Refining-Petrochemicals-Chemicals-Engineering

CHEMICAL REACTIONS OF CATALYTIC REFORMING

I - INTRODUCTION.............................................................................................................................1
II - TYPES OF CHEMICAL REACTIONS............................................................................................1
1 - Complete chemical reactions ............................................................................................................1
2 - Incomplete or balanced chemical reactions .....................................................................................2

III - DETAILED STUDY OF A BALANCED CHEMICAL REACTION..................................................7

1 - Reaction characteristics..................................................................................................................... 7
2 - Influence of the operating conditions on the state of equilibrium ....................................................9

IV - KINETIC ASPECT OF CHEMICAL CONVERSIONS..................................................................12

1
2
3
4
5

Definition of rates of reaction...........................................................................................................12

Factors influencing the rates of reaction.........................................................................................13
Balanced chemical reactions...........................................................................................................18
Formal kinetics - Expressions of rates of reaction .........................................................................20
Addition of a substance not taking an apparent part in the reaction.............................................24

V - MAIN CATALYTIC REFORMING REACTIONS..........................................................................25

1
2
3
4
5
6
7
8
9
10

Dehydrogenation of naphthenes .....................................................................................................25

Dehydrogenation of paraffins ..........................................................................................................27
Isomerization of naphthenes ...........................................................................................................29
Isomerization of paraffins.................................................................................................................30
Hydrocracking...................................................................................................................................30
Hydrogenolysis.................................................................................................................................31
Hydrodealkylation.............................................................................................................................32
Alkylation ..........................................................................................................................................32
Disproportionation ............................................................................................................................33
Coking...............................................................................................................................................33

VI - CATALYTIC REFORMING OPERATING VARIABLES ..............................................................33

1
2
3
4

Influence of operating conditions on the main catalytic reforming reactions................................ 33

Overall influence of operating variables..........................................................................................35
Evolution of reactions in catalytic reforming reactors ....................................................................39
Operating variables - Unit performance..........................................................................................39

SUMMARY...............................................................................................................................................41
RA REF - 00085_A_A - Rev. 3

23/02/2009

2009 - IFP Training

I-

INTRODUCTION
The influence of different factors such as temperature, pressure, electric tension, etc. can cause matter to
undergo transformations that modify to a varying extent the chemical species of which it is composed. During
these transformations, a rupture of the bonds between some atoms and the formation of new molecules are
observed. These transformations are called chemical reactions.
Lavoisiers studies (1743-1794) led him to conclude that a chemical reaction involves mass conservation i.e.
the mass of consumed reactants is equal to the mass of products produced.
In catalytic reforming most of the reactions are limited by a state of equilibrium. The conversion ratios
observed are often very different from those of equilibrium conversion, which shows that these reactions do
not always have time to reach their equilibrium, and consequently the rate of conversion has to be taken into
account.

II -

TYPES OF CHEMICAL REACTION

1-

COMPLETE CHEMICAL REACTIONS

Some chemical reactions are complete reactions, which means that during the reaction the reacting
substances are consumed until one of them totally disappears.
If we take the combustion of methane in oxygen, for example, the chemical equation is written as
follows:

Methane
CH4

Carbon monoxide
CO

Oxygen
O2

Water
H2O

D CH 1794 A

which leads to the following equation for chemical reactions:

1

CH4 + 2

O2
CO2 +

H2O

E = + 803 kJ/mol

The combustion of 100 moles of methane in the excess oxygen continues until the methane totally
disappears. The result of combustion is the formation of 100 moles of CO2 and 200 moles of water.
The initial and final conditions of the reaction are therefore as follows
INITIAL STATE = REACTANTS
FINAL STATE = PRODUCTS
100 moles of methane CH4

0 mole of methane
100 moles of CO2

Excess oxygen

200 moles of H2O

Non-consumed oxygen

The complete reaction takes place with excess oxygen and consumes 200 moles. Furthermore it is
characterized by a high rate of reaction.
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2-

INCOMPLETE OR BALANCED CHEMICAL REACTIONS

a - Definition
A number of chemical reactions encountered in industry are incomplete or balanced reactions. This
means that the conversion of the reactants is limited and stabilized at a state of equilibrium.
Let us study the conversion of cyclohexane into benzene.
The equation for the conversion of cyclohexane into benzene takes place in the gas phase and is
written as follows:

Cyclohexane
C6 H12

Benzene
C6 H6

Hydrogen
H2

D CH 1796 A

which leads to the following equation for chemical reactions:

1

C6H12

C6H6

H2

E = 209.3 kJ/mol

The double arrow indicates that the reaction is a balanced one.

The conversion yield depends on operating conditions. At the initial stage they are defined as follows
Temperature
Pressure
Molar ratio

T
P
H2
HC

= 450C
= 40 atm

= 10

H2
Since the reaction often takes place in the presence of hydrogen it is characterized by HC which is the
relative molar concentration of hydrogen molecules versus other hydrocarbon (HC) molecules:
cyclohexane and benzene. The term dilution hydrogen is also often used. The value of the molar ratio
H2
HC indicates the dilution ratio used.
H2
In this example, HC = 10 that means that 1 mole of hydrocarbon is diluted with 10 moles of
hydrogen.
The curves on the following page show the results obtained in this chemical reaction as a function of
the operating conditions. For the initial 100 moles of cyclohexane, 56.5 moles of benzene and 169.5
moles of hydrogen are obtained. The remaining 43.5 moles of cyclohexane are therefore not
converted.

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The initial and at equilibrium conditions are therefore as follows.

INITIAL STATE = REACTANTS
FINAL STATE = PRODUCTS

100 moles of cyclohexane

56.5 mole of benzene

1000 moles of dilution hydrogen

43.5 moles of cyclohexane

(not converted)
169.5 moles of hydrogen formed
1000 moles of dilution hydrogen
(present initially)

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300

350

10
P=

400

20 a

10

P=

20

40 a

30

P=

40

50

60

70

80

90

100

% of cyclohexane non converted

450

500

t C

tm

tm

atm

D CH 171 A

100
550

90

80

70

60

50

40

30

20

10

% of benzene production

H
Molar ratio 2
HC
H2
= 10
HC
H2
=5
HC

DEHYDROGENATION OF CYCLOHEXANE TO BENZENE

The final state is characterized by a chemical equilibrium resulting from two concurrent chemical
reactions.
The first reaction (1) involves the conversion of cyclohexane to benzene; this is the forward
reaction.
1

Benzene + 3 H2
Cyclohexane 

The second reaction (2) involves the reverse conversion, of benzene to cyclohexane. This
is the reverse reaction.
2
 Cyclohexane
Benzene + 3 H2 

These two concurrent reactions are represented by a double arrow in the chemical equation with the
following notation

1
2
It can be seen that the desired reaction in the direction 1 is limited by the reverse reaction in the
direction 2 and this double reaction results in incomplete reaction: the dynamic equilibrium is achieved
when the two concurrent reactions have the same velocity. Under the previous operating conditions,
the 100 moles of cyclohexane cannot therefore be fully converted into benzene and hydrogen.
b - Characterization of a balanced reaction

Conversion ratio at equilibrium

In order to characterize the state of equilibrium towards which the chemical system is moving, the
conversion ratio at equilibrium is defined as the number of moles of reactant that have disappeared,
at equilibrium, per initial 100 moles of reactant.
In a complete reaction the conversion ratio is obviously 100% (enough time is supposed to be
available).
In the previous example, the initial 100 moles of cyclohexane produce 56.5 moles of benzene and 43.5
moles of cyclohexane at equilibrium.
The ratio of conversion of cyclohexane into benzene is therefore 56.5%.
In a balanced chemical reaction, the ratio of conversion at equilibrium depends, as we shall see later,
on the operating conditions, i.e. temperature, pressure and proportion of products.

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Ratio of conversion observed

Under the previously mentioned conditions, it is interesting to examine the progress of the reaction until
it reaches a state of equilibrium.
The figure below shows the change in the number of moles of cyclohexane and of benzene with time.

Number of moles
100

75
Cy
clo
he
xan
e

56,5

Equilibrium
concentration
50

State of equilibrium
43,5

nz

en

Equilibrium
concentration

Time
0

t2

At zero on the time scale the reaction has not yet started, so there are:
100 moles of cyclohexane
0 mole of benzene
The gradual formation of benzene and the simultaneous disappearance of cyclohexane can then be
observed. The number of moles of benzene formed tends to stabilize (56.5 moles) from time t2. A
state of equilibrium is said to have been reached.
If the time allowed for the reaction is less than t2, say t1, the state of equilibrium has not yet been
reached and the conversion ratio observed is lower than the conversion ratio at equilibrium.
The chemical equilibrium is therefore a state to which the chemical system evolves. The equilibrium
cannot be reached, however, unless sufficient time is allowed for the reaction.

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D CH 169 A

Be

25

III -

DETAILED STUDY OF A BALANCED CHEMICAL REACTION

When the aim of a chemical conversion is to obtain a product with a conversion ratio that is as high as
possible, it is important to study the possible means of modifying the ratio of conversion at equilibrium as a
function of the operating conditions, i.e. temperature, pressure and the proportion of products.

1-

REACTION CHARACTERISTICS
The characteristics of the reaction of dehydrogenation of cyclohexane to benzene are the following.
a - It is endothermic
Thermal effect
Chemical reactions may have a thermal effect, which modifies temperature. Reactions may be:
-

endothermic i.e. reactions which need heat

exothermic i.e. reactions which produce heat
athermic i.e. reactions without any thermal effect

The dehydrogenation reactions are endothermic, i.e. are heat consuming.

A consequence is a natural trend of these reactions to decrease the temperature of the reaction
medium. The conversion consumes heat: 209 kJ/mol of cyclohexane converted.
This conversion consumes heat: 209 kJ/mol of cyclohexane converted.
With regard to this reaction, two processes can be used to achieve an endothermic conversion. For
example, it is possible:
-

to maintain a constant temperature

This involves an isothermal process which implies a supply of heat to compensate for the
endothermicity of the reaction.

to let the reaction take place with supplying any heat

The process is then adiabatic (without exchange of heat with the exterior) and the
endothermicity in this case results in a decrease in the temperature of the reaction medium.

b - It increases the number of moles

The disappearance of one mole of cyclohexane corresponds to the formation of one mole of benzene
and three moles of hydrogen.
The increase in the number of moles is therefore three moles for one converted mole.

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Variation in the number of moles

Reactants

Products

C6H12

C6H6 + 3 H2

Atomic balance

6 moles of carbon
12 moles of hydrogen

6 moles of carbon
12 moles of hydrogen

Mass balance

1 mole of benzene i.e. 78 g

1 mole of cyclohexane i.e. 84 g 3 mole of hydrogen i.e. 69
Total mass: 84 g

Molecular balance

100 moles of reactant

226 moles of product

+ 43.5 moles of reactant

Conservation

Conservation
Non
conservation

At equilibrium, the increase in the number of moles is therefore

269.5 100 = 169.5 moles
The dehydrogenation reaction occurs with an increase in the number of molecules.
A consequence is a natural trend of these reactions to increase the pressure because the reaction
medium is in gas phase.
c - Hydrogen production
H2
The reaction tends to increase the molar ratio HC . During the reaction the number of hydrocarbon
(HC) moles does not change since the disappearance of one mole of cyclohexane corresponds to the
formation of one mole of benzene. On the other hand the number of moles of hydrogen increases.
H2
H2
The ratio HC = constant therefore increases.
H2

HC =

H2/HC

d - Le Chateliers principle
Generally speaking, three variables can influence the state of equilibrium of a balanced reaction:
-

temperature
pressure
the proportions of reactants

Predicting the shift of a state of equilibrium requires the prior analysis of the tendencies of the reaction
governed by the reaction characteristics with respect to these three variables.
The general rule starting the effect of operating conditions on the conversion ratio at equilibrium,
known as Le Chateliers principle, can be expressed as follows:
In an equilibrium reaction, the conversion rate increases when operating conditions are
modified in a manner contrary to the natural trends of the reaction.
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The reaction tendencies are governed by the reaction characteristics and can be classified as follows:

Characteristics

2-

Action required to increase

conversion

Trends

Endothermic reaction

Temperature decreases

Temperature increases

Exothermic reaction

Temperature increases

Temperature decreases

Athermic reaction

No influence on temperature

No influence on temperature

Increasing number of moles

Pressure increases

Pressure decreases

Decreasing number of moles

Pressure decreases

Pressure increases

Reaction producing hydrogen

Increase in hydrogen
concentration of medium

Decrease in hydrogen
concentration of the medium

INFLUENCE OF THE OPERATING CONDITIONS ON THE STATE OF EQUILIBRIUM

It can be seen experimentally that in an equilibrium chemical reaction, the conversion ratio at
equilibrium depends on operating conditions. It can improve or deteriorate when they vary.
For the reaction considered on the final state of equilibrium, the influence of the following parameters is
studied:
-

temperature
pressure
presence of dilution hydrogen

The result of an experimental study is given by the curves in the previous graph (page 3) concerning
the dehydrogenation of cyclohexane to benzene. They can be used to complete the following tables.
The influence of the operating conditions on the state of equilibrium can be illustrated by performing
the following three exercises.
a - Influence of the temperature
H2
The dilution ratio and pressure are maintained constant: HC = 10

P = 40 atm

The temperature is increased.

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Point

Temperature

450

475

500

Conversion ratio at
equilibrium

2009 - IFP Training

Cyclohexane
not converted

Benzene
formed

Hydrogen
formed

10

The conversion ratio at equilibrium improves if:

temperature
b - Influence of pressure
The ratio of dilution and the temperature are maintained constant.
t = 450C

H2
HC = 10

The pressure is decreased.

Point

Pressure

40

20

10

Conversion ratio at
equilibrium

Cyclohexane
not converted

Benzene
formed

Hydrogen
formed

Benzene
formed

Hydrogen
formed

The conversion ratio at equilibrium improves if:

pressure
c - Influence of hydrogen molar ratio
Temperature and pressure are maintained constant
t = 450C

P = 40 atm

The molar ratio is decreased.

Point

H2
HC

40

20

Conversion ratio at
equilibrium

Cyclohexane
not converted

The conversion ratio at equilibrium improves if

H2
the ratio HC
In the case of this particular reaction, the state of equilibrium is shifted towards a higher
conversion ratio of cyclohexane to benzene if the temperature increases, pressure decreases
H2
and the ratio HC is lowered.
These important conclusions are directly predictable once the reaction characteristics are known.
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d - Summary
The conversion ratio of cyclohexane to benzene is influenced by the previous operating parameters.
The dehydrogenation reactions are endothermic, with increase in the number of molecules, and
production of hydrogen.
What one might expect from Le Chateliers principle, in the case of dehydrogenation reaction of
cyclohexane to benzene, is shown in the table below:

Trends

Action required to
increase the conversion

Endothermic reaction

T

T

Increasing number of moles from

1 (reactant) to 4 (products)

P

P

H2
[H2]   HC 

H2
[H2]
 HC

Characteristics

Reaction producing hydrogen

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IV - KINETIC ASPECT OF CHEMICAL CONVERSIONS

It can be experimentally shown that it requires a certain length of time for chemical reactions to take place, if
they are complete, or for them to reach their state of equilibrium if they are balanced reactions. Thus:
-

the combustion of methane in the oxygen in air

CH4 + 2 O2
CO2 + 2 H2O
is a practically instantaneous reaction since the rate of reaction is extremely high

but on the other hand, the alkylation of benzene by ethylene or the action of amines on
hydrogen sulfide are reactions that take longer to evolve towards their final state of
equilibrium.

It is essential to be aware of this evolution when designing industrial processes involving chemical reactions.
Achieving an acceptable degree of conversion entails

1-

allowing a sufficiently long time for the desired reactions, which governs the size of the
reactors

or, if the rate is really too slow, or if the reaction considered is competing with other equally
rapid, undesirable reactions, finding a means of accelerating, or if necessary of prioritizing,
the desired reaction. This is the function of the catalyst

DEFINITION OF RATES OF REACTION

For a reaction in homogeneous phase in which the reactants R (R1, R2, R3, etc.) are partially or
completely converted into products P (P1, P2, P3, etc.), the rate can be defined with respect to any
product of the reaction. The rate (Vp) represents the number of moles of product that have appeared
during the reaction per unit time and unit reactant volume.
VP =

moles of P produced during the reaction

(unit time) x (unit volume)

or
VP =

(increase in the concentration of P)

(unit time)

Measurements of reaction rates can therefore be expressed as measurements of concentrations

performed in time.
The rate of reaction can be defined in a similar way with respect to the reactants that disappear
VR =

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(decrease in the concentration of R)

(unit time)

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2-

FACTORS INFLUENCING THE RATES OF REACTION

Apart from the presence of substances that are neither reactants nor products and that can modify the
rate of reaction without undergoing any apparent conversion during the process, the factors that can
influence the rate of reaction are temperature, pressure and the proportions of reactants in the
feed. In order to break down the influence of these different terms, the rate of an elementary reaction
Reactants
Products is expressed by the product of a term depending on temperature (k) and by a
term depending on the reactant concentration
V = k x Creactants
Influence of the temperature - Arrhenius' equation
The term k, called the rate factor of the reaction, was introduced by Arrhenius to express the influence
of temperature on the rate of reaction. It can be seen experimentally that this influence varies greatly.
Some rates of reaction are very sensitive to the effect of temperature, other much less so. The
"sensitivity" of the rate of reaction to the temperature is linked to the concept of energy of activation
(symbol E, expressed in kJ/mol).
It is also called the thermal increment of the rate of reaction. The experimental equation of Arrhenius
is written as follows

 E
K = Ko.exp  RT
R represents the ideal gas constant and T absolute temperature.
In the figure below, the activation energy E can be said to express the minimum level of activation
energy required by the reactants to be able to convert themselves into products.
This energy E varies between a few kJ/mol to over 400 kJ/mol depending on the nature of the
reactants and products.

Energy

Activated state

E : activation energy
Final state
(products)

System states

D CH 167 A

Initial state
(reactants)

There is a sort of energy "barrier" that prevents the spontaneous initiation of chemical reactions (this is
what explains why some substances, which are unstable in ambient conditions, nevertheless exist).

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Variations in reaction rates with temperature

The (experimental) knowledge of activation energies makes it possible to quantify variations in the
rates of reaction with temperature.
Let us take a chemical reaction which, at a temperature t1 = 260C, is characterized by a constant k1
and a rate v1. We will determine the rate v2, the constant k2 at temperature t2.
The ratio F (t1 --> t2) of the rate constants at t2 and t1 is as follows:
k2
v2
F (t1
t2) = k = v
1
1
It represents the acceleration factor of the rate from t1 to t2 temperature. The value of F (t1 --> t2)
indicates by which numerical value the rate v1 at temperature t1 must be multiplied in order to obtain
the value of the rate v2 at temperature t2.
If E denotes the activation energy of the reaction of interest, F (t1 --> t2) can be expressed by applying
the Arrhenius equation.

F (t1 t2) =

E
Ko.exp  RT 
1

E
Ko.exp  RT 
2


E
exp  R (t + 273)
1
=



E
exp  R (t + 273)
2

The variation of F as a function of t2, for t1 = 260C, is shown on the following chart for two activation
energies: E = 63 and E = 105 kJ/mol.

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VARIATION IN THE RATE OF REACTION WITH TEMPERATURE

E=

63

kJ/

E=1

10

05 kJ

/mol

F(t 1

15

mo

20

t 2 ) acceleration factor with t 1 = 260 C

25

5
4
3

t 2 : Temperature C

0
260

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280

300

320

340

360

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380

400

420

D CH 173 A

16

For a rise in temperature of 20C between 260C and 280C, the chart shows the relative variation in
rate factors for these two reactions.

260

t

F (260  280)

280C

Reaction

1.7

Reaction 

2.4

The corresponding accelerations show that a rise in temperature always increases the rate of a
chemical reaction.
High activation energy reactions are very sensitive to temperature. Low activation energy
reactions are less sensitive.
It is also possible to find the acceleration factor between two temperatures t3 and t4 (with t4 higher than
t3). The acceleration factor is written as follows:
F (t3  t4)
and is equivalent to
k4
F (t3  t4) = k
3
That can be written
k4
k1
k4
F (t 1
t 4 )
F (t3  t4) = k = k =
3
3
F (t 1
t 3 )
k1
F (t3  t4) and F (t3  t4) can be read directly on the preceding chart.
Thus, for the same rise in temperature of 20C, but between 320 and 340C, the accelerations are as
follows:
t

320

340C

F (260  320)

F (260  340)

F (320  340) =

F (260
340)
F (260
320)

Reaction 1
Reaction 2

For the same temperature increase, the rate of a given chemical reaction is more sensitive at low
temperature than at high temperature.

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17

ol
kJ/m
293

221

40

30

20

16
12

10
9
8
7
6
5

6
10
9
8
7
6
5

105
84
63

4
3

4
3

42

ol
E = 21 kJ/m

350

400

450

250

500
300

550
350

Temperature in C

Influence of pressure and of reactant proportions

Pressure and reactant proportions determine the concentration of reactants in moles per unit volume.
The influence of the term C reactants on the rate of reaction
V = K x Creactants
does not allow us to define a simple general rule, as in the case of temperature.
Expressions such as "the component A is to the power p with respect to the rate of chemical
reaction" are often used. This means that the rate of reaction is proportional to the concentration of
component A to the power p, or in other words (CA)p.
or

V = K (CA)P

where p may be a natural number (1;2;3; ) or a fractional one (0,5;0,3; )

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D CH 172 A

20

100
90
80
70
60
50

20

30

335

40

E=

100
90
80
70
60
50

F acceleration factor

The following figure is more general. It can be used to determine the variation in rates for temperatures
varying from 230 to 350C and from 350 and 550C for reactions with activation energies between 21
and 335 KJ/mol.

18

The power p may be positive, negative or even zero.

-

If p = 0 the reaction is to the power zero with respect to the concentration of A. The rate of
reaction is then independent of the concentration of the substance A.

If p is positive the rate of the reaction is proportional to the concentration of A to the power
p. The greater the concentration of A the faster the rate of reaction.

If p is negative the rate of reaction is inversely proportional to the concentration of A to the

power p. The effect of A is therefore to slow down the reaction.

When reactions take place in the presence of a catalyst, the concentrations to be considered in
determining chemical reaction rates are the concentrations in the adsorbed phase. The expression
of the rate should therefore take into account the adsorption and desorption kinetics of the products
and reactants and possibly internal and external diffusion problems with respect to reactants and
products.

3-

BALANCED CHEMICAL REACTIONS

For a balanced reaction
reactants

products

2
The expression of the rate of reaction should take into account
-

the rate v of the reaction 1 giving rise to the reaction products (forward reaction)
the rate v of the reaction 2 destroying the reaction products (reverse reaction)

The overall rate of reaction is the difference between these two rates.
V of the rate =

The forward reaction, like the reverse reaction, are elementary reactions. Their rates can be expressed
as the product of a rate factor k and a term which is a function of the concentrations.
Thus, for a forward reaction
1
reactants

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products

19

The rate of this reaction can be expressed as follows:

v = k x Creactants
and for the reverse reaction by

v =

k x Cproducts

The overall rate of the balanced reaction is therefore

vreaction = k x Creactants

k x Cproducts

This expression of the overall rate of reaction explains the variation in reactant and product
concentration with time at fixed temperature, as shown below.

Concentration
State of
equilibrium

Initial
concentration
Equilibrium
concentration

ro d

uct

Rea
ctant
s

Initial
concentration

Time

D CH 168 A

Equilibrium
concentration

At time zero, the concentration of reactants is high and the concentration of products is zero. The rate
of the forward reaction is therefore significant. As the products gradually form, the rate of the reverse
reaction increases (higher concentration of products), and that of the forward reaction decreases
(lower concentration of reactants). The overall rate of the reaction, which is the difference between the
rate of the forward reaction and of the reverse reaction, therefore tends to decrease. Then, when the
rate of product formation becomes equal to the rate of product disappearance, the overall rate of
reaction cancels itself out. This means that the state of equilibrium has been reached.
Of course, it is not necessary to mention that the two values k and k are not equal, except by
chance.

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4-

FORMAL KINETICS - EXPRESSIONS OF RATES OF REACTION

A large number of chemical conversions are characterized by kinetics of simple order reaction: first
order or second order. In these two particular cases the variation in reactant and product
concentrations can easily be predicted over a period of time.
a - First-order reaction
In the case of a first-order reaction, the rate of reaction is directly proportional to the reactant
concentration C.
V

rate of reaction proportional to C

The rate of reaction can be expressed by the elementary variation in the reactant concentration C
during the infinitely small interval of time dt and can therefore be written
dC
V = dt
For a first-order reaction, the rate is proportional to the reactant concentration C
dC
V = dt = KC
where K, which has already been defined, is the rate factor of the considered conversion at the
reaction temperature.
The minus sign used before KC indicates that the rate of reaction decreases when the reactant
concentration decreases.
The preceding expression can be used to write the differential equation giving the relationship between
the time and the reactant concentration
dC
C = - K dt

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The resolution is particularly simple in this case. The following two boundary values are integrated:
for t = 0 initial reactant concentration: Co
for time t, concentration C

dC = K
Co C
i.e.

C
[LnC] C

dt
o

t
= K [t] o

LnC LnCo = K (t o)
C
Ln C = Kt
o

C
Kt
Co = e

or

C = Co e Kt
This relation expresses the concentration C of reactant as a function of the time that has elapsed since
the beginning of the reaction and of the initial concentration C.
Obviously, we find for:
and

t=0
:
t

:

C = Co
C
O

For first-order reactions it is customary to define the time of half-reaction
that corresponds to the
time elapsed since the initial moment until the moment when the concentration is equal to half of the
Co
initial concentration: C = 2

is easily determined
Co
K

2 = Coe
1
K

2 =e
1
Ln 2 = K

Ln2 = K

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22

Ln2

= K
Half-reaction time
is also called the reaction period. This relation is used in particular for the
disintegration of radioactive elements. They obey first order reaction kinetics. The term period of a
radioactive element is thus used to indicate the time elapsed for its activity to be dived by two.
The graph below shows the variation in the concentration of reactant with time for a first-order reaction.
It also shows the half-reaction time or period
.

Concentration
Initial concentration

Co

Fisrt order reaction

D CH 237 A

Co
2

Time

It can be seen that for each interval of time
the reactant concentration is divided by two. This is an
important characteristic of first-order reaction kinetics.
b - Second-order reaction
Similarly, second-order reaction kinetics involve a rate of reaction proportional to the square of the
concentration C of the reactant. This can be expressed by the formula
dC
V = dt = - KC2
The resulting differential equation is also particularly simple
dC
= - K dt
C2

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23

The boundary conditions are:

for t = 0
for the moment t

C = Co
concentration C

dt

dC K

Co

1 C
t
 C Co = K [t] o
1
1
C Co = Kt
Co Kt + 1
1
1
=
Kt
+
=
Co
Co
C
i.e.
Co
C = 1 + C Kt
o
This relation giving the variation in reactant concentration with time is characteristic of second-order
reaction kinetics.
c - Other cases
The order of a reaction is not necessarily a simple order since the reactants and products of a reaction
can involve a great variety of orders. Further, reaction mechanisms may be more complex than the
mere conversion
R  P
For instance, reactions may be successive
R  P  S
or concurrent
R

 P1

P2

just to mention a few of them. The corresponding equations are more complex and they cannot always
be easily integrated.

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5-

ADDITION OF A SUBSTANCE NOT TAKING AN APPARENT PART IN THE

REACTION
Two categories of product are involved:
-

inhibitors which are designed to reduce the rate of chemical reactions, e.g. PTE is added
to gasoline to delay ignition of the air fuel mixture

catalysts, which are substances that modify the rate of a chemical reaction

Note that a catalyst increases the rate of the forward reaction and that of the reverse reaction as well.
Consequently, a catalyst does not modify the final state of equilibrium as governed by
thermodynamics, but it enables this state to be reached much faster. This effect of accelerating the
rate of the forward reaction and that of the reverse reaction explains why in certain circumstances
platinum is a dehydrogenation catalyst and in other circumstances it acts as a hydrogenation catalyst.
The figure below illustrates the evolution of the dehydrogenation reaction of cyclohexane with a
platinum catalyst and without a catalyst under the same operating conditions (t, P, ).
Without a catalyst, equilibrium is reached after time t2. The implementation of a catalyst enables it to
be reached in time t1.

Number of moles
Without catalyst
With catalyst

100

P = 40 atm
t = 450 C
H2/HC = 10

75
Cy
clo
hex
ane

56.5

50

State of equilibrium

nz

en

43.5

Time
0

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t1
Equilibrium reached
with catalyst

2009 - IFP Training

t2
Equilibrium
reached

D CH 166 A

Be

25

25

V-

MAIN CATALYTIC REFORMING REACTIONS

For a chemical reaction, thermodynamics dictates the equilibrium that would be reacted theoretically (i.e. if
there is no time limit). Kinetics dictates the rate of the reaction, i.e. the possibilities to reach a state close to
equilibrium in a limited time.
The chemical reactions involved in catalytic reforming reactors are very numerous and complex. Nevertheless
the following are the dominant reactions that occur during the process can be classified in two types:
-

desirable reactions, i.e. reactions which lead to an increased octane number and to high
purity hydrogen production. These are the reactions to promote

adverse reactions, i.e. reactions which lead to decreased octane number, a decrease in
hydrogen purity or a loss in products yield. These are the reactions to minimize

A catalyst is being used to promote the desirable reactions at the expense of the adverse ones through its
action on reaction kinetics.

Desirable reactions

Adverse reactions

With production of hydrogen:

-

Cracking:

naphthenes dehydrogenation
paraffins dehydrocyclization

Without production of hydrogen:

-

1-

hydrocracking
hydrogenolysis

Hydrodealkylation
Alkylation
Disproportionation
Coking

n-paraffins isomerization
naphthenes isomerization

DEHYDROGENATION OF NAPHTHENES
a - Example of the reaction

NAPHTHENE C7H14
Methylcyclohexane
RON = 74.8

AROMATIC C7H8
Toluene
RON = 120

Hydrogen
3 H2

D CH 1008 G

Naphthenic hydrocarbons with 6 to 10 molecules are dehydrogenated to aromatics with 6 (benzene) to

10 carbon atoms with the production of 3 moles of hydrogen per mole of naphthene converted into an
aromatic.

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26

b - Characteristics
Thermodynamically the reaction is balanced, endothermic (~ 210 kJ/mol), involve an increase in
the number of moles and production of hydrogen.
It is favored by:
-

a rise in temperature

reduction of pressure

H2 
decrease in the hydrogen ratio HC

At a pressure of 5 bar abs. and a hydrogen ratio of 3, the equilibrium conversion ratios for cyclohexane
naphthenes with 6, 7, 8 and 9 carbon atoms, at a temperature of 380C, are as follows
Equilibrium conversion
ratio (%)
6C
7C
8C
9C
The formation of aromatics is favored by the increase in the number of carbon atoms.
From kinetic view point, the rate of reaction increases with temperature.
The rate is high, increases slightly with temperature (average activation energy = 105 kJ/mol) and
decreases slightly with the increase in the number of carbon atoms, but remains very high in
comparison with other reactions.
Hydrogen partial pressure has no influence on the rate of these reactions.
At reforming operating conditions, the conversion of naphthenes into aromatics is very fast and almost
complete.
The reaction is promoted by the metallic function of the catalyst
c - Constraints
Due to the high endothermicity of the reaction, the temperature drops heavily and rapidly.
Consequently, the catalyst needs to be distributed among several reactors with intermediate reheaters.

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2-

DEHYDROCYCLIZATION OF PARAFFINS
a - Example of the reaction
It is illustrated by the aromatization of n-heptane

n-PARAFFIN C7H16
n-heptane
RON = 0

AROMATIC C7H8
Toluene
RON = 120

Hydrogen
4 H2

This reaction concerns paraffins with 7 to 10 carbon atoms. It produces 4 moles of hydrogen per mole
of paraffin converted.
b - Characteristics
Thermodynamically, the reaction is balanced, very endothermic ( 250 kJ/mol) and involves an
increase in the number of moles and production of hydrogen.
It is therefore favored by:
-

a rise in temperature

reduction of pressure

H2 
decrease of the hydrogen ratio HC

At a total pressure of 5 bar abs., a temperature of 400C and a hydrogen ratio of 3, the equilibrium
conversion ratio is
nC7
nC9
Note that for the nC6 under the same conditions the equilibrium conversion ratio is only 38%.
From kinetic point of view, the rate increases considerably with temperature (high activation energy
= 147 kJ/mol) and with a decrease in hydrogen partial pressure.
At high temperature and low hydrogen partial pressure the reaction is approximately 15 times slower
than the naphthene dehydrogenation reaction.

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D CH 1008 F

28

The mechanism of this reaction implies first the production of an olefin, with production of 1 mole of
hydrogen, then modification of the structure by cyclization of the olefin formed into a naphthene which
is then dehydrogenated into an aromatic. The mechanism can be illustrated below, based on nheptane as reactant.

+
-HEPTANE C7 H16

HEPTENE 2
C7 H16

HEPTENE 2
C7 H16

H2

METHYL-CYCLOHEXANE

METHYL-CYCLOHEXANE

TOLUENE

3H2

The first and third stage of the reaction depend on the metal function of the catalyst, the second on the
acid function.
The formation of an olefin intermediate explains the presence of small amounts of olefins in the
reformate.
The potential gain in octane is very high (RON nC7 = 0; RON toluene = 120), but the actual gain is
limited by the rates of reaction which are not very high.

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D CH 1187 F

29

3-

ISOMERIZATION OF NAPHTHENES
The isomerization of cyclopentanic naphthenes with at least 6 carbon atoms in the molecule into
cyclohexanic naphthenes implies a rearrangement of the molecule. This reaction does not produce
hydrogen. For example:

n-PARAFFIN C8 H18
n-octane RON < 0

NAPHTHENE C7 H14
Methylcyclohexane
RON = 74.8

ISOPARAFFIN C8 H18
Isooctane RON = 100

D CH 1185 D

NAPHTHENE C7 H14
Dimethylcyclopentane
RON = 92

The balanced, slightly exothermic reaction is theoretically limited by reforming temperatures, but the
cyclohexanic naphthenes formed dehydrogenate into aromatics. This has a great advantage because it
enables cyclopentane naphthenes to be converted into aromatics.
Theoretically, at the selected operating temperature (about 500C), the thermodynamics limit the
alkylcyclohexane formation. But the subsequent dehydrogenation of the alkylcyclohexane into an
aromatic shifts the reaction towards the desired direction.
The complete reaction steps are shown below.

NAPHTHENE C7 H14
Dimethylcyclopentane
RON = 92

NAPHTHENE C7 H14
Methylcyclohexane
RON = 74,8

It uses both functions of the reforming catalyst.

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2009 - IFP Training

AROMATIC C7H8
Toluene
RON = 120

Hydrogen
3H2

D CH 1185 E

30

4-

ISOMERIZATION OF PARAFFINS
Isomerization reactions are balanced, slightly exothermic. Thermodynamically, these reactions are
not favored by the high reforming temperatures. Whereas from a kinetic view point, high temperature
favors isomerization. Then, it is very important to respect the reforming temperature to promote the
desirable product (thermodynamically). The acidic function of the catalyst support is a way to increase
the reaction speed (kinetic).
The isomerization ratio increases with the number of carbon atoms of the paraffins, but the resulting
gain in octane is very low.
The pressure has no effect.
The reaction is slightly jeopardized by a reduction in hydrogen partial pressure, and slightly accelerated
by a rise in temperature (activation energy = 105 kJ/mol).
Both functions of the catalyst are used in the reaction.

5-

HYDROCRACKING
It affects both paraffins and naphthenes. Aromatic rings are very stable and only the branches on the
rings can be separated from the ring. This type of reaction is a hydrodealkylation.
The hydrocracking reaction is illustrated below by means of two examples:

+
H2

n-PENTANE C5 H12
RON = 61.7

+
ETHYL CYCLOHEXANE C8 H16
RON = 46.5

n-BUTANE C4 H10
Gaseous

+
2 H2

METHYLBUTANE C5 H12
RON = 92.3

n-PROPANE C3 H8
Gaseous

The reaction is complete, consumes hydrogen and is exothermic. The rupture in the C-C bonds results
in the formation of LPG with the paraffins, paraffins from naphthenes by the opening of the naphthene
ring and therefore a potential loss of aromatics.
Hydrocracking is favored by the acidity of the carrier but its mechanism requires both functions of the
catalyst. It is very sensitive to the action of temperature (activation energy
45 kcal/mol) but its rate is
slow and it decreases even further when hydrogen partial pressure decreases.
The rate increases when the number of carbon atoms increases.
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D CH 1187 D

n-NONANE C9H20
RON < 0

31

6-

HYDROGENOLYSIS
The reaction is similar to that of hydrocracking but with the difference that it produces light
hydrocarbons (C1 and C2).
It can be can be illustrated by:

+
n-OCTANE C8 H18

H2

+
n-NONANE C9H20

METHANE
C H4

H2

ETHANE C2 H6

n-HEPTANE C7 H16

D CH 1187 E

n-NONANE C9H20

and

+
H2

n-PENTANE C5 H12
RON = 61.7

+
ETHYL CYCLOHEXANE C8 H16
RON = 46.5

n-BUTANE C4 H10
Gaseous

+
2 H2

METHYLBUTANE C5 H12
RON = 92.3

n-PROPANE C3 H8
Gaseous

The reaction is complete, exothermic (
42 kJ/mol) and consumes hydrogen. It is favored by high
temperatures and pressures.
It depends on the metal function of the catalyst.

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D CH 1187 D

n-NONANE C9H20
RON < 0

32

7-

HYDRODEALKYLATION
Hydrodealkylation is the breakage (or cleavage) of the branched radical ( CH3 or C2H5) of an
aromatic ring.
Xylene (two radical groups) can be dealkylated into toluene (one radical group) which in turn can be
dealkylated benzene.
The standard representation is:

C8 H10

Toluene

Hydrogen
H2

C7 H8

C7 H8

CH4

+
Toluene

Methane

Benzene

Hydrogen
H2

Methane

C6 H6

CH4

D CH 1064 A

Xylene

Hydrodealkylation consumes hydrogen and produces methane. It is favored by high temperature and
high pressure and promoted by the metallic function of the catalyst.

8-

ALKYLATION
Alkylation is a condensation reaction which adds an olefin molecule on an aromatic ring. It results in an
aromatic with an increased molecular weight. The reaction proceeds as follows:

Benzene
C6 H6

Propylene
C3 H6

Isopropylbenzene (Cumene)
C9 H12

This reaction, promoted by the catalyst metallic function, is not hydrogen consuming. But it leads to
heavier molecules which may increase the end point of the product. In addition the high molecular
weight hydrocarbons also have a high tendency to form coke. This reaction must be avoided.

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D CH 1065 A

33

9-

DISPROPORTIONATION
Two toluene rings (one branched CH3 radical) can disproportionate to produce one benzene ring (no
branched radical) and one xylene ring (two branched radicals), as shown:

Toluene

Toluene

Benzene

Xylene

C7 H8

C7 H8

C6 H6

C8 H10

This reaction, promoted by the catalyst metallic function, occurs mainly in very severe conditions of
temperature and pressure.

10 - COKING
Coke formation is related to the presence of heavy products, i.e. polycyclic components (aromatic or
naphthenic). These products may originate in the feed and in this case their presence is due to a high
end point, and/or to poor fractionation of heavy gasoline/kerosene, or they may be produced during
some reforming reactions (dehydrocyclization). Traces of heavy olefins or diolefins resulting from some
reforming reactions (dehydrocyclization, alkylation for instance) may also associate with benzene rings
and produce polyaromatic coke precursors.
The end point of gasoline is limited most of the time to 180C. A high end point requires special care
with respect to the quality of the fractionation between gasoline and kerosene.
Coke formation is accelerated by a rise in temperature (activation energy
150 kJ/mol) and by a
reduction in hydrogen partial pressure.
The coke deposit reduces access to the active sites and thus lowers catalyst activity.

VI - CATALYTIC REFORMING OPERATING VARIABLES

The following study sets out firstly to analyze each of the reactions by pointing out its main characteristics,
and secondly to analyze in an overall manner the effect of the unit operating variables on conversions.

1-

INFLUENCE OF OPERATING CONDITIONS ON THE MAIN CATALYTIC

REFORMING REACTIONS
See following table.

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D CH 1066 A

00085_A_A

iP

N into C6

2009 - IFP Training

A + 4 H2

HC lights

COKE FORMATION

+ H2

HYDROCRACKING

nP

DEHYDROCYCLISATION OF PARAFFINS

nP

HYDRO
ISOMERISATION N into C5

A + 3 H2

+ 41

Exothermic

250

Endothermic

REACTION

TOTAL

TP

T

to P

+ 16
+8

not very sensitive

TP

THERMODYNAMIC
EQUILIBRIUM
favored by

Exothermic

210

Endothermic

DEHYDROGENATION OF NAPHTHENES

HEAT OF
REACTION in
kJ/mol

TYPE OF REACTION

RELATIVE RATE
OF REACTION

150

170

146

85

105

85

ACTIVATION
ENERGY
kJ/mol.K



T

V

considerably

V
considerably

V

slightly

V  slightly

V  slightly

little
influence

P

V
considerably

V

V
considerably

V

V

nC 

INFLUENCE ON THE REACTION RATE V

CATALYTIC REFORMING - ELEMENTARY REACTIONS

METAL + ACID
CARRIER

METAL + ACID
CARRIER

METAL + ACID
CARRIER

METAL

CATALYTIC
SITES

34

35

2-

OVERALL INFLUENCE OF OPERATING VARIABLES

For a given feed the main operating variables that allow action on reactor operation are the following:
-

reactors
temperatures
feed flow rate
hydrogen recycle
(possibly) operating pressure

The following tables are designed to show the influence of the modification of one of these variables
on:
-

the evolution of each of the conversions studied from both the standpoint of the equilibrium
conversion ratio and the rate of the reaction.

the consequences for the unit:

-

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octane number
reformate yield
hydrogen production
LPG production
catalyst coking
hydrogen purity

2009 - IFP Training

00085_A_A




Influence on the equilibrium

conversion ratio

Influence on the rate of

reaction

2009 - IFP Training









Octane Number

sp. gr

H2 production

Conclusions:

LPG production

Recycle G. diluted



Complete

Hydrocracking

Isomerization of paraffins and

cyclopentane naphthenes

Gas production

Yield

from paraffins

Aromatic content

Consequences

from naphthenes

Aromatics formation

Increase in the reaction

temperature

Operating variable

Cycle length

Coke build up 



Complete  precursor
favorization

Coking

36

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Gas production

LPG production

average

H2 production

fast

Isomerization of paraffins and

cyclopentane naphthenes

Cracking
=
Hydrocracking
+
Hydrogenolysis

Yield

sp. gr.






slow

from paraffins

Octane Number

Aromatic content

Consequences

Influence on the rate of

conversion observed

very fast

Influence on the equilibrium

conversion ratio

Relative rates

from naphthenes

Aromatics formation

Decrease in feed flow rate

(or decrease in HSV or
increase in contact time)

Operating variable

Cycle length

Coke 
build up



very slow

Coking

37

00085_A_A

2009 - IFP Training

Coke build up

H2
(*) or the ratio HC . Its influence is exerted in the same sense as that of total pressure.

Conclusions:

LPG production



H2 production

Gas production



sp. gr.



Complete



Octane Number

Isomerisation of paraffins and

cyclopentane naphthenes

Cracking
=
Hydrocracking
+
Hydrogenolysis

Yield



Aromatics content

Consequences

Influence on the rate of

reaction



from paraffins

Aromatics formation

from naphthenes

operating

Influence on the equilibrium

conversion ratio

Decrease
in
pressure (*)

Design variable

Coke build up 
Cycle length 



 Promotors

Coking

38

39

3-

EVOLUTION OF REACTIONS IN CATALYTIC REFORMING REACTORS

The differing rates of the various reactions and the high endothermicity of the fastest reactions calls for
a substantial supply of heat if a satisfactory reaction temperature is to be maintained.
Heat is supplied by heaters located between several reactors (for example 3 reactors). Each reactor
therefore represents only part of the total reaction section.
In the first reactor the temperature drops rapidly and stabilizes when the cyclohexane naphthene
dehydrogenation equilibrium is reached. The catalyst volume in the first reactor represents 10 to
15% of the total volume.
After being reheated the effluent enters the second reactor and this is mainly where the isomerization
and dehydrogenation reactions of cyclopentane naphthenes take place. The drop in temperature is
less pronounced than in the first reactor. The catalyst volume in the second reactor represents 20 to
30% of the total volume.
Before entering the next reactor the effluent is again reheated in another heater. The dehydrogenation
and hydrocracking reactions more or less balance each other out thermally, hence minor differences in
temperature occur. The catalyst volume in the third reactor is between 55-70% of the total
volume.
Owing to the nature of the main reactions in each reactor and of the average level of temperature, coke
formation increases from reactor 1 to reactor 3. Recycling of hydrogen-rich gas provides sufficient
hydrogen partial pressure to prevent coke forming too rapidly on the surface of the catalyst.

4-

OPERATING VARIABLES - UNIT PERFORMANCE

The purpose of the catalytic reforming operation is normally to obtain high octane reformate. In a given
unit, the result depends on the following main operating variables
-

temperature of the reaction

feed flow rate

The nature of the feed also plays an important part:

-

chemical composition of the feed, generally indicated by its reformability index: N + 2 A. The
higher this index, the easier the reforming operation is.

volatility of the feed: a heavy feed is more easily reformable than a light one.

The effects of the operating variables on unit performance are explained by what follows.

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40

a - temperature of the reaction

The main variable used in the unit is the temperature of reaction which can be adjusted by means of
furnaces installed upstream of the reactors.
An increase in the octane number is obtained for the same feed flow rate by increasing the
reaction temperature which accelerates the chemical reactions of aromatization and also of
hydrocracking, with the following consequences:
-

reduction in reformate yield

larger production of gas and LPG

At the same temperature, a naphthenic feed lends itself better to reforming than a paraffinic feed
and produces a higher octane number. The same octane number can thus be obtained with this type of
feed at a lower temperature, providing a higher reformate yield and less production of gas.
b - Feed flow rate - space velocity
Space velocity is characterized by the residence time of the feed to be converted in the reactors
containing the catalyst, in other words the time allowed for the chemical reactions to develop.
Obviously a lower VVH and hence a longer contact time induces greater development of the chemical
reactions and therefore increased conversion of the hydrocarbons contained in the feed.
From the operating point of view, the only parameter that can modulate the residence time and
consequently the VVH is the feed flow rate.
Conversely, and this applies to all catalytic units, a reduction in the feed flow rate increases operating
severity resulting in an increase in the reformate octane number and also a decrease in its yield. If the
same octane number is to be maintained, the temperature must be lowered.
c - Operating pressure
Pressure itself is not an operating variable in an existing unit, but it is nevertheless a decisive
parameter in the evolution of the catalytic reforming process.
A reduction in pressure leads to better selectivity of reforming conversions:
-

increased production of hydrogen and aromatics

less formation of light gas

Unfortunately, however, the coking rate increases considerably as pressure is reduced. Catalyst coking
is therefore accelerated, resulting in a drop in activity which drastically reduces the life of cycles
between two regenerations.
The use of more stable catalysts has made it possible to operate reforming units at lower pressure and
to take advantage of the gain in selectivity due to the reduction in operating pressure.

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41

SUMMARY

Main catalytic reforming reactions are:

Naphthene dehydrogenation
Paraffins dehydrocyclization
Paraffins and cyclopentanic naphthene isomerization
Hydrocracking and hydrogenolysis
Coking
The three first reactions are octane "producers". At the opposite the hydrocracking
and hydrogenolysis do not produce octane, but concentrate the high octane
components and therefore reduce the reformate yield.
According to kinetic and thermodynamic characteristics of these reactions:
the reforming reactor contains more and more catalyst:
R1 < R2 < R3
the temperature decreases less and less in reactors

T1 >
T2 >
T3
To adjust the unit efficiency, two variables may be changed:
the reaction temperature which increases the reformate octane number
the feed flow
The pressure is favorable in a short time to the yield and the octane number. But it
reduces the cycle length. The pressure is not much used as operating variable.

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