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Advanced Chemical Reaction Engineering
Lecturer : 郭修伯
Lecture 1
Syllabus
• Fundamentals of CRE– Ideal reactor types and
design equations
• Interpretation of rate data
• Non-elementary homogeneous reactions
• Non-isothermal reactors• Multiple reactions
• Non-ideal reactors• Catalysis and catalytic
reactors• External diffusion effects
on heterogeneous reactions• Diffusion and reaction in
porous catalysts• Residence time
distributions
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.
What is Chemical Reaction Engineering (CRE) ?
Chemical process
Rawmaterial
SeparationProcess
SeparationProcess
Products
By products
J. Wood at Bham Univ.
Text book and Recommended Books
• Elements of Reaction Engineering, 2nd Edition.H.Scott Fogler, Prentice Hall.
• Chemical Reaction Engineering, 2nd or 3rd Edition. Octave Levenspiel, John Wiley and Sons.
• Reactor Design for Chemical Engineers. J.M. Winterbottom and M.B. King
Fundamentals
• Ideal Reactors :– Perfectly mixed batch reactor (Batch)– Continuous stirred tank reactor (CSTR) or Backmix reactor– Plug flow reactor (PFR)– Packed bed reactor (PBR)
• Chemical kinetics– All reactions are presented as being homogeneous reactions.
• Multiple reactors• Isothermal ideal Batch, CSTR, and PFR
• It has neither inflow nor outflow of reactants or products which the reaction is being carried out.
• Perfectly mixed
• No variation in the rate of reaction throughout the reactor volume
BATCH
Ideal Reactor Types
Batch Reactor
• All reactants are supplied to the reactor at the outset. The reactor is sealed and the reaction is performed. No addition of reactants or removal of products during the reaction.
• Vessel is kept perfectly mixed. This means that there will be uniform concentrations. Composition changes with time.
• The temperature will also be uniform throughout the reactor - however, it may change with time.
• Generally used for small scale processes, e.g. Fine chemical and pharmaceutical manufacturing.
• Low capital cost. But high labour costs.
• Multipurpose, therefore allowing variable product specification.
NaOH CH3COOC2H5
Sodium hydroxide + ethyl acetate = sodium acetate + ethanol
C2H5OHCH3COONa
andUnreacted NaOH
CH3COOC2H5
Example of a liquid phase batch reaction.
Typical Laboratory Glass Batch Reactor
Typical Laboratory High Pressure Batch Reactor
(Autoclave)
Typical Commercial Batch Reactor
• Normally run at steady state.
• Quite well mixed
• Generally modelled as having no spatial variations in cencentration, temperature, or reaction rate throughout the vessel
CONTINUOUS STIRRED TANK REACTOR (CSTR) BACKMIX REACTOR
Ideal Reactor Types
•Usually employed for liquid phase reactions.
•Use for gas phase usually in laboratory for kinetic studies.
Schematic representation of a CSTR
Assumption: Perfect mixing occurs.
FA0
(CA0)
FA
(CA)CA
CA
CA
Vr, lVr, g
Backmixed, Well mixed or CSTR
?
Characteristics
• Perfect mixing: the properties of the reaction mixture are uniform in all parts of the vessel and identical to the properties of the reaction mixture in the exit stream (i.e. CA, outlet = CA, tank)
• The inlet stream instantaneously mixes with the bulk of the reactor volume.
• A CSTR reactor is assumed to reach steady state. Therefore reaction rate is the same at every point, and time independent.
• What reactor volume, Vr , do we take?
– Vr refers to the volume of reactor contents.
– Gas phase: Vr = reactor volume = volume contents
– Liquid phase: Vr = volume contents
Cutaway view of a Pfaudler CSTR/ Batch Reactor
PLUG FLOW REACTOR (PFR), TUBULAR REACTOR
Ideal Reactor Types
• Normally operated at steady state
• No radial variation in concentration
• Referred to as a plug-flow reactor
• The reactants are continuously consumed as they flow down the length of the reactor.
• There is a steady movement of materials along the length of the reactor. No attempt to induce mixing of fluid element, hence at steady state:– At a given position, for any cross-section there is no pressure,
temperature or composition change in the radial direction.
– No diffusion from one fluid element to another.
– All fluid element have same residence time.
Used for either gas phase or liquid phase reactions.
PFR, Tubular reactor
The plug flow assumptions tend to hold when there is good radial mixing (achieved at high flow rates Re >104) and when axial mixing may be neglected (when the length divided by the diameter of the reactor > 50 (approx.))
N.B.In the case of a gas phase reaction, the pressure history of the reaction must be noted in case the number of moles change during the reaction.
e.g. A B + C
As the reaction progresses the number of moles increases. Therefore at constant pressure, fluid velocity must increase as conversion increases.
Rate law for rj
• rA = the rate of formation of species A per unit volume [e.g., mol/dm3-s]
• -rA = the rate of a disappearance of species A per unit volume
• 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
Design equations for the ideal reactors:
based on material balance
Conversion
• Conversion is defined to answer the questions:– How can we quantify how far a reaction has progressed?
– How many moles of product C are formed for every mole reactant A consumed?
• The conversion XA is the number of moles of A that have reacted per mole of A fed to the system:
fedAofmoles
reactedAofmolesX A
(1) (2) (3) (4)
Rate of accumulation of reactant = Rate of reactant flow – Rate of reactant flow – Rate of reactant LOSS due toin element of volume INTO OUT OF Chemical Reaction element of volume element of volume within the element of volume
Reactants leaveReactants enter
Reactant accumulateswithin the element
Reactant disappears due to reaction within the element
Material Balance for Any Simple Ideal Reactor - Isothermal
Element of reactor volume
Rate of accumulation ofreactant A in reactor
Rate of reactant A loss by reaction in reactor= -
(1) (4)
Mole Balance - Batch Reactor
• No material enters or leaves the reactor.• If composition in uniform (i.e. perfect mixing) -
material balance can be written over whole reactor.• No flow in or out of reactor. Terms (2) and (3) = 0.
dtAdN
Where NA = moles of A in system
NA = NA0 (1-XA)
Where NA0 is the initial moles
XA = fractional conversion of A = (NA0-NA)/NA0
NA = moles of A at conversion XAdNA = -NA0 dXA
dt
dXN
dt
dN AA
A 0
Rate of accumulation of A, [moles/time]
Rate of disappearance of A, [moles/time]
Rate of disappearance = (-rA) Vrwhere (-rA) = moles A reacting / (unit volume) (time) Vr = Reactor volume, but really refers to the volume of fluid in reactor.
rAA
A VrdX
N )(dt
0 rAA
A VrdX
N )(dt
0
If system is constant volume, then 00
Ar
A CV
N Where CA0 is the initial concentration of A (mol/m3)
Integrating the equation gives the design equation for the batch reactor
CSTR (at steady state) - NO ACCUMULATION.
Accumulation = Input - Output - Disappearance by reaction0 = FA in - FA out - (-rA)Vr
FA = FA0 (1-XA)FA0 = FA + (-rA)Vr
FA0 XA = (-rA) Vr
Mole Balance - CSTR
dVr
CA0
FA0
XA0= 0
FA
XA
FA+dFA
XA+dXA
CAf
FAf
XAf
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 dVr .
INPUTInput of A, moles/time = FA
Conversion of A = XA
OUTPUTOutput of A, moles/time = FA + dFA
Conversion of A = XA + dXA
Disappearance of A by reaction, moles/time = (-rA) dVr
Mole Balance - PFR
PFR (at steady state) - NO ACCUMULATION.
Accumulation = Input - Output - Disappearance by reaction0 = FA - (FA+dFA) - (-rA)dVr
- dFA = (-rA)dVr
dFA = -FA0 (dXA)
)(0 A
A
A
r
r
dX
F
dV
The heart of the design of an ideal reactor:
(-rA) as a function of conversion (concentration, partial pressure etc.)
We will discuss this issue in the next course.
Factors Involved in Reactor Design
• Feedstock composition – Single feedstock– Reactant in a solvent– Multi-component feedstock
• Scale of process– output of product
• Process kinetics– Effect of composition
(concentration)– Effect of temperature– Catalyst– Thermodynamics
• Reactor type– Batch / continuous
– Semi batch / Semi continuous
– Isothermal, non-isothermal, adiabatic
– Single pass / recycle
– Multiple reactors
• Others– Materials of construction
– instrumentation
– safety
Example Reactor Types
• Noncatalytic homogeneous gas reactor
• Homogeneous liquid reactor
• Liquid-liquid reactor
• Gas-liquid reactor
• Non-catalytic gas-solid reactor
– Fixed bed
– Fluidised bed
• Fixed bed catalytic reactor
• Fluid bed catalytic reactor
• Gas-liquid-solid reactor
• Ethylene polymerisation
(high pressure)
• Mass polymerisation of styrene
• Saponification of fats
• Nitric acid production
• Iron production
• Chlorination of metals
• Ammonia synthesis
• Catalytic cracking (petroleum)
• Hydrodesulphurisation of oils
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 volumn (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
• Fluidised bed reactor (circulating fluidised bed CFB)
Mole balances on 4 common reactors
Reactor Mole Balance Comment
Batch Vrdt
dNj
j No spatial variation
CSTRj
jj
r
FFV
0 No spatial variation,steady state
PFRj
j rdV
dF Steady state
PBR jj r
dW
dF Steady state