May need to use inter-bed heat
Exchange or incremental feed of
one component or heat sinks

Isothermal More difficult to build & operate

Use for exothermic

Catalyst

Robust Fixed Bed OK

 Fixed Conversion Reactor

For each reaction r, define

l(r) which is the limiting
reactant and normalized
stoichiometric coefficient

r= 1,…, NR, where NR is the number reactions,

Is the fraction converted per pass in

terms of reactants, r= 1,…, NR
 Fixed Conversion Reactor
Example

While remaining one are