Chapter II

Classification of chemical reactors. Material balances in ideal reactors.

[Link]
Reactors are devices that allow for a chemical reaction to take place, that is to say
to say the transformation of products with given characteristics into other products of
different characteristics and properties.

II.2. Classification of chemical reactors

The table below gathers the types of chemical reactors and their criteria.
classification.

Criteria Features

Circulation of Discontinued (or closed)
mixture Semi-continuous (or semi-closed)
reactive Continuous (or open)
Evolution in the Transitional regime (discontinuous operation or startup or
time stop
Permanent regime (continuous operation of open reactors)
Degree of mixing Perfectly stirred reactor (Perfect batch reactor
stirred tank reactor (RDPA), perfectly stirred continuous stationary reactor

(RCPA), of uniform concentrations and temperature)

Continuous tubular stationary piston flow reactor
(RCP) or piston reactor (RP) (load progression without
mixture)
Nature of phases Single-phase reactor: gas (G), liquid (L).
in the presence Biphase reactor: G+L, L1+L2, G+S (solid), L+S,…
Multiphase reactor: [G+L+S], [G+ L1+L2],
[S+L1+L2],…
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

II.3. Monophasic Reactors

We will deal here with homogeneous reactors: a single phase (liquid or gas).
We only consider here the intermittent or flow operating modes.
stationary.

II.3.1. Closed reactor (RF, batch reactor)

In a closed reactor, the reactants can be introduced all at once and the reaction can be carried out.

draining, also in one go, at the end of the reaction. The system remains closed during the
reaction; in this sense that there is no gain of material. This method is also known as
static method. It is the simplest equipment that one can envisage for achieving
a chemical transformation. It consists of a container in which the reactants are introduced
at the beginning of the operation; after conditioning of temperature and pressure, the
transformation takes place until the desired conversion rate is achieved. The closed reactors
batch processes are widely used in the chemical, petrochemical, or biochemical industry for the
production of products of various qualities. The processes involved are discontinuous and
versatile. They have a limited production volume and reaction systems
complex and sometimes unpredictable.
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

The essential elements make up this equipment which are:

A container capable of holding a volume of reaction mixture.
A usable surface for thermal exchange.
A stirring system to mix the reagents at the beginning of the operation and facilitate the
thermal transfer through the exchange surface.

II.3.2. Semi-closed reactor (RSF, semi-batch reactor)

A semi-closed reactor (semi-batch) is a device that allows for the realization of a
chemical transformation, in which a reactant is added or a product is extracted during the process
Operation. The semi-continuous reactor differs from batch operation only by the equipment.
annexes, it is frequently used in various industries (pharmacy, biotechnology,
Specialty chemistry, formulations, fine chemistry, agri-food, etc.). It is also
recommended in the case of a violent and dangerous reaction.
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
II.3.3. Perfectly Stirred Open Reactor (PSTR, Continuous Stirred Tank)
Reactor) :
The perfectly mixed continuous reactor is characterized by a composition and a state
instantaneous reaction mixture snapshots perfectly uniform throughout its entire volume
offer. The added reagents are mixed in an infinitely short time, we have the same
instantaneous composition at the output as well as inside the reaction mixture. This apparatus is
equipped with a continuous supply of reagent and a continuous withdrawal of the reaction mixture
containing the products of the reaction.

II.3.4. Piston Reactor (RP, Plug Flow Reactor)

Unlike the ROPA, the RP is a non-mixed reactor. The composition of the fluid
varies along the reactor. The mixture progresses through the device in slices that do not exchange
no matter between them. The piston reactor model is that of a tubular reactor, with
the interior through which the fluid flows as if pushed by a piston.
This reactor is characterized by the non-uniformity of the concentrations, which vary with the
longitudinal composition z along the flow. Since the composition of the fluid is
uniform on a section of the reactor, but varies axially between the inlet and the outlet of the reactor,
The material balance must be carried out on a differential volume element.
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
II.4. Material balance in ideal reactors
II.4.1. General formulation of the balance
The material balance equation is the basic tool for the chemical engineer to analyze.
the performance and behavior of the reactor.
The balances are expressions of the laws of conservation in chemical processes.
physical. In a chemical reaction, the total mass remains constant (except in reactions
nuclear!) "Lavoisier's Law." In Reactor Engineering, balances are generally written
at the macroscopic scale, on the compounds (reactants and products)
Writing in bulk or in moles is then equivalent.

-Writing in moles is the most practical, since the stoichiometry of the reaction can be considered.
directly taken into account.

Thus, through a balance equation, we can relate the composition of the reaction mixture to the flows.
of matter entering and exiting the reactor and the rates of chemical transformation.
For each component, the material balance equation (molar) is expressed by the formulation
following based on the principle of conservation of matter:
[Incoming flow into V] + [Production rate] = [Outgoing flow from V] + [Accumulation rate]

Assessment of a chemical constituent j

+ = + (II.1)

IFlux of the element at the reactor inlet [mole/s];

js Flow of the element at the reactor output [mole/s];
V: Volume of the reaction mixture in the reactor [m3] ;
Reaction rate of the reagent with respect to the volume V [mole/s.m3] ;
= ν r is the overall reaction rate,

Accumulation flow.
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
Example 1:
In the case of a simple reaction (irreversible with a single reactant) A→B:

1 [ ] 1 [ ] 1
=− = ( )=− → =−

rAis the rate of disappearance of reactant A.

The balance with respect to reagent A is therefore written as:

1
− = +

So:

− = +

Subsequently, in each balance equation, we try to make the term (-R [Link] order to
replace it directly byAin the case of a simple reaction.

II.4.2. The terms of the material balance

1. The terms of entry and exit represent the flows of material that enter and exit the
system with currents (convective flow) (kg.s-1, mol.s-1) :
A system is said to be open (continuous) when these terms are non-zero (at least for one
current

A system is said to be closed (discontinuous) when these terms are zero.

2. The term variation of mass represents the accumulation or depletion of matter in
the system with time (kg.s-1, mol.s-1In open systems under stationary regime, or
permanent, this term is equal to zero...

II.5. Characteristic equations of ideal reactors

II.5.1. Characteristic equation of the closed reactor (CR)
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
The reactor is perfectly mixed, generally in the liquid phase. The concentration is
uniform in the reactor.
Assessment of the Aj constituent on the entire reactor:
E + P = S + Acc
In this reactor, there is neither an inlet flow nor an outlet flow. The balance is reduced to:

[Production] = [Accumulation]

= (II.2)

With:
= in the case of a simple reaction
=∑ in the case of multiple reactions

Example 2:
Single reaction case
Let it be a simple reaction: A → products
The material balance on the key reagent A is written as:

= →− =
−
= (II.3)

By integration, we can calculate the residence time [Link] to obtain a final quantity

nOf:

=−∫ (II.4)
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
[Link] of stay as a function of the generalized advancement χ

= (II.2)

= + → =

−(− ) =

∫ =− ∫ (II.5)
(− )

If V is constant

∫ =− ∫
(− )
The length of stay:

=− ∫ (II.6)
(− )

If V is not constant, V = VT= V0β (1 + αχ)

∫ =− ∫
(− ) ( + )

The length of stay:

=− ∫ (II.7)
(− ) ( + )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
Exemple 3 :
For a simple reaction: A → products
ν =−1
If V is constant

∫ = ∫ → = ∫
(− ) (− )

If V is not constant, V = VT= V0β (1 + αχ)

∫ = ∫ → = ∫
(− ) ( + ) (− ) ( + )

II.5.1.2. Length of stay as a function of conversion rate xc

= (II.2)

= − → =−

So from (II.2)

−(− ) =−

∫ =∫
(− )

∫ =∫
(− )

∫ = ∫ (II.8)
(− )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

If V is constant

∫ = ∫ → = ∫ (II.9)
(− ) (− )

If V is not constant, V = VT= V0β (1 + αχ)

∫ = ∫
(− ) ( + )

Where from =−

1
∫ = C0∫ 1 C0
0 0 (− ) 0 (1 - A )
0

So

= ∫ (II.10)
(− ) ( − )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

Example 4:
A→B (simple reaction of first order) V=constant

∫ = ∫ → = ∫ (II.9)
(− ) (− )

So

∫ = ∫
(− )

On a :
1
= = (− )=− →− =

1 1
=− =− = = [ ]
-1
Where from
[ ][ =] (1
0 -x ) So = [ -]x0 )
(1

∫ = [ ] ∫
[ ]0(1-x )

So

= ∫
(1 - x )

= ∫ = (− ( − )) =− [( − −) ( ])
( 1-x )

=− ( - )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
II.5.2. Characteristic equation of the semi-closed reactor (RSF, semi-
batch reactor

In this reactor, there is no output flow.

E + P = S + Acc
The summary amounts to:

[Input] + [Production] = [Accumulation]

+ = (II.11)

On a :

=− C0

= −
0 0

So:

− + =− (II.12)

Example 5:
For a simple reaction: A → products

0− 0 + Rj V = − 0

0− 0 − (-Rj )V = − 0

So

0(1 - x ) − (-R j )V =− 0
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
II.5.3. Characteristic equation of the perfectly stirred open reactor
(RPA, Continuous Stirred Tank Reactor)

Before addressing the material balance in open reactors operating in regime

permanent, it is important to define the operational parameters for measuring the
processing capacity of these reactors.

Passage time τ
In these reactors, the volume of the reactor (V) is traversed by a volumetric flow rate Q.0(m3.s-1).
The passage time of the reactor "τ" is defined by:

= ( . )
Similarly to the ts, in the case of the batch reactor, τ represents a measure of
performances of a flow reactor.

The balance includes terms of entry and exit, but no accumulation, because we are working in
permanent regime.
E + P = S + Acc
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
The assessment is reduced to:

[Input] + [Production] = [Output]

The material balance on constituent A throughout the reactor is written as:

+ = (II.14)

− =

On a

= −

= −

So

− =− = −(− )

C0= C0 C0

So we can write
νj
νj νC 0 xCs
0 C0xCs = (− ) → =
νC (− ) 0

So
νj
νC 0 xCs
= (II.15)
(− )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
Example 6:
For a simple reaction: A → 2B
νj
x
νC C0 Cs
=
(− )

(− )= = [ ]

0(1 - x )
[ ] = =
0 (1 + phi)

A → 2B products therefore =
So
0(1 - x )
[ ] =
0 (1 + fix )

T and P are constants, so β=1 and α=1.

0(1 - x )
[ ] =
0 (1 + x )

Passing time
νj νA
x [ ] x
νC C0 Cs νA 0 A
= → =
(− ) 0 (1 -x )
0 (1 + x )

0[ ]0xA (1 + x )
=
0 (1-x )

0 xA (1 + x )
=
0 (1−x )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

II.5.3.1. Passage time as a function of conversion rate xc

Unique reaction case
Let the reaction be: A → products
The flow of material of component A as a function of xAis written:
At the entrance of the reactor∶ = ( − )
At the reactor outlet∶ = ( − )
By replacing the expressions of FAeand FAsin the material balance equation on the constituent
A, Vet writes to you:
( − )
= (II.16)

( − )
= (II.17)

II.5.3.2. Passage time as a function of CA

Unique reaction case
Let the reaction be: A → products
In steady state, the material balance for component A throughout the reactor is written as:
− =
− =
In the presence of inert constituents: =
-If the mass volume ρ ≠ Constant⇒ QAe≠ QAsnot equal Q0(case of a gaseous phase)
Where from:

−
= (II.18)
If ρ = Constant⇒ QAe= QAsQ0(case of a liquid phase)
( − )
= (II.19)
From where:

( − )
= (II.20)
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
II.5.3.3. Passage time as a function of the generalized advance χ
Unique reaction case
Let the reaction be: A → products
The material flow of constituent A as a function of χ is expressed as:

At the entrance of the reactor∶ = +

At the reactor outlet∶ = +
The total molar flow of active constituents in the reference state:F0Fj0 ∑j
By replacing the expressions of FAeand FAsand rAby in the material balance equation
on the constituent A, we obtain:
+ + = +
The expression of VRit is written then:

( − )
= (II.21)

and that of τ:
( − )
= (II.22)

Such as :

= and =

II.5.4. Equation caractéristique du Réacteur Piston (RP)

This reactor operates at a steady state, so there is no accumulation.

E + P = S + Acc
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
The balance is reduced to:

[Input] + [Production] = [Output]

The axial coordinate z is used:

|+ = | + (II.23)

|+ = |+

= S is the surface of a section

=
ν
SheFj= Fj0- FC0 xCj
νC

νj
−(− ) =−
νC0
C
νj
−(− ) = − C0
νC
νj
(− ) =
νCC0
νj 1
∫ =∫
0 C0νC 0 (− )

νj 1
=∫
C0νC 0 (− )

νj 1
=∫
0 C0νC 0 (− )

νj 1
=ν C0 ∫0 (II.24)
C (− )
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.

Example 7 :
For a simple reaction: A → 2B (T and P constant) (β=1, α=1)

(− )= = [ ]

0 (1− )
[ ] = =
0 (1+ )

0(1 - x )
[ ] =
0 (1 + fax )

T and P constants therefore

0(1 - x )
[ ] =
0 (1 + x )

Passing time

νA 1
= [ ] 0∫
νA 0 [ ]

νA 0 1
= ∫
νA 0 0 0 (1
-x )
0 (1 + x )

(1 + x )
=∫
0 (1 − x )
Reactor volume
On a

νj 1
=∫
C0νC 0 (− )
So regarding the key reagent
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
νA 1
=∫
0 νA 0 (− )

νA 1
=∫ 0
νA 0 (− )

1
=∫ 0
0 [ ]

1
=∫ 0
0 0 (1 -x )
0 (1 + x )

0 (1 +x )
=∫
0 (1 - x )

II.5.4.1. Passage time as a function of the conversion rate xC

Unique reaction case
Let the reaction be: A → products
+ = +

By replacing FA= FA0(1̶xA) in the balance equation we obtain:

= ∫ II.25
(− )

Let:

== ∫ (II.26)
(− )

II.5.4.2. Transition time as a function of CA

Single reaction case
Let the reaction be: A → products
Chapter II
Classification of chemical reactors. Material balances in ideal reactors.
+ = +
By replacing FAby QCAThe balance equation is written as:

=( )

=∫ (II.27)
( )

= = ∫ (II.28)
( )

Same expression as in closed reactor

Note: In the case of a uniform flow Q = Q0
II.5.4.3. Passage time as a function of the generalized advancement χ
Single reaction case
Let the reaction be: A → products
+ = +

From the expression of the flux FA depending on χ:

= +
The balance equation is written as:

=∫ = ∫ (II.29)
Where from:

== ∫ (II.30)

With: