Chemical reaction engineering is the branch of chemical engineering which deals with chemical reactors and their design, especially by application of chemical kinetics to industrial systems.
Overview
There are a couple of main basic
vessel types:
- A tank
- A pipe or tubular reactor (laminar flow reactor(LFR))
Both types can be used as continuous
reactors or batch reactors, and either may accommodate one or more solids (reagents, catalyst, or inert
materials), but the reagents and products are typically fluids. Most commonly,
reactors are run at steady-state, but can also be operated in a transient
state. When a reactor is first brought
into operation (after maintenance or inoperation) it would be considered to be
in a transient state, where key process variables change with time.
There are three main basic models
used to estimate the most important process variables of different chemical
reactors:
- batch reactor model (batch),
- continuous stirred-tank reactor model (CSTR), and
- plug flow reactor model (PFR).
Furthermore, catalytic reactors
require separate treatment, whether they are batch, CST, or PF reactors, as the
many assumptions of the simpler models are not valid.
Key process variables include
- Residence time (τ, lower case Greek tau)
- Volume (V)
- Temperature (T)
- Pressure (P)
- Concentrations of chemical species (C1, C2, C3, ... Cn)
- Heat transfer coefficients (h, U)
A chemical reactor, typically
tubular reactor, could be a packed bed.
The packing inside the bed may have catalyst to
catalyze the chemical reaction. A chemical reactor may also be a fluidized bed;
see Fluidized bed reactor.
Chemical reactions occurring in a
reactor may be exothermic, meaning giving off heat, or endothermic,
meaning absorbing heat. A chemical reactor vessel may have a cooling or heating
jacket or cooling or heating coils (tubes) wrapped around the outside of its
vessel wall to cool down or heat up the contents.
Types
CSTR
(Continuous Stirred-Tank Reactor)
In a CSTR, one or more fluid
reagents are introduced into a tank reactor (typically) equipped with an impeller while the
reactor effluent is removed. The impeller stirs the reagents to ensure proper mixing. Simply dividing the volume of the tank by the average volumetric flow rate through the tank gives the residence time, or the
average amount of time a discrete quantity of reagent spends inside the tank.
Using chemical kinetics, the reaction's expected percent
completion can be calculated. Some important aspects of the CSTR:
- At steady-state, the mass flow rate in must equal the mass flow rate out, otherwise the tank will overflow or go empty (transient state). While the reactor is in a transient state the model equation must be derived from the differential mass and energy balances.
- The reaction proceeds at the reaction rate associated with the final (output) concentration, since the concentration is assumed to be homogenous throughout the reactor.
- Often, it is economically beneficial to operate several CSTRs in series. This allows, for example, the first CSTR to operate at a higher reagent concentration and therefore a higher reaction rate. In these cases, the sizes of the reactors may be varied in order to minimize the total capital investment required to implement the process.
- It can be demonstrated that an infinite number of infinitely small CSTRs operating in series would be equivalent to a PFR.
The behavior of a CSTR is often
approximated or modeled by that of a Continuous Ideally Stirred-Tank Reactor
(CISTR). All calculations performed with CISTRs assume perfect mixing.
If the residence time is 5-10 times the mixing time, this approximation is
considered valid for engineering purposes. The CISTR model is often used to
simplify engineering calculations and can be used to describe research
reactors. In practice it can only be approached, particularly in industrial
size reactors in which the mixing time may be very large.
PFR
(Plug Flow Reactor)
In a PFR, one or more fluid reagents
are pumped through a
pipe or tube. The chemical reaction proceeds as the reagents travel through the
PFR. In this type of reactor, the changing reaction rate creates a gradient with
respect to distance traversed; at the inlet to the PFR the rate is very high,
but as the concentrations of the reagents decrease and the concentration of the
product(s) increases the reaction rate slows. Some important aspects of the
PFR:
- All calculations performed with PFRs assume no upstream or downstream mixing, as implied by the term "plug flow".
- Reagents may be introduced into the PFR at locations in the reactor other than the inlet. In this way, a higher efficiency may be obtained, or the size and cost of the PFR may be reduced.
- A PFR typically has a higher efficiency than a CSTR of the same volume. That is, given the same space-time (or residence time), a reaction will typically proceed to a higher percentage completion in a PFR than in a CSTR. This is not always true for reversible reactions.
For most chemical reactions of
industrial interest, it is impossible for the reaction to proceed to 100%
completion. The rate of reaction decreases as the reactants are consumed until
the point where the system reaches dynamic equilibrium (no net reaction, or
change in chemical species occurs). The equilibrium point for most systems is
less than 100% complete. For this reason a separation process, such as distillation,
often follows a chemical reactor in order to separate any remaining reagents or
byproducts from the desired product. These reagents may sometimes be reused at
the beginning of the process, such as in the Haber process.
In some cases, very large reactors would be necessary to approach equilibrium,
and chemical engineers may choose to separate the partially reacted mixture and
recycle the leftover reactants.
Continuous oscillatory baffled reactor (COBR) is a tubular plug flow reactor. The mixing in COBR
is achieved by the combination of fluid oscillation
and orifice baffles, allowing plug flow to be achieved under laminar flow
conditions with the net flow Reynolds number
just about 100.
Semi-batch
reactor
A semi-batch reactor is operated
with both continuous and batch inputs and outputs. A fermenter, for example, is
loaded with a batch of medium and microbes which constantly produce carbon
dioxide that must removed continuously. Analogously, driving a reaction of gas
with a liquid is usually difficult, since the gas bubbles off. Therefore, a
continuous feed of gas is injected into the batch of a liquid. One chemical
reactant is charged to the vessel and a second chemical is added slowly (for
instance, to prevent side reactions).
Catalytic
reactor
Although catalytic
reactors are often implemented as plug flow reactors, their analysis requires
more complicated treatment. The rate of a catalytic reaction is proportional to
the amount of catalyst the reagents contact, as well as the concentration of
the reactants. With a solid phase catalyst and fluid phase reagents, this is
proportional to the exposed area, efficiency of diffusion of reagents in and
products out, and efficacy of mixing. Perfect mixing usually cannot be assumed.
Furthermore, a catalytic reaction pathway often occurs in multiple steps with
intermediates that are chemically bound to the catalyst; and as the chemical
binding to the catalyst is also a chemical reaction, it may affect the
kinetics. Catalytic reactions often display the so-called falsified kinetics,
i.e. the apparent kinetics differ from elementary chemical kinetics due to
physical transport effects.
The behavior of the catalyst is also
a consideration. Particularly in high-temperature petrochemical processes,
catalysts are deactivated by sintering,
coking, and
similar processes.
A common example of a catalytic
reactor is the catalytic converter following an engine. However, most petrochemical reactors
are catalytic, and are responsible for most of industrial chemical production
in the world, with extremely high-volume examples such as sulfuric acid,
ammonia,
reformate/BTEX (benzene,
toluene, ethylbenzene and xylene) and alkylate gasoline
blending stock.
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