Chapter 1

NTRODUCTION

1.1 Naphtha
Naphtha is transformed into reformate by catalytic reforming. This process
involves the reconstruction of low-octane hydrocarbons in the naphtha into more
valuable highoctane gasoline components without changing the boiling point
range.Naphtha and reformate are complex mixtures of paraffins, naphthenes, and
aromatics in the C5 -C12 range, naphtha composition. Paraffins or alkanes are
saturated aliphatic hydrocarbons with the general formula CnH2n+2. They are
either straight-chain (n-paraffins) or branched structures (i-paraffins). The boiling
point increases by about 25-30o C for each carbon atom in the molecule, and the
boiling point of an n-paraffin is always higher than that of the i-paraffin with the
same carbon number. The density increases with increasing carbon number as
well. Olefins or alkenes are unsaturated aliphatic hydrocarbons. Like the paraffins,
they are either straight chains or branched structures, but contain one or more
double bonds. Mono-olefins have the general formula CnH2n. Naphthenes or
cycloalkanes are saturated cyclichydrocarbons that contain at least one ring
structure. The general formula for mononaphthenes is CnH2n.The most abundant
naphthenes in petroleum have a ring of either five or six carbon atoms. The rings
can have paraffinic side chains attached to them. The boiling point and the
density is higher than for any paraffin with the same number of carbon atoms.
Aromatics have the general formula CnH2n-6 and contain one or more
polyunsaturated rings (conjugated double bonds). These benzene rings can have
paraffinic side chains or be coupled with other naphthenic or aromatic rings. The
boiling points and the densities of these polyunsaturated compounds are higher
than that of both paraffins and naphthenes with the same carbon number. The
reactivity of the unsaturated bonds make the C6, C7, and C8 aromatics or BTX
(benzene, toluene, xylenes) important building blocks for the petrochemical
industry, Aromatics have high octane numbers. The composition of a given
naphtha depends on the type of crude oil, the boiling range of the naphtha, and
whether it is obtained directly from crude oil distillation or produced by catalytic
or thermal cracking of heavier oil fractions. A typical straight-run medium
naphtha contains 40 - 70 wt % paraffins, 20 -50 wt % naphthenes, 5 - 20 wt %
aromatics, and only 0 - 2 wt % olefins. Naphtha produced by fluid catalytic
cracking (FCC), coking, or visbreaking may contain 30 - 50 wt % olefins
1.2 Catalytic Reforming
Catalytic reforming is the process of transforming C7–C10 hydrocarbons
with low octane numbers to aromatics and iso-paraffins which have high
octane numbers. It is a highly endothermic process requiring large amounts
of energy. A schematic presentation of the feedstock, products and process
condition is shown in Figure1.1. The process can be operated in two modes:
a high severity mode to produce mainly aromatics (80–90 vol%) and a
middle severity mode to produce high octane gasoline (70% aromatics
content).

1.2.1 Reformer Feed Characterization

Feeds are characterized by the Watson characterization factor (K),
naphthenes (N) vol% and aromatics (A) vol% in which (N þ 2A) must be
defined. In addition, initial boiling points (IBP) and end points (EP) for
feeds must be characterized. Feeds can be also characterized by the
hydrocarbon family and their number of carbon atoms. Naphthenic
feeds give a much higher yield than paraffinic feeds. The main feed
comes from hydrotreated heavy naphtha, and some feed comes from
hydrotreated coker naphtha.

Figure 1.1 catalytic reforming process

1.2.2 Role of Reformer in the Refinery and Feed Preparation
The catalytic reformer is one of the major units for gasoline production
in refineries. It can produce 37 wt% of the total gasoline pool. Other
units such as the fluid catalytic cracker (FCC), the methyl ter-butyl ether
(MTBE) production unit, alkylation unit and isomerization unit, also
contribute to this pool. These units will be covered in other chapters of
the book. The straight run naphtha from the crude distillation unit is
hydrotreated to remove sulphur, nitrogen and oxygen which can all
deactivate the reforming catalyst. The hydrotreated naphtha (HTN) is
fractionated into light naphtha (LN), which is mainly C5–C6 , and heavy
naphtha (HN) which is mainly C7–C10 hydrocarbons. It is important to
remove C6 from the reformer feed because it will form benzene which is
considered carcinogenic upon combustion. Light naphtha (LN) is
isomerized in the isomerization unit (I). Light naphtha can be cracked if
introduced to the reformer. The role of the heavy naphtha (HN)
reformer in the refinery is shown in Figure 1.2. Hydrogen, produced in
the reformer can be recycled to the naphtha hydrotreater, and the rest
is sent to other units demanding hydrogen

1.2.3 Research Octane Number

The research octane number (RON) is defined as the percentage by
volume of iso-octane in a mixture of iso-octane and n-heptane that
knocks with some intensity as the fuel is being tested. A list of the RON
of pure hydrocarbon is given in Appendix D. It is seen from this appendix
that the RON of paraffins, iso-paraffins and naphthenes decrease as the
carbon number of the molecule increases. Aromatics have the opposite
trend. This is shown in Figure 1.3.
Figure1.2 Role of reformer in refinery

Figure1.3 Variation of research octane number(RON)

1.2.4 Reforming Reactions

1.2.4.1 Naphthene Dehydrogenation of Cyclohexanes

1.2.4.2 Paraffin Dehydrogenation

1.2.4.3 Dehydrocyclization

1.2.4.4 Isomerization

Isomerization is a mildly exothermic reaction and leads to the increase of an

octane number

1.2.4.5 Hydrocracking Reactions

Hydrocracking reactions are the main sources of C4 hydrocarbons (C1 , C2 , C3
and C4 ). The reactions are highly exothermic and consume high amounts of
hydrogen. Cracking results in the loss of the reformate yield. Paraffin
hydrocracking.

1.2.4.6 Coke Deposition

Coke can also deposit during hydrocracking resulting in the deactivation of the
catalyst. The catalyst in this case has to be re-activated by burning off the
deposited coke. The catalyst is selected to produce a slow hydrocracking reaction.
Coke formation is favoured at low partial pressures of hydrogen. Hydrocracking is
controlled by operating the reaction at low pressure between 5–25 atm (74–368
psia), not too low for coke deposition and not too high in order to avoid cracking
and loss of reformate yield. A summary of reformer reactions and interactions is
shown by the reaction network in Figure1.4
Figure1.4 Network of reforming reaction

1.2.5 Thermodynamics of Reforming Reactions

The dehydrogenation reactions are the main source of reformate product and are
considered to be the most important reactions in reforming. These are highly
endothermic reactions and require a great amount of heat to keep the reaction
going. For this reason three reactors are usually used in the reforming process
with heating the product from each reactor before entering the other.

The dehydrogenation reactions are reversible and equilibrium is established

based on temperature and pressure. It is usually important to calculate the
equilibrium conversion for each reaction. In reforming, a high temperature
around 500C (932F) and a low hydrogen pressure are required. The minimum
partial pressure of hydrogen is determined by the amount of the desired
aromatics conversion
1.2.6 Reaction Kinetics and Catalysts
The catalyst used for reforming is a bifunctional catalyst composed of platinum
metal on chlorinated alumina. Platinum acts as the centre for the
dehydrogenation reaction, and chlorinated alumina acts as an acidic site to
promote structure changes, such as cyclization of paraffins and isomerization of
the naphthenes. Recently additional elements have been added to platinum to
promote additional properties for the catalyst. Iridium (Ir) is added to boost
activity, Rhenium (Re) is added to operate at lower pressures and Tin (Sn) is
added to improve yield at low pressures. The use of Pt/Re is now most common in
semi-regenerative (SR) processes with Pt/Sn is used in moving bed reactors. The
quantity of chlorine used is approximately 1 wt% of the catalyst and the quantity
of platinum is from 0.2 to 0.6 wt%. Impurities that might cause deactivation or
poisoning of the catalyst include: coke, sulphur, nitrogen, metals and water.
Because of these problems, the reformer feed has to be severely hydrotreated to
remove most of these impurities, and the reformer should be operated at high
temperature and low pressure to minimize coke deposition. Paraffin and
naphthene dehydrogenation reactions are very rapid and usually occur in the first
reactor. The isomerization of paraffin and naphthenes is fast, whereas
hydrocracking is slow and takes place in the last reactor. The effect of operating
conditions on reaction rate and other properties is shown in Table1.2

1.2.7 Process Technology

There are several commercial processes available for reforming. These include
Platforming (UOP), Powerforming (Exxon), Magna forming (Engelhard), Catalytic
reforming (IFP), Rheniforming (Chevron) and Ultra forming (Amoco). The old
technologies are fixed bed configuration. Moving bed technology has also
recently been introduced.

1.2.7.1 Semi-regenerative Fixed Bed Process

The schematic flow diagram of this process is shown in Figure1.5. The name semi-
regenerative comes from regeneration of the catalyst in the fixed bed reactors
after shut down by burning off the carbon formed on the catalyst surface.
Reactions such as dehydrogenation of paraffins and naphthenes which are very
rapid and highly endothermic (Table1.2) occur in the first reactor, with high
temperature drop. Reactions that are considered rapid, such as paraffin
isomerization and naphthens dehydroisomerization, give moderate temperature
decline in the second reactor. Furthermore, slow reactions such as
dehydrocyclization and hydrocracking (Table1.2) give low temperature decline in
the third reactor.
 Figure1.5 Semi-regenerative (SR) fixed bed reforming process

Table 5.1 Thermodynamic and kinetic comparison and effect of operating

condition on main reactions and products

The temperature and concentration profile in each reactor is shown in Figure1.6.

To prevent catalyst coking, the hydrogen partial pressure is maintained at a level
such that the hydrogen-to-hydrocarbon ratio by weight (H2/HC) is greater than 25
for monometallic catalyst. This is done by recycling some of the hydrogen
produced (Figure 5.5). Some light hydrocarbons (C1–C4 ) are separated from the
reformate in the stabilizer. At the top of the stabilizer residual hydrogen and C1 to
C4 are withdrawn as condenser products, which are then sent to gas processing,
and part of the liquid product (C3 and C4 ) is returned from the reflux
Figure1.6 (A) Furnace and reactor layout for fixed bed reformer (B) Variation of
temperature in the reactors. (C) Variation in effluent compositions; P0 , initial
Paraffins; N0 , initial Napthenes and A0 , intial Aromatics

drum back to the stabilizer (Figure1.6). The main product of the column is
stabilized reformate, which is sent to the gasoline blending plant. A slight
modification to the semi-regenerative process is to add an extrareactor to avoid
shutting down the whole unit during regeneration. Three reactors can be running
while the forth is being regenerated. This modified process is called the ‘‘cyclic
fixed bed’’ process.
 CHAPTER 2

EX.
kJ
G = -106.3 mol

P = 20 atm

T = 796 K
C 6 ↔ B +4 H 2

The Gibbs free energy of a reaction is defined as :

G = -RTln(K)

Using This equation, The equilibrium constant can be evaluated as:

-106.3=(-0.008314) (796) ln (K) K = 9458178.489

The equilibrium conversion is calculated as follows

42 gal
(
Mole of ( C 6) =1 bbl 1 bbl ¿)(
cm )
3 )(
0.779 g
1 mol
84.16 g
)=1471.63 mol

10,000 scf 1 mol

Mole of ( H 2) =( 1bbl
)( 379 scf )( 1bbl of C 6 ) = 26.39 mol

We will assume “ X “ mols is transformed to ( B ) and ( 4X ) to ( H 2) , The

equilibrium constant can be expressed as :
4
P B PH
K= 2

PC6

The mol fraction of products are:

Mole of ( B ) = X

Mole of ( C 6 ) = 1471.63-X
Mole of ( H 2) = 4X+26.39

Total mole = 1498+4X

The equilibrium constant of be expressed as:

X
K= ( y B PT )¿ ¿ 9458178.489 = ( 1498+4 X )¿ ¿
X=1460.9 mol

This value (( X”)) was extracted by numerical methods using Newton Raphson

mol of (C 6 )reacted 1460.9

Equilibrium conversion of ( C 6 ) = mol of C feed = 0.992
( 6) 1471.63

Using the same steps, values were extracted for the other reactions as shown in the table
 Table

Interactions G Equilibrium constant Value of (( X )) Conversion

(( K ))
C 6 ↔ B +4 H 2 -106.3 KJ/mol 9458178.489 1460.900 mol 0.992

CT ↔ T + 4 H 2 -93.7 KJ/mol 1409119.789 1407.616 mol 0.956

C8↔ X + 4 H2 -83.0 KJ/mol 279752.192 1224.801 mol 0.832

C 9 ↔ 1 ,3 , 5 MB+ 4 H 2 75.4 KJ/mol 88722.300 976.855 mol 0.663

C 10 ↔ Para−cummene + 4 H 2 -71.0 KJ/mol 45633.96 817.022 mol 0.555

C C 6 ↔ B+3 H 2 -78.2 KJ/mol 135450.112 1076.338 mol 0.731

1 ,1−MCC 6 ↔ X +3 H 2 -69.5 KJ/mol 36379.147 764.565 mol 0.519

1 ,3 ,5−MCC 6 ↔ 1, 3 , 5−MB +3 H 2 -63.9 KJ/mol 15608.435 589.080 mol 0.400

1 , 2, 3 , 4−TMCC 6 ↔ Para−cummene+3 H 2 -58.3 KJ/mol 6696.782 451.358 mol 0.306

C 6+ H 2 ↔ iC 5+ C1 -100.5 KJ/mol 3937219.237 1447.147 mol 0.983

C 7+ H 2 ↔ iC 5+ C2 -92.9 KJ/mol 1248673.493 1400.162 mol 0.951

C 8+ H 2 ↔ iC 5+ C3 -85.2 KJ/mol 390072.926 1279.225 mol 0.869

C 10+ H 2 ↔i C5 +C 4 -77.6 KJ/mol 123710.084 1055.545 mol 0.717

C 10+ H 2 ↔2 iC 5 -72.2 KJ/mol 54706.219 860.085 mol 0.584

 mol
componats quanties ( hr ¿ Net
feed product
‫‪componat‬‬ ‫‪feed‬‬ ‫‪R1‬‬ ‫‪R2‬‬ ‫‪R3‬‬
‫‪C6‬‬ ‫فقط مواد‬ ‫قمية الداخل‬
‫الفييد‬
‫البارفينات ال‬
‫تتغير‬