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Catalytic Reforming

Chapter · January 2017

DOI: 10.1007/978-3-319-49347-3_18

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 CATALYTIC REFORMING FOR FUELS AND AROMATICS
Pierre-Yves Le Goff1*, William Kostka2, and Joseph Ross3
1. Axens SA, Rueil Malmaison, France
2. Axens North America, Houston, Texas, USA
3. Axens North America, Princeton, New Jersey, USA
* Pierre-Yves.LE-GOFF@axens.net

1 INTRODUCTION

Catalytic reforming of naphtha is a key process in refineries throughout the world to produce high
octane gasoline and aromatics. This chapter provides an overview of this technology with sections
dedicated to:
 The role of catalytic reforming in the refining and petrochemicals industries
 Naphtha feedstock characteristics
 Reforming reactions
 Reforming catalysts
 Catalyst contaminants
 Process and catalyst evolution
 Catalyst regeneration

2 OBJECTIVE OF CATALYTIC REFORMING

The major objective of catalytic reforming is to transform low octane naphtha (C6-C10 hydrocarbons)
into high octane gasoline and by-product hydrogen. The principle means of obtaining the increase in
octane is the conversion of paraffins and cycloparaffins (naphthenes) into aromatics (see Figure 1).
Catalytic reforming accounts for a large share of the world’s gasoline production and is the most
important source of aromatics for the petrochemical industry. Reforming is also a major source of
refinery hydrogen, the demand for which is growing rapidly as a result of escalating hydrotreatment
requirements.

Figure 1. Simplified Main Reactions in Catalytic Reforming

In order to achieve these objectives, specialized multi-functional precious metal catalysts are
employed in fixed bed or moving bed reactors. As a result of catalyst aging or deactivation by coke
deposition, the catalyst must be periodically or continuously regenerated in a process referred to as Semi-
Regenerative, Cyclic or Continuous Catalyst Regeneration (CCR) catalytic reforming.

2.1 Role of Reforming in the Motor Gasoline Pool

The petroleum refining industry now processes almost 90 Million barrels per day (BPD) of crude
oil to supply the transportation motor fuels and other petroleum based products to meet the world
demands. The main transportation fuels are Gasoline, Jet and Diesel, and each has a set of specifications
on physical and chemical properties for their efficient use in engines. Although motor gasoline demand
accounts for about 25% of the crude oil processed, it is not found in the required amount or quality in
the raw crude oil. The refining industry has therefore developed processes to transform and/or convert
much of the crude oil into high quality gasoline meeting engine and regulatory requirements.
There are over 600 petroleum refineries worldwide employing varying process configurations to
produce gasoline and other products. Gasoline, like other fuels, is a composite of several blending
components from within the refinery forming a product pool meeting both volume and quality
requirements. An example of a refinery gasoline pool configuration is shown in Figure 2. Today there
are over 700 catalytic reforming units in operation for fuels and aromatics production.

Figure 2. Gasoline Pool & Naphtha Complex

The catalytic reforming unit plays an important role in upgrading or reforming low octane material
that boils in the gasoline range but does not meet finished product specifications. As shown in Figure 2,
the reforming unit is typically part of an integrated ‘Naphtha Complex’ to upgrade not only ‘straight
run’ naphtha found in the crude oil, but also cracked naphtha produced by thermal or catalytic conversion
of heavier crude components: Delayed or Fluid Coking (Coker), distillate or resid Hydrotreating (HDT)
or Hydrocracking (HC). Various local regulations on quality often require additional processing of
gasoline components, such as Hydrodesulfurization (HDS) of naphtha from Fluid Catalytic Cracking
(FCC), isomerization of light naphtha and benzene saturation of the reformer product.
The gasoline pool must meet final product specifications, but individual blend components may not.
In fact each processing unit has certain product gasoline characteristics which complement each other
to make a pool that meets specification. Table 1 shows a worldwide average gasoline composition with
typical component property ranges and typical pool specification. Other specifications on fuel boiling
range, sulfur content, stability, corrosion characteristics and much more also apply.
The hydrocarbon liquid product from the reformer (Reformate) is a vital gasoline blend component
to meet pool octane requirements and is the only process unit with wide flexibility in product octane,
typically 90 to 102. Higher severity operation is possible with octane greater than 102, but this is
typically reserved for reformers dedicated to aromatics production as discussed later. On the other hand,
reformer gasoline or reformate is the leading source of gasoline aromatics and benzene which are both
subject to regulatory controls.
 Table 1. Typical Gasoline Pool Composition & Properties

Average Octane Olefin Aromatic Benzene RVP

vol% RON (1) vol% vol% vol% Psia
Butane 5% 93 0 0 0 52
Naphtha 16% 65 – 70 0 1 – 10 1 – 10 11
Isomerate 5% 83 – 87 0 0 0 13
Alkylate 9% 95 - 98 0 0 0 5
Reformate 27% 90 – 102 0–2 60 – 70 0.5 – 5+ 3
FCC Gasoline 30% 90 – 94 20 – 40 20 – 35 0.5 – 1 5
MTBE (2) 2% 118 0 0 0 9
Ethanol 6% 132 0 0 0 11
Pool Specs (3) 100% 90 – 100 < 10 < 35 0.6 – 1 6–9
(1) Research Octane Number ASTM D2699. The United States (US) and Canada use the average of Research and
Motor Octane, (R+M)/2 ≈ RON-5 at retail locations
(2) Banned in the United States
(3) Regional variations apply and in the US the Environmental Protection Agency (EPA) ‘Complex Model’ may
supersede specific limits

2.2 Reforming for Aromatics Production

The other major application for catalytic reforming is aromatics production for petrochemicals and
polymers. The most important aromatics are the so-called BTX components: Benzene, Toluene and
Xylenes. Historically BTX has been readily available as a by-product mainly from ethylene plants (so
called steam crackers) that thermally convert feedstock into light olefins and by-product pyrolysis
gasoline, or PyGas. When the ethylene plant feedstock is naphtha, the aromatics-rich PyGas yield can
be on the order of 25-40% thereby supplying valuable aromatics for the petrochemical and polymer
industry. In recent years, low cost ethane from the Middle East and North American Shale-Gas has
caused ethylene plants to shift toward ethane cracking which produces very little by-product PyGas. As
the worldwide demand for BTX and particularly paraxylene (PX) has rapidly grown, on-purpose
production of aromatics has become the norm in large aromatics complexes based on the catalytic
reforming of naphtha.
Today, catalytic reforming has established itself as the most important process for the production of
aromatics with more than one third of all worldwide reformers configured for maximum aromatics
production. Figure 3 shows the worldwide demand for BTX and the strong dependence on reformate
from catalytic reformers to supply BTX and particularly Xylenes.
 Figure 3. Worldwide Supply of BTX aromatics by Source

The demand for polyethylene terephthalate (PET) polymer accounts for the largest consumption of
xylenes, and in particular paraxylene. With worldwide growth of PET projected to be an impressive 6%
per year, on-purpose aromatics production is growing rapidly. Highly integrated complexes with high
severity catalytic reformers coupled with aromatics transformation processes are able to produce BTX.
When desired, such complexes can be designed to selectively produce around 55 - 65 % of paraxylene
from a typical naphtha feedstock.
The following figure (Figure 4) provides a very simplified scheme for an aromatics complex.

Figure 4. Simplified scheme of an aromatic complex

3 FEEDSTOCK CHARACTERISTICS AND TREATMENT

The reforming unit processes a naphtha cut or petroleum fraction with an initial and final boiling
point range from about 80°C up to 200°C, roughly corresponding to C6 to C10 hydrocarbons.
 In a straight-run naphtha cut, the main hydrocarbon types are paraffins, naphthenes (cycloparaffins)
and aromatics. Naphtha originating from thermal or catalytic cracking (coking, visbreaking, pyrolysis,
FCC) also contain olefinic hydrocarbons. An important characteristic of naphtha is the octane number
as this relates to combustion performance in an engine, where a higher octane is preferred. Research
Octane Numbers (RON) for representative components in the C6 - C8 range are shown in Table 2. Linear
paraffins have the lowest RON and aromatics the highest.[1],[2] Paraffin-rich naphtha therefore has a low
octane and requires reforming to increase the aromatics content and RON to meet motor gasoline
requirements, typically over 90 RON.

Table 2. Research Octane Number, RON, for selected hydrocarbon1

Carbon Number C6 C7 C8

Normal Paraffin 25 0 -192

Iso Paraffin(single branch) 74 53 253

Alkyl cyclopentane 91 67 – 84 31-81

Alkyl cyclohexane 83 75 46-81

Aromatics2 99 124 120-146

Note 1: API Research Project 45

Note 2: Blending RON value
Note 3: 2,2,4 Trimethylpentane is commonly called ‘iso-octane’ and has a RON of 100 by definition
A convenient measure of the quality of a reformer feed and indication of octane potential is its
content of Aromatics (A) plus Naphthenes (N) which are readily converted to aromatics in the reforming
unit. A useful correlating parameter for feed quality is the combination N + 2A in the feed which
represents the sum of the naphthene content and two times the aromatic content. Higher values of this
parameter correspond directionally to more easily converted or reformed feeds resulting in higher octane
gasoline product.
The main sources of naphtha for catalytic reforming are:

 Straight Run (SR) naphtha

 Naphtha produced in Hydro processing units (HDT and HC)
 Coker naphtha (naphtha produced in delayed or fluid coking unit)
 VB naphtha (naphtha produced in a vis-breaker unit)
 Selected portions of FCC naphtha (naphtha produced in a FCC unit)
 PyGas from an ethylene plant or steam cracker

These naphtha streams have widely different elemental and molecular compositions and
contaminant levels as shown in Table 3. Sulfur, nitrogen and silicon are harmful contaminants to the
precious metal reforming catalyst and therefore must be removed in an upstream Naphtha Hydrotreating
Unit (NHT). The limits on S and N are typically 0.5 ppm weight to limit precious metal catalyst
inhibition and salt formation leading to corrosion and fouling in the catalytic reforming unit. Olefins are
saturated to less than 0.5 – 1 wt% in order to minimize coke formation in the reforming unit.

Table 3. Typical Naphtha Properties

Naphtha Source SR Coker Vis Breaker Hydro- FCC PyGas
Cracker

S, ppm weight 100-1,000 >5,000 > 4000 <1 100 - 3,000 100 – 300
N, ppm weight < 10 50 – 1,000 50 – 700 <1 50 - 200 < 10
Si, ppm weight 0 5 - 10 0 0 0 0

Paraffins & 80 - 90 35 - 55 40 - 55 95 - 100 25 – 55 5 – 20

Naphthenes, %
Olefins, % <1 30 - 40 30 - 40 0 20 – 40 15 – 20
Diolefins,% 0 1–4 1–4 0 0.5 - 2 10 – 25
Aromatics, % 10 - 20 15 - 20 15 - 20 5 - 10 25 - 35 55 – 70
Diolefin wt% ≈ Diene Value / 2 ≈ Maleic Anhydride Value / 8

When comparing cracked naphtha to SR naphtha, the first obvious difference is that the sulfur and
nitrogen levels can be much higher, especially in thermal cracked naphtha. The sulfur can be readily
removed in the NHT, but the nitrogen compounds are more problematic with cracked stocks containing
more basic, cyclic nitrogen compounds such as pyridines and anilines. These nitrogen species require a
two-step reaction of ring saturation and opening followed by nitrogen removal as controlled by an
overall equilibrium relationship that is favored by higher pressure. The combined effect of these
compositional differences has a significant impact on the NHT design and pressure requirements.
Thermally cracked naphtha from vis-breaker or coking units, and FCC naphthas contain a high
concentration of olefins, and some diolefins that require very specific NHT catalysts and designs to
overcome gum and coke formation due to diolefin polymerization, and handle the high exotherm from
diolefins and olefins saturation.
Additional precautions must be taken when processing coker naphtha that contains silicon from
antifoaming additives injected in the coking process. Silicon is a poison to both the NHT catalyst and
the downstream reforming catalyst. A silicon guard bed at the inlet of the NHT, and in extreme cases a
separate guard reactor can be mandatory to protect the downstream catalyst. As seen in Figure 5 and
Figure 6, the presence of these contaminants has a significant impact in NHT unit design.
In a straight run NHT flowscheme the feed and hydrogen are heated before entering the reaction
section. The reactor effluent is cooled by preheating the feed in the feed-effluent exchanger and then in
an air or water cooler before entering a separator drum. The hydrogen rich gas leaving the drum is
recycled to the reactor, while the liquid phase is sent to the stripper where small amounts of light ends
are removed. There is a make up of hydrogen (M/U H2) to compensate for hydrogen consumption by
chemical reaction and dissolution, while in the stripper section methane and ethane (FG - Fuel Gas)
together with H2S and NH3 are removed.
 Figure 5. Typical straight run naphtha hydrotreating unit

When processing coker naphtha, a lead liquid phase diolefin reactor is used to saturate the diolefins
present in the feed and avoid fouling, coking and pressure drop in the downstream main hydrotreating
reactor. The gas phase HDT reactor is more complex than the straight run feed case with multiple
catalysts beds to complete olefin saturation, trap silica contaminants and finally remove sulfur and
nitrogen.
In the case of a highly olefinic feed, a quench system can be added between catalyst beds to control
the exotherm from olefin saturation.

Figure 6. Typical coker naphtha hydrotreating unit

After pre-treatment in the NHT, the naphtha product should have essentially no sulfur, nitrogen or
olefins. The molecular composition in terms of Paraffin, Naphthene, and Aromatics, or PNA, will then
determine the potential yield in the reforming unit subject to its design, catalyst type and operation.
 An illustration of the importance of feedstock quality on reformer performance is shown in Figure
7. A feed rich in paraffins (low N+2A content) is more difficult to reform into high octane aromatics
than a low paraffin feed. When processing a paraffin-rich naphtha, the severity of the process
(temperature and/or catalyst contact time) must be higher to attain the desired RON octane resulting in
a yield loss to undesirable light byproducts. Reformate RON octane is therefore the commonly used
measure of overall unit severity. When the feed is rich in naphthene and aromatics (low in paraffins)
milder operating conditions can be used to achieve the same RON and with a higher reformate yield.

Figure 7. Impact of N+2A and RON on reformat yield

An important concept is that the product reformate yield decreases as the severity of the unit is
increased to produce a higher octane reformate. The economics based on feed quality determines the
practical RON that can be obtained as balanced against yield loss and rate of coke formation that will
limit unit operation.

Although N+2A is a convenient feed parameter and naphthtenes are relatively easier to covert to
aromatics than paraffin, the type of naphthenes are important in terms of reaction kinetics and potential
products. Looking in greater detail into molecular composition, cracked naphthas have a much lower
ratio of naphthenes with a six-carbon ring (cyclohexanes) to naphthenes with a five-carbon ring
(cyclopentanes) than SR naphthas as shown in Table 4. The cyclohexanes are much more easily
transformed into aromatics than the cyclopentanes. As a consequence, cracked naphtha is more difficult
to reform.

Table 4. Impact of Naphtha Source on Naphthene Repartition

Ratio Naphthenes with C6 ring / Naphthenes with C5 ring, (typical values)

Carbon Hydrocracking
SR Naphtha Coker Naphtha FCC Naphtha
Number Naphtha
6 1.5 0.5 0.3 0.1
7 1.7 0.3 0.5 0.3
8 2.0 0.6 1.5 0.5

4 MAIN REFORMING REACTIONS

 There are many possible chemical reactions in the reforming process. For any chemical reaction the
thermodynamics dictates the possibility of its occurrence and the amount of products and unconverted
reactants. Under certain conditions (pressure and temperature) some reactions are 100% completed, i.e.,
all the reactants are converted into products. Others are in equilibrium, i.e., only a part of the reactants
are converted. Note that the thermodynamic equilibrium does not mention the time required to reach the
equilibrium or the extent of a reaction.
Kinetics dictates the rate of a chemical reaction (i.e., the amount of feed that disappears in, say, one
second). Kinetics (rate of reaction) is dependent upon operating conditions but can also be widely
modified through the use of properly selected catalysts. One reaction (or a family of reactions) is
generally enhanced by a specific catalyst.
In other words, thermodynamics dictates the ultimate equilibrium composition assuming the time is
infinite. Kinetics enables the prediction of the composition after a finite time. Since time is always
limited, when reactions are competing, kinetics is generally predominant.
As for all processes, the chemical reactions involved in reforming are of two types:
 Desirable reactions, i.e. reactions which lead to an increased aromatics production and octane
number as well as a high purity hydrogen production. These are the reactions to promote.
 Undesirable reactions, i.e. reactions which lead to a decreased octane number, a decrease in
hydrogen purity or a loss in desired products yield. These are the reactions to minimize.
Moreover these chemical reactions can also be sorted in two others families:
 Endothermic reaction, these reactions require heat energy to proceed and according to the Le
Chateleir Principle are promoted at high temperature
 Exothermic reaction, these reactions give off heat and according to the Le Chatelier Principle
are thermodynamically hindered at high temperature.
In the case of catalytic reforming, most of the desirable reactions are endothermic while most of the
undesirable reactions are exothermic.

4.1 The Role of the Catalyst

The role of the catalyst is to improve the rates of desirable reactions while reducing the rates of
undesirable reactions, but it does not change the thermodynamics. In reforming dehydrocyclization,
cycloparaffin dehydrogenation, and isomerization reactions are desirable as they increase RON,
produce aromatics and hydrogen as shown in Figure 1. The undesirable side reactions are mainly
hydrogenolysis and hydrocracking which are to be avoided as they produce low-value gases and
consume hydrogen.[3] Both reaction types are summarized in Figure 8.
 Figure 8. Desirable and undesirable catalytic reforming reactions

Reforming catalysts are composed of active metallic crystallites supported on an alumina (Al-OH)
matrix which is acidic in nature and modified by the addition of chloride to achieve a complex catalyst
system of metallic and acid reaction sites. The metallic catalyst particles can include one or more active
catalyst components to achieve the desired activity and selectivity.
In the following sections, when a reaction is promoted by:
 the metallic function of the catalyst, (m) is written on the reaction scheme.
 the acidic function of the catalyst, (a) is written on the reaction scheme.
As a reminder, an acid is a compound which can donate a proton to a base. In the reforming system the
acid is an Al-OH group while the base is mostly an olefinic-type compound.

4.2 Desirable Reactions

4.2.1 Naphthene dehydrogenation to aromatics

Naphthenic compounds i.e. cyclohexane, methyl cyclohexane, dimethyl cyclohexane up to C10

naphthenes are dehydrogenated respectively into benzene, toluene, xylenes, C9 and C10 aromatics with
the production of 3 moles of hydrogen per mole of naphthene. The methyl cyclohexane reaction, for
instance, proceeds as follows:

Figure 9. Methyl cyclohexane aromatization

Thermodynamically, the reaction is highly endothermic and is favored by high temperature and low
pressure. In addition, higher carbon number cyclohexanes yield higher aromatics production at
equilibrium.[4]
 From a kinetic view point, the rate of reaction increases with temperature and is not affected by the
hydrogen partial pressure. The dehydrogenation reaction rate is high compared to other reforming
reactions as discussed in Section 4.5.
The kinetic and thermodynamic effects are complex with adsorption and desorption of reaction
intermediates influencing the reaction rate. The competing effects as influenced by the main parameters
governing the dehydrogenation reactions are summarized in Table 5 below.
Under normal reformer operating conditions the reaction is very fast and almost complete. It is
promoted by the metallic function of the catalyst. Since it produces aromatics with a high octane,
promoting this reaction is most desirable.

Table 5. Impact of operating parameters on naphthene dehydrogenation

Effect on dehydrogenation due to

Increase of
thermodynamics kinetics
Pressure decreases unaffected
Temperature increases increases
H2/HC ratio* slightly decreases slightly decreases

* Ratio of pure hydrogen (mole) to hydrocarbon feed (mole).

4.2.2 Paraffins dehydrocyclization

The dehydrocyclization of paraffins is perhaps the most important reaction in reforming, and the
most difficult. This is a multiple step process which applies either to the normal paraffins (linear) or
isoparaffins (branched). It involves a dehydrogenation with a release of one hydrogen mole followed by
a molecular rearrangement to form a naphthene and the subsequent dehydrogenation of the naphthene.
The molecular rearrangement to build a naphthene is the most difficult reaction to promote but the
subsequent aromatization of the naphthene yields a noticeable octane increase.[5] It is important to note
that most of the naphthenes initially formed are built on a five-carbon ring nucleus which are
thermodynamically favored.
[5]
The reaction can be summarized as shown in Figure 10 :

Figure 10. Dehydrocyclization of paraffins

The paraffin dehydrocyclization step becomes easier as the molecular weight of the paraffin
increases; however the tendency of paraffins to hydrocrack increases concurrently (discussed later
related to Figure 22 ).
Kinetically, the rate of dehydrocyclization increases with low pressure and high temperature
(discussed later related to Figure 20 and Figure 21), but at typical operating conditions this rate is much
lower than that of naphthene dehydrogenation by a factor of roughly 30:1. The reaction is promoted by
both metallic and acidic functions of the catalyst with the formation of the naphthene being the rate
controlling step. The table below summarizes the impact of operating parameters on the
dehydrocyclization reaction.

Table 6. Effect of parameters on paraffin dehydrocyclization

Effect on dehydrocyclization due

Increase of
to thermodynamics to kinetics
Pressure decreases decreases
Temperature increases increases
H2/HC ratio slightly decreases slightly decreases

The positive impact of pressure and temperature on the thermodynamics is, as for the naphthenes,
explained by the Le Chatelier Principle. Opposite to naphthenes dehydrogenation, the pressure has a
negative impact on the reaction rate due to a more complex reaction scheme and formation of specific
intermediates.

4.2.3 Linear paraffin isomerization

The acid promoted isomerization reaction is important to convert linear paraffins into higher octane
branched paraffins. The reaction can be seen as follows:

Figure 11. Paraffin isomerization simplified scheme

If the intermediates are taken into account, the actual scheme becomes:

Figure 12. Paraffin isomerization mechanism

These reactions are fast, slightly exothermic and the number of carbon atoms does not change. The
thermodynamic equilibrium of isoparaffins to normal paraffins depends mainly on the temperature (low
temperature favorable) and increases with the carbon number of the paraffin as shown in Table 7. The
pressure has no effect on the equilibrium.

Table 7. Impact on paraffin carbon number on equilibrium

Isoparaffin - normal paraffin equilibrium

Carbon atom C4 C5 C6 C7 C8
% Isoparaffin at 500°C 44 58 72 80 88

The paraffins isomerization results in an increase of the octane number. From a kinetic view point
(Figure 20 and Figure 21) high temperature favors isomerization but hydrogen partial pressure has no
effect. These reactions are promoted by the acidic function of the catalyst support.
4.2.4 Napththenes isomerization

The isomerization of an alkylcyclopentane into an alkylcyclohexane involves a ring rearrangement

and is desirable because of the subsequent dehydrogenation of the alkylcyclohexane into an aromatic.
Owing to the difficulty of the ring rearrangement, the risk of ring opening resulting in paraffin is high.
The reaction is slightly exothermic and can be summarized as follows:

Figure 13. Naphthene isomerization

Theoretically, at typical reforming operating temperature (about 500°C) the thermodynamics limits
the alkylcyclohexane formation. However the subsequent dehydrogenation of the alkylcyclohexane into
an aromatic is very fast and shifts the reaction towards the desired direction. This type of reaction is also
easier for higher carbon number molecules.
The octane number increase is significant when considering the end product (aromatics) as shown
below:

Table 8. Octane number increase following aromatization: C7 example

RON MON
Ethyl cyclopentane = 67.2 61.2
Methyl cyclohexane = 74.8 71.1
Toluene = 120 103.5

4.3 Undesirable Reactions

4.3.1 Hydrocracking

Hydrocracking affects either paraffins (normal or iso) or naphthenes. It involves both the acid and
metallic functions of the catalyst. It is, to some extent, a parallel reaction to paraffin dehydrocyclization.
As shown in Figure 14, hydrocracking can be represented schematically by a first step of
dehydrogenation which involves the metallic function of the catalyst, followed by a cleavage of the
resulting olefin and the hydrogenation of the subsequent short chain olefin. The second step of the
reaction is promoted by the acidic function of the catalyst. [6]

Figure 14. Schematic representation of paraffin cracking

 At the selected operating conditions, hydrocracking reactions would be almost complete according
to thermodynamics. Fortunately, however, the cracking reactions are somewhat limited by kinetics.
Compared to its desirable concurrent reaction (dehydrocyclization), hydrocracking becomes even more
significant as the temperature increases.
The main effects of hydrocracking are:
 a decrease of paraffins in the reformate which results in an increase of the aromatics by
concentration, i.e. an increase in octane and a loss of reformate yield.
 a decrease in hydrogen production.
 an increase of LPG production.

4.3.2 Hydrogenolysis

This undesirable reaction has some similarity with hydrocracking since it involves hydrogen
consumption and cleavage of bonds. However, it is promoted solely by the metallic function of the
catalyst and, as opposed to hydrocracking, leads to lighter C1 + C2 hydrocarbons which are even less
valuable than LPG (C3 + C4).
It can be represented schematically as follows:

Figure 15. Schematic representation of the hydrogenolysis of paraffin

Hydrogenolysis also affects the naphthenes, mainly C5 ring naphthenes. The carbon-carbon bond
cleavage results in opening of the ring and formation of paraffinic products. The overall reaction can be
summarized as follows:

Figure 16. Schematic representation of naphthene cracking

In this latter case an increase of the hydrogen partial pressure has a positive effect on the reaction
kinetics.

4.3.3 Alkylation & dealkylation of aromatics

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:

Figure 17. Schematic representation of alkylation & dealkylation

 This reaction, promoted by the catalyst acid function, does not consume hydrogen, 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 that deposits on the catalyst and suppresses
activity. This reaction must be avoided.
On the other hand, dealkylation, the reverse reaction, occurs mainly for alkyl chains having more
than three carbon atoms on an aromatic ring and results in reduction of liquid and hydrogen yield and
increased production of benzene (see Figure 17). Operation at higher pressure and temperature favors
dealkylation and presents a challenge in meeting low benzene in gasoline regulations.

4.3.4 Coking

Coke formation on the catalyst results from a very complex group of chemical reactions, the detailed
mechanism of which is not fully known. The coke has a negative impact on catalyst performance as it
remains on the catalyst, covers the active surface area and hence reduces catalyst activity.
In reforming two types of coke can be distinguished according to their combustion temperature. The
coke located on or nearby the metallic function contains relatively more hydrogen and burns at a low
temperature of around 300°C, whereas coke on the alumina support contains relatively less hydrogen
and requires a high temperature from 400 – 500°C to oxidize during regeneration. Moreover the coke
deposited on the alumina is not homogenous, indeed even at high overall coke content on the catalyst,
there are areas on the alumina support free of coke.[7]
The coke is characterized by its hydrogen to carbon ratio, on a mole basis the ratio is around 1- 1.2
indicating a polyaromatic deposit.
According to Nuclear Magnetic Resonance (NMR) spectroscopy coke is made from condensed
aromatics rings with some methyl groups. A typical representation of a “high temperature” coke is given
below (Figure 18), with the stacking of aromatic rings.

Figure 18. Schematic representation of the high temperature coke

Even if there is no detailed coke formation mechanism, coke formation is linked to the presence of
heavy unsaturated products such as polynuclear aromatics resulting either from the feed or from the
reforming reactions. Traces of heavy olefins or diolefins produced by the reforming reactions will
promote coke formation.
The presence of cyclopentanes also promotes coke formation. At the light end of the feed spectrum,
large quantities of methylcyclopentane and cyclopentane can promote naphthalene (diaromatic)
formation via ring reorganization and condensation. At the other end of the spectrum, heavy molecules
with more than nine carbon atoms can intracyclize to make indene type components, which are also
coke precursors.
With their high ratio of five-carbon ring naphthenes versus six-carbon ring naphthenes, coker and
FCC naphthas make more coke compared to straight run naphthas. Straight-run naphtha and
hydrocracked naphtha also contain five-carbon ring naphthenes, but their overall better reformability
reduces operating temperature requirement and results in less coke formation.
 As mentioned earlier, coke is linked to the formation of heavily dehydrogenated compounds,
therefore low hydrogen partial pressure and high temperature favor coke formation when all other
parameters remain constant.
Other factors leading to coke formation include poor gas distribution that leads to stagnant zones
in a reactor, and increased acidity from excessive moisture and chloride on the catalyst.

4.4 Reaction Network

As described above, many reactions take place in the reforming process. The resulting complex
reaction network involves both metallic and acidic reaction sites. Hence, a reforming catalyst must be
bifunctional.
Figure 19 summarizes the general reaction scheme in terms of acid-catalyzed and metal-catalyzed
reactions. Reactions taking place in the horizontal direction are metal-catalyzed and those taking place
in the vertical direction are acid-catalyzed.

Figure 19. Global reforming reaction scheme.

4.5 Parametric Effects

The effects of the main operating conditions on the rate of the reactions involved in the reforming
process are summarized below.

4.5.1 Effect of hydrogen partial pressure

Figure 20 shows the relative rate of the various reactions as a function of hydrogen partial pressure
on a logarithmic scale. The dehydrogenation rate of a naphthene to aromatic is used as reference and
taken at 100 (Log 100 = 2). Other reaction rates are measured against this reference.
 Figure 20. Relative rate of reaction versus hydrogen partial pressure

At lower hydrogen partial pressure (10 bar), the dehydrogenation of naphthene is about 10 times
faster than isomerization, 30 times faster than the desired dehydrocyclization reaction of paraffins and
50-60 times faster than the undesirable cracking reactions (hydrocracking and hydrogenolysis).[3] Note
that the main cause of increased cracking as the hydrogen partial pressure increases is linked to C5
naphthene ring opening.

Figure 20 shows that there is an incentive to operate at low pressure where the cracking rate is
relatively low and the slower dehydrocyclization of paraffin rate increases. Thermodynamics also favors
low pressure for dehydrogenation and dehydrocyclization. The only drawback of low pressure is the
higher coking rate which is the reason why low pressure reformers are equipped with a Continuous
Catalyst Regeneration (CCR) system.

Table 9. Heat of reaction - relative rate of reaction

Heat of Reaction Relative Rate

REACTIONS
(1) Kcal/mole (2) Approx.
Naphthenes dehydrogenation - 50 30
Paraffin dehydrocyclization - 60 1 (base)
Isomerization: Paraffins +2
3
Naphthenes +4
Cracking + 10 0.5
(1) If the heat of reaction is negative the reaction is endothermic
(2) For pressure below 12 barg.
4.5.2 Effect of temperature

Temperature influences the rate of the various reactions as shown in Figure 21. The activation
energy can be calculated from the slope of the curves. Dehydrogenation has moderate activation energy
(~ 20 Kcal. mole-1) as isomerization (~ 25 Kcal. mole-1) and consequently temperature only slightly
increases the rate of these reactions. Dehydrocyclization has a higher activation energy (~35 Kcal mole-
1) and consequently temperature has a greater impact on the rate of this reaction.[8]
Cracking and coking have higher activation energies (~45 and 35 Kcal. mole-1 respectively). The
rate of these undesirable reactions is more significantly increased by increasing temperature.

Figure 21. Relative rate of reaction versus temperature

Considering the activation energy, highly active new or freshly regenerated catalyst and low severity
permit lower temperature operation which favors the desirable reactions over the side reactions. As the
catalyst deactivates or severity increases, higher operating temperature is required which favors the
undesirable reactions and yield selectivity to desired products declines.

4.5.3 Effect of carbon number

The kinetic study of the chemical reactions becomes even more complicated owing to the presence
of molecules with different numbers of carbon atoms.
As is the case for thermodynamic equilibrium, the rates of the reactions are affected by the length
of the carbon chain of the reactant. Figure 22 presents the rates of dehydrocyclization and cracking of
C6 to C10 paraffins relative to that of n-heptane.
 Figure 22 shows that the cracking reaction rate (the curve represents the sum of hydrocracking and
hydrogenolysis) increases regularly with the number of carbon atoms, whereas the dehydrocyclization
rate exhibits a sudden sharp increase between hexane and heptane as well as between heptane and octane,
while the variation between the higher homologues remains relatively slight.
As a result, the dehydrocyclization of C6 paraffins to benzene is more difficult than that of C7
paraffin to toluene, which itself is more difficult than that of C8 paraffin to xylenes. Accordingly the
most suitable reactive fraction to feed a reforming process is the C7-C10 fraction. Conversion of the C6
paraffin to aromatics is one of the most difficult reactions in reforming.

Figure 22. Relative rate of reaction versus carbon number

4.5.4 Impact on catalyst distribution in reactors

Thermodynamics and kinetics have shown that there is an optimum operating temperature range of
approximately 480°C-535°C in order to simultaneously favor the rate of the desirable reactions and limit
the undesirable ones to an acceptable level.
Due to the highly endothermic nature of the most important and desirable reactions (naphthene
dehydrogenation and paraffin dehydrocyclization) this optimum temperature cannot be sustained
throughout the whole catalyst volume in an adiabatic system (Figure 23). Upon entering the reactor and
contacting the catalyst, the fast dehydrogenation reaction results in a rapid drop in process temperature.
In order to restore the catalyst activity when the temperature has dropped below a critical level, the
partially converted reactor feed must be reheated. To achieve this, the catalyst is distributed into several
reactors (3 or 4 as shown in the figure below) and intermediate heaters are provided. The resulting
conversion profile for the feed into products is also shown as a function of percentage of total catalyst
contacted.
 Figure 23. Endotherm, catalyst distribution & hydrocarbon conversion

So, in a somewhat simplified but practical way, and for operational guidance, the main reactions
that take place in the various reactors can be represented in the following order:

Table 10. Reactions distribution as a function of the reactor number

1st Reactor 2nd Reactor 3rd & 4th Reactor

Dehydrogenation Dehydrogenation Cracking
Isomerization Isomerization Dehydrocyclization
Cracking
Dehydrocyclization

From the above analysis it can be concluded:

 Dehydrogenation reactions are very fast, about one order of magnitude faster than the other
reactions and with a high endotherm.
 Low pressure favors all desirable reactions and reduces cracking. To compensate for the
detrimental effect of low pressure on coking, a low pressure reformer requires continuous catalyst
regeneration.
 An increase in temperature favors the kinetics of dehydrogenation, isomerization, and
dehydrocyclization, but accelerates the degradation reactions (cracking, coking) even more.
Consequently an increase in temperature leads to higher octane reformate product but is also
associated with a decrease in reformate yield.
 The reaction rates of important reactions such as paraffins dehydrocyclization increase noticeably
with the number of carbon atoms. Cyclization is faster for C8 paraffin than for C7, and for C7 than
 for C6. Consequently the C7 - C10 fraction is the most reactive feed and C6 paraffin is the last to be
dehydrocyclized to aromatics in the last reactor.

5 REFORMING CATALYST OVERVIEW

5.1 Metallic Function

As mentioned previously, reforming reactions require the presence of a metal function

dehydrogenation catalyst and an acid function catalyst for dehydrocyclization and isomerization. Table
11 shows the relative dehydrogenation activity of several active metals. The most effective
dehydrogenation catalyst is platinum and despite its high price, it is the metal of choice for the reforming
application.

Table 11. Relative catalyst naphthene dehydroisomerization activity [9]

Dehydrocyclization
Metal
activity ratio
Pt 1
Ir 0.7
Re 0.3
Pd 0.15

In order to efficiently utilize the precious metal, platinum is present as very small aggregates with a
size close to or even below 1 nm, modelisation of such clusters has been recently achieved by quantum
calculations.[10, 11]

5.2 Acid Function

The origin of the catalyst acidity comes from the carrier itself. The carrier is a high purity γ-alumina
doped with chlorine. At reforming conditions, the surface of the alumina is partially hydroxylated and
partially chlorinated. These hydroxyl groups act as the acid sites. The strength of their Brønsted acidity
is inversely related to their O-H bond strength: a stronger bond makes a weaker acid. By itself, this
hydroxyl group does not exhibit sufficient acidity to catalyze the acid-base reactions at a reasonable rate.
Thus the addition of chloride to the catalyst promotes the required acidity since the chloride weakens
the O-H bond strength by polarizing electron density away from it to help satisfy its nearly complete
outer valence shell. Hence the presence of chlorine induces a weakening of the hydrogen network of the
OH groups on γ-alumina and makes them more available for protonation as shown by recent quantum
simulations.[12] Catalyst acidity is controlled by the amount of chloride added to the support and the
water partial pressure in the reactor. A schematic representation of a reforming catalyst is given in Figure
24.
It is worth mentioning that chloride is also helpful to stabilize the platinum cluster.

Figure 24. Simplistic representation of reforming catalyst acidity

5.2.1 Acidity control

 The relative balance between the Al-OH and Al-Cl groups is critical to ensure appropriate catalyst
activity and selectivity.[13] The number of acid sites is controlled by the water partial pressure above the
catalyst. Higher moisture level in the gas results in more acid sites on the surface. The water-to-chloride
ratio of the gas above the catalyst determines the catalyst chloride content. Lower water-to-chloride
ratios result in more chloride on the catalyst.[12]
Catalyst surface area and temperature also impact the moisture and water-to-chloride ratio required
to achieve the appropriate number and strength of acid sites. As catalyst surface area declines with age
(number of regenerations), higher chloride partial pressure and lower water-to-chloride ratio is required
to maintain appropriate acidity. As catalyst temperature is increased to increase reactivity, higher
chloride partial pressure and lower water-to-chloride ratio is again required to maintain appropriate
acidity.
As a basic rule any increase of catalyst chloride content will increase the acidity and therefore the
cracking, on the other hand any increase of the water content in the feed without appropriate chloride
increase to maintain the appropriate water-to-chloride ratio will strip chloride from the catalyst and
consequently reduce the acidity and catalyst activity (Figure 25).

OH Cl OH OH

Al Al +H O Al Al + HCl
2

O O

Figure 25. Water and chloride balance

In reforming, optimum acidity is typically obtained when the recycle gas moisture is in the range of
15 - 25 ppm volume. The associated recycle gas HCl content should be approximately 0.2 to 0.5 ppm
volume depending on temperature, catalyst surface area and contaminants.

5.2.2 Benefits of a stable surface area

The catalyst carrier provides the surface area over which the acid and metal sites are distributed and
the activity and selectivity controlled. As previously mentioned, the catalyst carrier is γ-alumina and has
a fresh surface area on the order of 200 m2/gm. As the catalyst ages and is subjected to regeneration
cycles, the surface area slowly declines primarily due to hydrothermal exposure during periodic
regenerations. As the catalyst surface area drops with each successive regeneration cycle, catalyst
acidity, Pt dispersion and coke tolerance become progressively less effective. Thus, a catalyst with
superior hydrothermal stability maintains its high surface area which facilitates hydroxyl and chloride
retention to provide the requisite acidity and Pt dispersion for superior performance. It has also been
confirmed that chlorine itself improves the stability of small Pt particles.[14]
6 CONTAMINANTS & UNIT TROUBLE SHOOTING

The importance of feed contaminants was discussed in general terms in section 4. A more detailed
review of the impact of contaminants on reforming catalysts is considered in this section.
Catalyst contaminants are classified into three categories, temporary poisons (sometimes called
inhibitors), semi-permanent and permanent poisons.[15]

Figure 26. Difference between inhibitors and permanent poisons

Temporary poison: green curve; Semi-permanent poison: yellow curve; Permanent poison: black curve.

Temporary poisons are those which can be removed from the catalyst, either by dilution or release
when the source of the contaminant is removed. Normal catalyst activity and selectivity is substantially
or fully restored once the contaminant disappears.
The most common temporary poisons (inhibitors) of reforming catalysts are sulfur, organic nitrogen,
water and oxygenated organics. When the contaminant is no longer introduced, normal operation of the
unit will return.
Coke is a type of temporary poison that requires interruption of unit operation to regenerate the
catalyst and renew catalyst performance. As a result of this discontinuity in operation, it is considered
to be a semi-permanent poison.
Permanents poisons are those which induce a loss of performance which cannot be recovered, even
with regeneration and which is so severe that the catalyst must be replaced.
For conventional fixed bed catalysts as well as for continuously regenerated catalysts, the main
permanent poisons are arsenic, lead, copper, iron, sodium, potassium and silicon. Some of these, like
silicon from Coker naphtha, only become an issue once the upstream hydrotreater catalyst becomes
overloaded with the contaminant.
Both the metallic and acidic sites on reforming catalyst are subject to poisoning. A summary of the
main poisons and the type of site each impacts is shown in Figure 27.

Inhibitors & Temporary Poisons Permanent Poisons

Metal Impaired
Sulfur Metals: Fe,Cu, As, Pb, Si
metal

chlorinated Al2O3

Nitrogen Acidity Impaired Na, K

Figure 27. Main reforming catalyst contaminants

6.1 Impact of the Main Temporary Poisons

6.1.1 Sulfur

Sulfur is the most common impurity found in the feed of any reforming unit. The maximum
allowable concentration is typically specified as 0.5 ppm weight expressed as S. Whenever possible, it
is recommended to operate the NHT feed treater to attain an even lower sulfur content and provide
additional catalyst stability and selectivity.
Poisoning is caused by H2S, either contained in the unit feed or resulting from the decomposition of
sulfur compounds contained in the feed. H2S reacts with platinum according to the following equilibrium
reaction (Figure 28) and consequently it reduces the activity of the catalyst by decreasing the number of
active metallic sites available to catalyze reactions as PtS is inactive for promoting dehydrogenation.

Pt + H2S PtS + H2

Figure 28. Interaction between sulfur and platinum

Catalyst contamination by sulfur is indicated by:

 A decrease in hydrogen yield,
 A decrease in recycle gas purity (gas yield increase),
 An increase in hydrocracking (LPG yield increase),
 An increased coking rate,
 A reduced temperature drop in the reactors, especially the first reactor where rapid naphthene
dehydrogenation occurs, and sometimes an increase of temperature drop across the second reactor
as this reaction shifts to the second reactor.
Normally, sulfur removal is achieved by pretreating the naphtha feed in a hydrotreating unit (NHT).
Poor operation of the NHT or mechanical issues can result in sulfur breakthrough to the reforming
catalyst. Possible causes for this breakthrough include:
 Low activity of the hydrotreater catalyst or low hydrogen partial pressure,
 Change in NHT feed quality: higher final boiling point, sulfur or nitrogen content,
 Excessive NHT temperature resulting in recombinant sulfur formation (H2S reaction with olefins
to produce mercaptans near the reactor outlet),
 A leak in the NHT feed-effluent heat exchanger that allows untreated naphtha to bypass the reactor
 Poor operation of the hydrotreater stripper resulting in dissolved H2S and H2O carryover to the
reforming unit
Whenever H2S contamination is present, the reformer temperature should be maintained in the
normal temperature range (despite a drop in octane) to avoid excessive coking of the catalyst. The
recycle gas compressor rate should also be maximized to increase the sulfur stripping effect and
minimize catalyst coke formation.
These conditions must be maintained until the cause of the upset has been found and corrected. High
severity operating conditions can be resumed once the H2S content in the recycle gas is lower than 1 –
1.5 ppm volume.

6.1.2 Nitrogen

In contrast to sulfur, organic nitrogen is less frequently present in the reforming feed and scarcely
present in straight run naphtha. It is a common impurity of cracked naphtha and may also result from
injection of amine based corrosion inhibitors.
The maximum allowable concentration of organic nitrogen in the feed is typically specified at 0.5
ppm weight. Molecular nitrogen (N2) has no detrimental effect.
Organic nitrogen is a problem because NH3 forms by decomposition of organic nitrogen compounds
in the presence of hydrogen on the reforming catalyst. In the reaction section NH3, which is alkaline,
reduces the acidity of the catalyst and increases its rate of chlorine loss. The increase of dechlorination
is linked to the lower HCl partial pressure. Overall, these two effects reduce the catalyst activity. In the
cold section of the unit NH3 reacts with chlorine to form NH4Cl which becomes solid below 80°C. The
resulting salt deposition can foul downstream coolers, separators, recycle gas compressor, export gas
compressor valves, and cold trays in the stabilizer creating mechanical problems. For a 25,000 BPD
reformer, 0.5 ppm weight of organic nitrogen in the feed can lead to approximately 2 T/y of NH4Cl
deposition. Ammonium chloride deposits also raise the risk for under deposit corrosion with trace
moisture present. Failure to replenish this lost chloride will reduce the acidic function of the catalyst and
result in decreased catalyst activity.
Indicators of nitrogen contamination include:
 Decrease in octane,
 Slightly increased hydrogen and C5+ production.
Like sulfur, organic nitrogen removal is achieved by NHT pretreating of the feed; however, nitrogen
removal is more difficult than sulfur removal and often requires the use of a Ni-Mo catalyst operating
at higher hydrogen partial pressure than a typical NHT with Co-Mo catalyst. Naphtha with high nitrogen
content requires a NHT specifically designed for high nitrogen feed.
When nitrogen contamination is detected in the reformer:
 Avoid increasing reformer reactor temperature to compensate for lost catalyst chloride and the
concomitant drop in reformate octane number as this will only increase the loss of chlorine.
 Take the necessary actions in the NHT to lower the nitrogen content down to the acceptable level
of 0.5 ppm weight.
 Increase organic chloride injection into the reformer naphtha to compensate for the lost chloride.
 Reduce the end point of high nitrogen containing naphthas to the NHT to reduce nitrogen in the
reformer feed.

6.1.3 Water upset

The acidity of the catalyst is controlled by two main factors; the moisture in the feed and the chloride
on the catalyst. An increase of the feed moisture without a compensating increase in the feed chloride
content will strip chloride from the catalyst, thereby reducing its acidity. Conversely, too little moisture
in the feed will severely dehydroxylate the catalyst, thereby reducing its overall acidity despite the fact
that its chloride level may be building if no parallel adjustment has been made in feed chloride level.
This phenomenon is most likely to occur in a fixed bed reformer. Proper control of the water/chloride
balance is crucial to maintain the correct metal/acid balance on the catalyst. Insufficient on-stream
chloride, moisture addition or both can ultimately compromise the acid function, and as a result, the
metal function will become dominant producing increased formation of methane (C1) and ethane (C2)
relative to propane (C3) and butanes (C4). Conversely, excess on-stream chloride addition, moisture
addition, or both can ultimately increase catalyst acidity to the point where it begins to overwhelm the
metal function, and as a result, C3 and C4 formation will overtake C1 and C2 production.

The water content of reformer feed is a combination of the intrinsic moisture found in the naphtha
and the moisture added to the feed. Feed moisture should be controlled to achieve approximately 20
ppm volume in the recycle gas for typical conditions.
Water removal is usually achieved in the stripper of the NHT. Generally contamination by water
results from poor operation of this equipment. Water can also be introduced indirectly in the form of
oxygenates which will be reacted to form water in the reformer.
When feeding a reformer unit with low sulfur naphtha from storage, the naphtha should be routed
through the NHT stripper or splitter to remove any water present.
If recycle gas water content exceeds 50 ppm volume, the reactor inlet temperature must be lowered
to reduce the chlorine elution (leaching) from the catalyst and sintering of the metallic sites. The
following guidelines are generally accepted:
> 50 ppm volume water, limit reactor inlet temperature to 500°C
> 100 ppm volume water, limit reactor inlet temperature to 480°C
 If recycle gas moisture drops too far below 10 ppm volume, the catalyst surface becomes sufficiently
dehydroxylated to limit its acidity. Injection of 1 ppm weight water in the feed will increase recycle gas
moisture by 2-5 ppm volume depending on the operating conditions.

6.1.4 Coke

The coke which deposits on the catalyst is a temporary poison since its detrimental effect is
reversible through regeneration. Since coke formation is inherently associated with the reforming
reactions, there is no real way to avoid it. One can only minimize coke formation.
Operating conditions directly impact coking rate. Higher severity (temperature) operation
accelerates coke formation while higher hydrogen partial pressure and hydrogen recycle gas rate retards
its formation due to coke’s hydrogen deficiency.
The feed end boiling point can have a significant impact on coking rate. High end point naphtha,
especially cracked naphtha, tends to accelerate coke formation due to the incremental presence of
heavier aromatics and polyaromatic precursors.
Unfortunately D86 final boiling point doesn’t provide sufficient information in the case of mixed
feeds. Each feed must be analyzed separately to know the true final boiling point of each stream to be
able to specifically limit the heavy components in the cracked feeds. Very often mixed feeds are
responsible for short catalyst cycle life, even though the final boiling point of the mixture stays within
acceptable values.

6.2 Permanent Poisons

Permanent poisons have been defined as contaminants which irreversibly damage the catalyst.

Table 12 lists the main permanent poisons as well as their acceptable level in reformer feed and their
most likely source.

Table 12. Main contaminant max level in feed and origin

Poisons Max. level (wt) Source

Arsenic 5 ppb max SR, cracked naphthas, or gas condensates
Lead 1 ppb max Recycled slops
Iron < detection limit Corrosion, metal dusting
Sodium < detection limit Crude
Fixed Bed regeneration with caustic carryover
Silicon < detection limit Additives (anti-foaming)

Most metals poison the metal functions (platinum and promoter) of the catalyst. Their impact tends
to progress sequentially through the reactors in a fixed bed reformer. The first reactor is typically the
reactor where the poisoning is first detected. In a CCR reformer unit with circulating catalyst, poisons
can affect the whole catalyst inventory if the cause of pollution is not found.
Metal contamination is characterized by:
 A dramatic decrease of the T (temperature drop) in the first reactor associated with an increased
T in the second reactor, then decrease of T with 2nd reactor, etc.
 A decrease in octane number.
 An increase in liquid product yield.
 A decrease of hydrogen production and purity.
In addition to poisoning the catalysts functions, mechanical problems may result from the collection
of corrosion products (scale, rust...) in the top layer of the first catalyst bed in a fixed reactor system, or
the accumulation of scale or rust in the stagnant zone of the first reactor.
 The contaminants and the source of contamination are listed in Table 12 above. Prevention consists
of adequate feed pretreatment in a NHT and appropriate material selection to limit corrosion. Metal
poisons are generally partially retained on the upstream hydrotreating catalysts. However their retention
capacity is limited and breakthrough may occur. Such a breakthrough would result in a very harmful
situation for the unit since these poisons would not be eliminated by the catalyst regeneration.
It is very important to periodically check the metal content of the hydrotreater feed and product.
Monitoring the performance of the hydrotreater with regard to demetallization not only protects the
reformer but also gives an indication of when the hydrotreatment catalyst needs to be replaced.

7 REFORMING EVOLUTION

7.1 Commercialization of Catalytic Reforming

Perhaps the earliest reference to catalytic reforming is found in US patent 2288336 entitled
“Catalytic Reforming of Naphthas” filed in 1939 by Standard Catalytic Company, a subsidiary of
Standard Oil. The process was developed as a means of producing aviation gasoline and toluene to meet
the demands of World War II. The “Hydroforming” process was commercialized in 1941 utilizing
molybdenum-alumina and chromium-alumina catalyst in fixed bed reactor systems. Rapid catalyst
deactivation led to the development and commercialization of moving bed and fluid bed units by some
of the major oil companies in the early 1950’s.
The modern catalytic reforming process was first commercialized by UOP in 1951 using a bi-
functional catalyst composed of platinum impregnated on a slightly chlorinated γ-alumina.[16] The
process trademarked by UOP as Platforming represented a significant improvement in catalyst activity
to produce high octane gasoline. The process was widely applied for gasoline and aromatics production,
however frequent catalyst regeneration was required to maintain activity. Operation at relatively high
pressure with recycle of product hydrogen was necessary to suppress coking reactions due to the poor
stability of the catalyst system. Cyclic reformers with the capability to isolate and regenerate individual
reactors while the remainder of the unit remained on oil were developed and commercialized by
Standard Oil of Indiana (Ultraforming) and Standard Oil of New Jersey (Powerforming) in the early
1950’s.
Development work on promoted or multi-metallic catalyst formulations resulted in Chevron’s
commercialization of rhenium promoted platinum catalysts in 1969 (Rheniforming). The significant
improvement in catalyst stability (lower coke formation) obtained by using other metals, such as
rhenium, in combination with the primary reforming catalyst metal, platinum, prompted a rapid
development in catalyst formulations. With bi-metallic catalysts fixed bed catalytic reforming processes
could achieve cycle lengths of 1 to 2 years at higher severity operation before coke build-up on the
catalyst reduced activity to the point where periodic shut down and catalyst regeneration was required.
These units are referred to as Semi-Regenerative reforming processes.

7.2 Semi Regenerative Catalytic Reforming

A typical configuration of a fixed bed semi-regenerative reforming process is shown in Figure 29.
 Figure 29. Fixed bed catalytic reforming process scheme

In the flow scheme above, hydrotreated naphtha feed is combined with hydrogen-rich recycle gas,
preheated by heat exchange with the reactor effluent and then further heated in a fired heater before
entering the first reactor. As the endothermic reforming reactions cool the feed and product mixture, the
effluent from the first reactor must be reheated to the required reaction temperature in a fired heater
before entering the second reactor, and similarly for the last reactor (refer also to Figure 23).
The product liquid and gases are cooled and separated in a simple flash separator into a hydrogen-
rich gas stream and a liquids product stream. Some of the hydrogen-rich gas is recycled to the reactors
to suppress coke formation and the remaining product or ‘make gas’ is sent to the refinery hydrogen
system. The separator liquids are stabilized to recover a C5+ reformate product stream and LPG by-
product stream, along with a small off-gas stream.
Over time, the catalyst in the fixed bed reactors age (deactivate due to coke) and when the
performance is no longer economic the unit is shut down and the catalyst regenerated on a periodic or
semi-regenerative basis. The catalyst may be removed for ex-situ regeneration and subsequent reloading,
or regenerated in-situ. Catalyst regeneration can be a rather complex and precise operation as will be
described later.

7.3 CYCLIC CATALYTIC REFORMING

A typical configuration for a fixed bed, cyclic reforming process is shown in Figure 30.

This process scheme utilizes a “swing” reactor in addition to the 3 to 5 on-oil reactors and a separate
regeneration system to maintain continuous operation of the reaction system while individual reactors
are regenerated in the regeneration system. As a reactor becomes sufficiently deactivated, the “swing”
reactor replaces it in the on-oil reactor series through a sequence of valve movements in the reaction and
regeneration headers. At the same time, a parallel sequence of valve movements transfers the
deactivated reactor from the reaction header to the regeneration header for regeneration. The tail
reactors are typically regenerated more frequently than the lead reactors, and the “swing” reactor is
regenerated as often as needed to maintain on-oil performance. Units operating at high enough severity
to require continuous operation of the regeneration section are said to be in full cyclic mode. As severity
drops below the threshold for full cyclic operation, discontinuous use of the regeneration section
becomes possible and the unit operates in semi-cyclic mode. At low enough severity, the unit operates
more like a semi-regenerative reformer, and occasionally regenerates the full complement of reactors
one at a time.
 In a cyclic reformer, reaction system H2O and H2S concentrations spike well above the desired
operating target and catalyst performance declines for the duration of the disturbance every time a
freshly regenerated reactor swings into on-oil service. Addition of a dryer in the recycle gas loop,
regeneration loop or both reduces the magnitude and impact of this disturbance.

Figure 30. Typical cyclic reforming process scheme

S: Swing reactor ; In red regeneration process line ; In black reaction process line

7.4 Radial Flow Reactor Design

The first reforming reactors were spherical due to the high pressure of operation with mono-metallic
catalysts. Catalyst loading and distribution problems associated with spherical reactors and thin reactor
beds then led to cylindrical, axial flow fixed bed reactors.
As the catalyst technology improved and lower pressure operation was possible for improved yield
selectivity, the problem of catalyst bed pressure drop and recycle compressor duty led to the introduction
of radial flow reactors Figure 31. The gas is introduced through the top and flows down along the outer
wall of the cylindrical reactor and then flows radially inward through the thin annular catalyst bed.
Screens are used to contain the catalyst in the annular bed and allow reactants to enter from the wall,
pass through the bed, and then enter a center pipe collection tube to exit the vessel at the bottom. This
design provides intimate and controlled contact between the feed and catalyst with a low pressure drop
across the thin bed of catalyst.
 Figure 31. Typical radial flow reactor

7.5 Evolution of Reforming Catalyst

The need to operate mono-metallic units at relatively high pressure and with high hydrogen recycle
to suppress coke formation was at odds with the thermodynamically preferred low pressure. As noted
above, catalyst development focused on ways to improve stability and therefore allow for operation at
more favored lower pressure. The first step of combining promoter metals such as Rhenium was very
successful and Pt-Re catalysts are widely used today for semi-regenerative or fixed bed reforming.[17]
The explanation for the improvement obtained following the addition of rhenium can be understood
by the following graph.[18]

Figure 32. Platinum stability improvement with Re addition

As the reaction proceeds, the platinum accessibility reduces due to coke formation on the catalyst.
When only platinum is used, the activity or platinum accessibility declines rapidly. Note that recent
quantum simulations have quantified the impact of H2 partial pressure on the stability of hydrocarbon
species present on the Pt nanoparticles: only high H2 partial pressure may prevent the formation of
undesired carbon species adsorbed on the Pt particle.[19, 20] When rhenium is introduced along with the
platinum, the platinum cluster is by far more stable with much more of the platinum accessible over a
longer period of time.
Thus the desirable dehydrogenation/hydrogenation activity is more stable which can been seen by
the reduced coke make (Figure 33).[18]
 Figure 33. Impact of Rhenium on coke make (n-heptane feed)

Further development work discovered other metal combinations with even greater yield selectivity
and activity than either Pt alone or Pt-Re as shown in Figure 34. When Pt was combined with tin (Sn)
the desired dehydrogenation reactions were greatly enhanced but this benefit only occurred at low
pressure. Indeed as seen in Figure 34 Pt-Sn catalyst promotes the relative rate of aromatization of
naphthene at the expense of their hydrogenolysis over a wide pressure range, but it is only at low pressure
that their activity surpasses that of Pt or Pt-Rhenium catalyst.
The challenge of lower pressure is that coke formation on the catalyst increases sharply and stability
declines. This challenge was met with the introduction of Continuous Catalyst Regeneration technology
in the early 1970’s.

Figure 34. Impact of metal complexes with Pt on selectivity and activity

7.6 Continuous Catalyst Regeneration (CCR) Design

In order to realize the benefits of the new Pt-Sn catalyst, a means of operating at reduced pressure
and with more frequent catalyst regeneration was required. A moving catalyst bed design was
commercialized in the early 1970’s so that a Continuous Catalyst Regeneration (CCR) scheme could be
implemented. This innovation allowed for the development of more selective ultra-low pressure designs
utilizing customized catalysts to achieve higher yields of C5+ reformate, aromatics and hydrogen.
The CCR reforming process is offered by two licensors: Axens with a side-by-side reactor
configuration under the trade names Octanizing™ and Aromizing™, and a stacked configuration offered
by UOP under the trade name CCR Platforming™ (Figure 34Figure 35).
 Figure 35. Reactor configuration in CCR unit

A CCR reformer design is similar to a fixed bed semi-regenerative design with heaters between each
reactor and a recycle gas compressor in order to reduce coke make. In order to ensure a continuous
operation of the unit, the catalyst must move or circulate through the reactors and a regenerator so that
coke is burned and the catalyst regenerated on a continuous basis.
The reactors (typically 3 or 4) can be configured in a side-by-side arrangement as practiced by
Axens, or stacked in a tower as offered by UOP as shown above. In both cases, catalyst is circulated
between the reactors and a regeneration section with catalyst flow within each reactor by gravity flow.
Like most modern fixed bed designs, radial reactors are used in CCR designs to optimize catalyst
and feed contact in a low pressure drop reactor design. However for CCR units the catalyst moves slowly
down and through the reactor and allowance must be made for the moving bed density. The CCR radial
reactor design naturally also has special mechanical means for introducing, distributing, and removing
catalyst from the annular radial bed.
In the regeneration section, four steps are performed on a continuous basis:
 coke burning to remove coke deposits,
 oxychlorination to adjust catalyst chloride and redisperse the active metals on the carrier support,
 calcination to dry the catalyst, and
 reduction to convert Pt oxide to active metal

7.7 From High Pressure to Low Pressure CCR

As was discussed in the Chemical Reaction section (Section 4), operation at high pressure causes a
decline in gasoline and hydrogen production and thus has a negative impact on the overall economics.
As new catalyst formulations allowed for greater stability, it was possible to reduce the reaction pressure
and hydrogen recycle while still achieving an acceptable cycle length. When the CCR design was
introduced, catalyst stability became less important and the operating pressure could be reduced as
dictated by thermodynamics. Figure 36 illustrates the trend in operating pressure as catalyst formulations
evolved.
 Figure 36. Pressure trend in reforming and catalyst evolution.

As catalyst improvements allowed for a change in process configuration from high pressure semi-
regenerative reforming to ultra-low pressure CCR reforming, the yields improved dramatically. Figure
37 demonstrates the improvement in yields with 10 wt% more reformate and a 50% (relative) increase
in hydrogen production as the average reaction pressure is reduced from 20 barg (275 psig) to 3.5 barg
(50 psig) at a constant 100 RON severity.

Wt%
100

95
H2
Cracking
90
Reformate

85

80
Semi Reg CCR Medium P CCR Ultra Low P

Figure 37. Yields trend versus pressure (100 RON severity, feed PNA=54/30/16 w%)

While the low pressure CCR provides the highest yields and economic return, the trade-off is the
need to circulate catalyst and operate a CCR system with a high regeneration frequency. In some ultra-
low pressure CCR units running at high severity for aromatics production, the entire catalyst inventory
circulates through the unit and regenerator every three to five days in order to maintain a coke on catalyst
level below about 5 wt%.
Most of the new reforming units are based on ultra-low pressure CCR design as it provides superior
yields and the highest economic return. The frequent regenerations with a CCR subject the catalyst to
severe conditions that reduce the carrier surface area and activity over time. Improvements in catalyst
formulation and regeneration system design have been necessary to ensure long catalyst and equipment
life.
Today, low pressure reforming with moving catalyst beds and CCR technology is the norm to realize
the benefits of new Pt catalysts using multiple promoter metals and optimized carrier systems.[21]
8 CATALYST REGENERATION

As the feedstock is converted, some of the hydrocarbons will form coke which will accumulate on
the catalyst as noted above. The lower the unit pressure and more severe the operation, the more rapidly
will coke deposit on the catalyst. Therefore the performance will decrease over time and at a given point
the catalyst needs to be regenerated. The coke level on catalyst prior to regeneration may be 20-30 wt%
in the case of fixed bed semi-regenerative catalysts and 3-7% for CCR catalyst.
Between a CCR and a fixed bed unit, the regeneration steps are fundamentally the same only the
frequency and mechanical equipment are different. For a CCR the regeneration can be every 3-7 days
while for a fixed bed unit it can be every 6 months up to 3 years.
There are four steps involved in the regeneration sequence,
 Combustion
 Oxychlorination
 Drying
 Reduction
A block diagram of a regeneration scheme is shown in Figure 38.

Figure 38. Schematic representation of catalyst regeneration steps

8.1 Combustion Step

The main objective of this step is to burn the coke. But in order to avoid a high exotherm from coke
burning or localized hot spots, the burning gas is recycled to limit the oxygen content which becomes
progressively more diluted with nitrogen as it recirculates. A typical oxygen content of less than 1 vol
% is maintained to achieve a controlled burn of the coke without damaging the catalyst. The catalyst
temperature during regeneration is generally limited to less than 600°C. Staged oxygen addition is also
implemented to limit the exotherm and protect the catalyst.
The regeneration process, consisting mainly of coke burning, has a negative impact on the surface
area of the catalyst due to hydrothermal instability of the alumina and potential hot spots created by
maldistribution. The reduction of the specific surface of the catalyst has a direct impact on the chloride
retention of the carrier and acid function of the catalyst. This can have several drawbacks for the day-
to-day operation of the unit (Figure 39). The activity of the catalyst will decline and this can lead to the
formation of olefins and heavy aromatic polymers referred to as green oil. As chloride is lost, more must
be injected resulting in downstream equipment corrosion and salt deposits that foul colder parts in the
recovery section.
 Figure 39. Impact of low chloride retention on day to day operation

Thus the catalyst and regeneration system must be designed to limit surface area loss during
regeneration, or an economic penalty of more frequent catalyst replacement will result.
The optimal design of the regeneration section is therefore of paramount importance for CCR
application with a high frequency of catalyst regeneration. Exposure to high temperature and particularly
in the presence of steam is a well-known cause of surface area reduction in alumina systems. One means
of reducing catalyst degradation as practiced in the Axens design, shown in Figure 40, is to reduce the
water partial pressure in the burning section by means of a dryer system and to implement staged
combustion (air injection) to avoid localized hot spots. In addition to these process changes, the catalyst
itself can be designed for high hydrothermal stability by the addition of promoters.

Figure 40. Typical Axens regeneration loop

8.2 Oxychlorination Step[22]

During the combustion step, the small platinum particles undergo sintering or agglomeration into
larger clusters due to exposure to high temperature, moisture in the combustion gas, and elution or loss
of chloride. As only the surface platinum atoms are active for reforming reactions, larger clusters must
be redispersed into smaller crystallites.
 This redispersion is done under an oxygen atmosphere, typically above 5 % vol, in the presence of
chloride at temperatures typically above 480°C. The proposed mechanism [23] assumes the formation of
an oxychlorinated platinum complex. At the end of this oxychlorination step the platinum is well
dispersed as small clusters on the carrier and in an oxide form (PtOxCly).

Figure 41. Typical picture of an oxychlorinated catalyst

8.3 Drying Step & Reduction Step

The final regeneration step is the reduction to convert the oxide form of platinum to the active
metallic form in order to ensure a good reduction, the catalyst needs to be dry and hence a calcination
or drying step precedes the reduction step.
The transformation of the catalyst during regeneration is illustrated in Figure 42 where the catalyst
color goes from creamy white when oxychlorinated to grey under reduced form to black when coked.

Figure 42. Catalyst cycle life in a reforming unit

8.4 Chloride Control

The control of chloride addition to the catalyst and loss to products and effluents is very important
for reformer design and operation.
Since some chlorine loss from the catalyst always occurs, the products of reforming will be
contaminated with chlorides. In order to protect process equipment in the reformer and downstream
processes and catalysts, it is common to install a chlorine guard or trapping mass in one or more locations
in the reforming unit. Figure 43 illustrates the possible locations of the trapping mass for vapor and
liquid.

Figure 43. Standard chloride trapping mass locations

9 CONCLUSIONS

Since its development over 60 years ago, the reforming process and catalysts have significantly been
improved.
Unit pressure has dropped from 40 bar g down to 3.5 bar g while reformate yields have been
increased by more than 10 wt % (absolute). Catalyst and process developments continue to improve
yield selectivity and catalyst stability to provide greater operational flexibility and profitability.
From an economic stand point reforming is still a key process in the refineries as it provides high
octane components for the gasoline pool and hydrogen for hydrocracking & hydrotreating units. For the
aromatics market it is the main producer of xylenes.

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Figure 1. Simplified Main Reactions in Catalytic Reforming ........................................................ 1

Figure 2. Gasoline Pool & Naphtha Complex ............................................................................. 2
Figure 3. Worldwide Supply of BTX aromatics by Source ........................................................... 4
Figure 4. Simplified scheme of an aromatic complex ................................................................... 4
Figure 5. Typical straight run naphtha hydrotreating unit ............................................................. 7
Figure 6. Typical coker naphtha hydrotreating unit...................................................................... 7
Figure 7. Impact of N+2A and RON on reformat yield ................................................................ 8
Figure 8. Desirable and undesirable catalytic reforming reactions ................................................10
Figure 9. Methyl cyclohexane aromatization .............................................................................10
Figure 10. Dehydrocyclization of paraffins ................................................................................11
Figure 11. Paraffin isomerization simplified scheme ...................................................................12
Figure 12. Paraffin isomerization mechanism .............................................................................12
Figure 13. Naphthene isomerization ..........................................................................................13
Figure 14. Schematic representation of paraffin cracking .............................................................13
Figure 15. Schematic representation of the hydrogenolysis of paraffin...........................................14
Figure 16. Schematic representation of naphthene cracking ..........................................................14
Figure 17. Schematic representation of alkylation & dealkylation .................................................14
Figure 18. Schematic representation of the high temperature coke ................................................15
Figure 19. Global reforming reaction scheme. ............................................................................16
Figure 20. Relative rate of reaction versus hydrogen partial pressure .............................................17
Figure 21. Relative rate of reaction versus temperature ................................................................18
Figure 22. Relative rate of reaction versus carbon number ...........................................................19
Figure 23. Endotherm, catalyst distribution & hydrocarbon conversion .........................................20
Figure 24. Simplistic representation of reforming catalyst acidity .................................................21
Figure 25. Water and chloride balance .......................................................................................22
Figure 26. Difference between inhibitors and permanent poisons ..................................................23
Figure 27. Main reforming catalyst contaminants ........................................................................23
Figure 28. Interaction between sulfur and platinum .....................................................................24
Figure 29. Fixed bed catalytic reforming process scheme .............................................................28
Figure 30. Typical cyclic reforming process scheme ...................................................................29
Figure 31. Typical radial flow reactor ........................................................................................30
Figure 32. Platinum stability improvement with Re addition ........................................................30
Figure 33. Impact of Rhenium on coke make (n-heptane feed)......................................................31
Figure 34. Impact of metal complexes with Pt on selectivity and activity .......................................31
 Figure 35. Reactor configuration in CCR unit .............................................................................32
Figure 36. Pressure trend in reforming and catalyst evolution. ......................................................33
Figure 37. Yields trend versus pressure (100 RON severity, feed PNA=54/30/16 w%) ....................33
Figure 38. Schematic representation of catalyst regeneration steps ................................................34
Figure 39. Impact of low chloride retention on day to day operation ..............................................35
Figure 40. Typical Axens regeneration loop ...............................................................................35
Figure 41. Typical picture of an oxychlorinated catalyst ..............................................................36
Figure 42. Catalyst cycle life in a reforming unit ........................................................................37
Figure 43. Standard chloride trapping mass locations ..................................................................37

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