300 IO Operating Instructions Rev0

August 2011
Job Number 04653/C-209

ATH-
DPH/MOB
PT ISTANA KARANG LAUT
CONDENSATE
FRACTIONATION PLANT
PROJECT
PETROMAX REFINERY
LIMITED -MONGLA,
BANGLADESH
SEMI-REG REFORMING UNIT
(CRU) - UNIT 300
50.3 kt/yr
OPERATING INSTRUCTIONS
Rev. Date Prepared by Checked by Approved by Comments

Name: Name: Name:
0 August 2011 A. THOMAS D.P. PHAM-THI X. DECOODT
Signature: Signature: Signature:
This document contains confidential proprietary material belonging to Axens which may only be made available
to personnel or organizations who have signed appropriate secrecy agreements.
FO-43.DOT / Rév. 6.6 du 15.07.2009 04653 300 IO Operating Instructions Rev0
Job Number Unit Type Page
04653 300 6IO 2
CLIENT : PT ISTANA KARANG LAUT Date By Check by Rev
CONDENSATE FRACTIONATION PLANT PROJECT – MONGLA, 26/08/11 ATH DPH 0
BANGLADESH
UNIT : SEMI-REG REFORMING UNIT (CRU)
SERVICE :
CONTENTS
6. OPERATING INSTRUCTIONS SECTION......................................... 4

6.1 Preface of section 6 ..................................................................... 4
6.1.1 General ..................................................................................... 4
6.1.2 Compulsory instructions and reference documents .................. 5
6.2 Purpose of the Process ............................................................... 7
6.3 Chemical reactions and catalysts .............................................. 8
6.3.1 Introduction ............................................................................... 8
6.3.2 Chemical reactions .................................................................... 9
6.3.3 Catalyst ................................................................................... 26
6.3.4 Process variables .................................................................... 38
6.4 Preparation for start-up ............................................................. 44
6.4.1 Chronology of operations ........................................................ 44
6.4.2 Equipment and unit inspection ................................................ 47
6.4.3 Preliminary operations............................................................. 52
6.4.4 Drying out of the unit ............................................................... 61
6.4.5 Catalyst loading ....................................................................... 65
6.4.6 Chloride adsorbers loading ..................................................... 76
6.4.7 Second leak test ...................................................................... 76
6.5 First start-up ............................................................................... 77
6.5.1 Status of the unit ..................................................................... 77
6.5.2 Chronology of start-up operations ........................................... 77
6.5.3 Stabilizer start-up on total reflux .............................................. 78
6.5.4 Deethanizer start-up on total reflux ......................................... 79
6.5.5 Catalyst drying ........................................................................ 79
6.5.6 Catalyst reduction.................................................................... 80
6.5.7 Catalyst sulfiding ..................................................................... 81
6.5.8 Oil-in ........................................................................................ 82
6.5.9 Start-up phase ......................................................................... 83
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6.5.10 Figures and drawings attached to putting the unit into service 84
6.6 Operation of the unit ................................................................. 91
6.6.1 Summary of operating conditions ............................................ 91
6.6.2 Control philosophy of the Process ........................................... 91
6.6.3 Operating parameters ............................................................. 91
6.6.4 Adjustment of operating conditions ....................................... 100
6.6.5 Troubleshooting .................................................................... 124
6.7 Shutdown and restart of the unit ........................................... 131
6.7.1 General ................................................................................. 131
6.7.2 Unit restart............................................................................. 135
6.7.3 Emergency shutdown ............................................................ 136
6.8 Catalyst specifications and special procedures .................. 140
6.8.1 Manufacter ............................................................................ 140
6.8.2 Catalyst specifications ........................................................... 140
6.8.3 Packaging, handling and storage .......................................... 140
6.8.4 Special procedures................................................................ 145
6.8.5 Chemicals ............................................................................. 163
6.9 Safety and health recommendations ..................................... 165
6.10 Analytical control ..................................................................... 166
6.10.1 Recommended methods and frequency................................ 166
6.10.2 Description of IFP/Axens analytical methods ........................ 171
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6. OPERATING INSTRUCTIONS SECTION

6.1 Preface of section 6
6.1.1 General
The aim of Section 6 « OPERATING INSTRUCTIONS » is twofold :
First, to provide Operation staff with the necessary background and information to
understand the process, prepare the unit for start-up, operate it and shut it down and prevent
or correct operation upsets. Special procedures for catalyst handling or treatment prior to
start-up as well as the relevant list of analyses and specific safety recommendations are also
included.
Second, to provide the Engineering Company in charge of the detailed engineering of the
unit with additional information to the process equipment specifications (section 2 of the
Process Book). This information will help to understand the reasons for the specific
requirements shown in the equipment specification sheets that do not stem from unit normal
operation.
This section will also justify the use of special equipment, if any, required by temporary
operations.
The information supplied in Section 6 « OPERATING INSTRUCTIONS », is valid for any
unit using the considered process. However, it is not a detailed Operating Manual
tailored to the equipment selected for a specific customer.
Such an Operating Manual would have to include specific equipment characteristics and their
relevant operating instructions (related to rotating machines for instance) as well as Unit
Owner requirements, specifications or rules which are not known at this stage. Such an
Operating Manual is beyond Axens’ responsibilities as a Process Licensor.
Some of the instructions given herein can be considered as a reminder. This is the case of
the instructions of a general nature such as those pertaining to the precommissioning and
commissioning of the equipment, except where Axens issues specific requirements clearly
identified. It is expected these tasks of a general nature will be performed by the Engineering
Company and/or Unit Owner in accordance with the prevailing codes and rules and with
good Engineering practice.
All and every instructions, which relate to the operation of the unit and have an impact
on the responsibilities of the licensor must be strictly followed, and can be altered
only by Axens’ representative within the range of the unit operating conditions.
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6.1.2 Compulsory instructions and reference documents

These compulsory instructions are essentially covered in the following chapters:
 Preparation for start-up :
- Equipment and Unit in spection
- Drying out of the unit
- Catalyst loading
 First start-up
 Operation of the unit
 Shutdown and restart of the unit
 Catalyst specifications and special procedures
Section 6 is part of the Process Book and the reader can refer to the other sections of the
Process Data Book, if required.
Reference documents
The present Operating Instructions are established consistently with all other documents
included in the Process Book issued by Axens.
Process Flow Diagrams: Reference number Rev.

REACTION SECTION 04653 300 5FD Design case 1_4 0
04653 300 5FD Check case 1_4 0
ABSORPTION SECTION 04653 300 5FD Design case 2_4 0
04653 300 5FD Check case 2_4 0
STABILIZATION SECTION 04653 300 5FD Design case 3_4 0
04653 300 5FD Check case 3_4 0
DEETHANIZER SECTION 04653 300 5FD Design case 4_4 0
04653 300 5FD Check case 4_4 0
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Piping and Instrumentation Diagrams:

FEED SECTION 04653 300 5PD Sheet 01_18 0
REACTION SECTION PREHEATER AND FIRST 04653 300 5PD Sheet 02_18 0
REACTOR
REACTION SECTION FIRST INTERHEATER 04653 300 5PD Sheet 03_18 0
AND SECOND REACTOR
REACTION SECTION SECOND 04653 300 5PD Sheet 04_18 0
INTERHEATER AND THIRD REACTOR
SEPARATION SECTION 04653 300 5PD Sheet 05_18 0
RECYCLE COMPRESSOR SECTION 04653 300 5PD Sheet 06_18 0
H2 COMPRESSORS 04653 300 5PD Sheet 07_18 0
RECONTACTING COOLING SECTION 04653 300 5PD Sheet 08_18 0
H2 RICH GAS CHLORIDE ADSORBERS 04653 300 5PD Sheet 09_18 0
LPG ABSORBER DRUM 04653 300 5PD Sheet 10_18 0
STABILIZER FEED PRE-HEATING 04653 300 5PD Sheet 11_18 0
STABILIZER COLUMN 04653 300 5PD Sheet 12_18 0
STABILIZER REFLUX DRUM AND 04653 300 5PD Sheet 13_18 0
DISTILLATE PUMPS
STABILIZER REBOILER AND STABILIZER 04653 300 5PD Sheet 14_18 0
REBOILER PUMPS
DEETHANIZER FEED PRE-HEATING 04653 300 5PD Sheet 15_18 0
DEETHANIZER COLUMN 04653 300 5PD Sheet 16_18 0
DEETHANIZER REFLUX DRUM AND DISTILLATE 04653 300 5PD Sheet 17_18 0
PUMPS
PACKAGES CHEMICALS INJECTIONS 04653 300 5PD Sheet 18_18 0
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6.2 Purpose of the Process

The reforming process is a catalytic process to convert low octane naphthas into higher
octane reformate products for gasoline blending. Naphtha feed to this unit is hydrotreated
heavy naphtha from NHT Hydrotreating Unit (Unit 200). A valuable by-product from this
process is the hydrogen released from the aromatic producing reactions. This hydrogen is
necessary to support the upstream hydrotreating unit which is necessary to prepare the
naphtha feed to be reformed.
This reforming process includes a reaction section, H2 purification and stabilization. The
reforming reactions take place in fixed catalyst beds under a hydrogen environment at a
moderately low pressure (15.6 kg/cm2 g at first reactor inlet). A high temperature in the
range 480-510 deg.C is required to promote the chemical reactions which improve the
octane number. Some of the desirable reactions are endothermic; this requires splitting the
bulk of the catalyst into several reactions with intermediate reheaters to re-establish the
reaction temperature.
This is the conventional, fixed bed, semi-regenerative process which requires a shutdown for
catalyst regeneration (coke removal) after the design cycle length has been reached.
This operating instructions manual includes the necessary instructions to operate the
conventional semi-regenerative unit.
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6.3 Chemical reactions and catalysts

6.3.1 Introduction
6.3.1.1 Objectives of this chapter
The aim of the information given in this chapter is to provide enough theoretical background,
in the simplest possible way, to supplement the instructions given in the chapters that follow,
i.e. Start-up of unit, Operation of the unit and Shutdown of the unit.
It is expected that this theoretical support helps the operators to better understand the
reasons of the operating instructions and enables them to make considered decisions,
should the circumstances deviate from what is covered in the Operating Instructions.
6.3.1.2 Thermodynamics and kinetics
For any chemical reaction the thermodynamics dictates the possibility of its occurrence and
the amount of products and unconverted reactants. Under certain conditions (P, T) some
reactions are 100% completed meaning that all the reactants are converted into products.
Others are in equilibrium so that part of the reactants is only converted. Thermodynamics
dictates the equilibrium. Thermodynamics does not predict the time required to reach
equilibrium or the full completion of a reaction.
Kinetics dictates the rate of a chemical reaction or the amount of feed that disappears in a
specified amount of time say, one second. Kinetics, which dictated the rate of reaction, is
dependant on operating conditions but can also be widely modified with 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 to forecast the composition after a finite time. Since time is
always limited, when several reactions proceed simultaneously, kinetics is generally
predominant.
A heterogeneous catalyst generally consists of a support (alumina, silica, magnesia,...) on
which (a) finely divided metal(s) is (are) dispersed.
The metal is always responsible for the catalytic action. Very often, the support, has also a
catalytic action linked to its chemical nature.
A catalyst is not consumed but can be deactivated either by impurities in the feed or by some
of the products of the chemical reactions involved, resulting in coke deposit on the catalyst.
The different chapters of the section describe:
• The various chemical reactions involved in the process as well as the effect of the
operating conditions.
• The catalyst characteristics.
• The catalytic mechanism or catalysis.
• The catalyst contaminants.
• The process variables.
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6.3.1.3 Catalyst activity, selectivity, stability

The main characteristics of a catalyst other than its physical and mechanical properties are:
 The activity which is the catalyst ability to increase the rate of the reactions involved. It is
measured by the temperature at which the catalyst must be operated to produce a product
on-specification, for a given feed, all other operating conditions being equal.
 The selectivity expresses the catalyst ability to favour desirable reactions rather than
others. It is measured by the quantity of desired product.
 The stability characterizes the change with time of the catalyst performance (i.e., activity,
selectivity) when operating conditions and feed are stable. It is chiefly polymers or coke
deposits that affect stability since they decrease the metal contact area. Traces of some
metals in the feed also adversely affect stability.
6.3.2 Chemical reactions

6.3.2.1 Fundamental reactions
The chemical reactions involved in reforming processes are of two types:
• Desirable reactions, i.e. reactions which lead to an increased octane number and to high
purity hydrogen production. These are the reactions to promote.
• Adverse reactions, i.e. reactions which lead to a decreased octane number, a decrease
in hydrogen purity or a loss in products yield. These are the reactions to minimize.
The heat of the reactions mentioned hereafter as well as their relative rate is necessary to
understand the process. They are listed for the ease of reference in Table 1, below. A
catalyst is being used to promote the desirable reactions at the expense of the adverse ones
through its action on reaction kinetics.
TABLE 1
REFORMING REACTIONS
HEAT OF REACTION - RELATIVE RATE OF REACTION
REACTIONS HEAT OF RELATIVE RATE
REACTION (2) APPROX.
(1) KCAL/MOLE
Naphthenes dehydrogenation - 50 30
Paraffin dehydrocyclization - 60 1 (base)
Isomerization: Paraffins +2 
3
Naphthenes +4 
Cracking + 10 0.5
(1) Heat of reaction lower than 0 = endothermic reaction.
(2) For pressure below 15 bar.
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A) Desirable reactions with hydrogen production

(m) Catalyst metallic function
(a) Catalyst acidic function
a) Naphthenes dehydrogenation
Naphthenic compounds i.e. cyclohexane, methylcyclohexane, dimethylcyclohexane 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 cyclohexane reaction, for instance, proceeds as follows:

CH CH
2
HC CH (m) HC
2 2 CH
+ 3H
2
HC CH HC CH
2 2
CH CH
2
Cyclohexane Benzene
Note: Cyclohexane and benzene are generally schematically represented as follows:
Cyclohexane Benzene
Thermodynamically the reaction is highly endothermic and is favored by high temperature

and low pressure. In addition the higher the number of carbon atoms, the higher the
aromatics production at equilibrium.
From a kinetic view point, the rate of reaction increases with temperature (Refer to figure 2)
and is not affected by the hydrogen partial pressure (Refer to figure 1). The rate of reaction
is high compared to other reactions (table 1). It also increases with the number of carbon
atoms.
At the selected operating conditions the reaction is very fast and almost total. It is promoted
by the metallic function of the catalyst. Since it yields a high octane product, promoting this
reaction is most desirable: refer to octane number below:
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Note that cyclopentane, present in feeds having a low ASTM D86 IBP, is an undesirable
component as either it does not react or its cycle is broken and results in low carbon parafins
or olefins and hydrogen consumption.
RON MON
• Cyclohexane = 83 77.2
• Methylcyclohexane = 74.8 71.1
• 1.3 dimethylcyclohexane = 71.7 71.0
• Benzene = 114.8 > 100
• Toluene = 120 103.5
• m-Xylene = 117.5 115.0
RON : Research Octane Number
MON : Motor Octane Number
Note : Throughout this document, "octane" is generally used for "octane number"
b) Paraffins dehydrocyclization
This is a multiple step process which applies either to the normal paraffins (linear) or iso-
paraffins (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.
The reaction can be summarized as follows:
CH CH CH (m) CH CH CH
2 2 2 2 2
+H
CH CH CH CH CH CH CH 2
3 2 2 3 3 CH 2 3
CH CH
7 16 7 14
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CH CH
2 2
CH CH CH (a) CH
2 2
HC CH
2 3
CH CH CH CH
3 2 3 CH CH
2 2
Methylcyclohexane
CH CH CH CH
2 2
(m) C
HC CH CH
3 HC CH + 3H
2 3 2
CH CH CH CH
2 2
Toluene
The paraffin dehydrocyclization step becomes easier as the molecular weight of the paraffin
increases; however the tendency of paraffins to hydrocrack increases concurrently (Refer to
figure 3).
Kinetically, the rate of dehydrocyclization increases with low pressure and high temperature
(figures 1 and 2), but altogether, at the selected operating conditions, this rate is much lower
than that of naphthene dehydrogenation (30/1). The reaction is promoted by both catalytic
metallic and acidic functions.
c) Effect of parameters on naphthene dehydrogenation

The tables below summarize the effect of the main parameters governing the
dehydrogenation and dehydrocyclization reactions.
Thermodynamics dictates the equilibrium which could be theoretically reached (i.e. if the time
was infinite). Kinetics dictates the rate of reaction, i.e. the possibilities to reach a state close
to equilibrium in a finite time.
Increase of Effect on dehydrogenation due

to thermodynamics to kinetics
Pressure decreases unaffected
Temperature increases increases
H2/HC ratio (1) slightly decreases slightly decreases
(1) Ratio of pure hydrogen (mole) to hydrocarbon feed (mole).
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d) Effect of parameters on paraffin dehydrocyclization
Increase of Effect on dehydrocyclization due

to thermodynamics to kinetics
Pressure decreases decreases
Temperature increases increases
H2/HC ratio slightly decreases slightly decreases
B) Desirable reactions without hydrogen production

a) Linear paraffins isomerization
Reaction is as follows: (a)
CH
7 16 CH
7 16
These reactions are fast, slightly exothermic and do not affect the number of carbon atoms.
The thermodynamic equilibrium of isoparaffins to paraffins depends mainly on the
temperature. The pressure has no effect.
Iso-N paraffin equilibria

Carbon atom C4 C5 C6 C7 C8
% Isoparaffin at 44 58 72 80 88
500deg.C
The paraffins isomerization results in a slight increase of the octane number. From a kinetic
view point (figures 1 and 2), high temperature favors isomerization but hydrogen partial
pressure has no effect. These reactions are promoted by the acidic function of the catalyst
support.
b) 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 a paraffin is high.
The reaction is slightly exothermic. The reaction can be summarized as follows:
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(a)
CH3
CH3
Alkylcyclopentane Alkylcyclohexane
(Ethylcyclopentane) (Methylcyclohexane)
Theoretically, at the selected operating temperature (about 500deg.C) the thermodynamics

limits the alkylcyclohexane formation. But the subsequent dehydrogenation of the
alkylcyclohexane into an aromatic shifts the reaction towards the desired direction. This type
of reaction(is also easier for higher carbon number.(
The octane number increase is significant when considering the end product (aromatics) as
shown:
RON MON
• Ethylcyclopentane = 67.2 61.2
• Methylcyclohexane = 74.8 71.1
• Toluene = 120 103.5
C) Adverse reactions
a) Cracking
Cracking reactions include hydrocracking and hydrogenolysis reactions.
Hydrocracking affects either paraffins (normal or iso) or olefins. It involves both the
acid and metallic function of the catalyst. It is, to some extent, a parallel reaction to paraffin
dehydrocyclization.
It 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 reaction is promoted by the
acidic function of the catalyst.
(m)
+H
2
CH CH
7 16 7 14
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(a)
+
+H
2
CH CH CH
7 14 4 8 3 8
(m)
+H
2
CH CH
4 8 4 10
The first reaction involves the same reactants as the dehydrocyclization and is likewise
catalysed by the metallic function.
Hydrocracking also affects the naphthenes, the overall reaction can be summarized as
follows:
+H or
2
CH - C H CH
3 5 9 6 14
or
+H or
2
CH - C H CH
3 6 11 7 16
At the selected operating conditions, hydrocracking reaction could be almost complete.
Fortunately it is somewhat limited by its kinetics. Compared to its desirable concurrent
reaction (dehydrocyclization), hydrocracking becomes significant as the temperature
increases. It is also favored by high pressure.
The main effects of hydrocracking are:
• A decrease of paraffins in the reformate which results in an increase of the aromatics
percentage (i.e. an increase in octane) and a loss of reformate.
• A decrease in hydrogen production.
• An increase of LPG production.
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b) Hydrogenolysis
This undesirable reaction has some similarity with hydrocracking since it involves hydrogen
consumption and cleavage of bonds. But it is promoted by the metallic function of the
catalyst and leads to lighter hydrocarbon C1 + C2 - even less valuable than LPG
(C3 + C4).
It can be represented schematically as follows:
(m)
+H CH +
2 4
CH
7 16
m CH
6 14
or )
(m)
+H CH +
2 2 6
CH
7 16
m CH
5 12
)
Like hydrocracking it is exothermic and favored by high pressure and high temperature.
c) Hydrodealkylation
Hydrodealkylation is the breakage (or cleavage) of the branched radical (-CH3 or -C2H5) of an
aromatic ring.
Xylene (two radical groups) can be dealkylated into toluene (one radical group) which in turn
can be dealkylated to benzene.
The standard representation is:
(m)
+H + CH
2 m 4
)
Xylene Toluene
(m)
+H + CH
4
2 m
)
Toluene Benzene
Hydrodealkylation consumes hydrogen and produces methane. It is favored by high
temperature and high pressure and promoted by the metallic function of the catalyst.
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d) Alkylation
Alkylation is a condensation reaction which adds an olefin molecule on an aromatic ring. It
results in an aromatic with an increased molecular weight. The reaction proceeds as follows:
CH
(m) 3
+ CH = CH - CH HC
2 3
CH
3
Benzene Propylene Isopropylbenzene
This reaction, promoted by the catalyst metallic function, is not hydrogen consuming. But it
leads to heavier molecules which may increase the end point of the product. In addition the
high molecular weight hydrocarbons also have a high tendency to form coke. This reaction
must be avoided.
e) Transalkylation (Alkyl disproportionation)

Two toluene rings (one branched CH3 radical) can disproportionate to produce one benzene
ring (no branched radical) and one xylene ring (two branched radicals), as shown:
(m)
+ +
m
Toluene Toluene ) Benzene Xylene
This reaction, promoted by the catalyst metallic function, occurs mainly in very severe
conditions of temperature and pressure.
f) Coking
Coke formation on the catalyst results from a very complex group of chemical reactions, the
detailed mechanism of which is not fully known yet.
Coke formation is linked to heavy unsaturated products such as polynuclear aromatics (or
polycyclics which can be dehydrogenated) resulting either from the feed or from the
polymerization of aromatics involved in some of the reforming reactions (dehydrocyclization,
disproportionation,...). Traces of heavy olefins or diolefins may also result from the reforming
reactions (dehydrocyclization, alkylation, for instance) and promote coke formation.
A high end boiling point of the feed means greater amount of polyaromatics and then a
higher coking tendency. Since condensation is promoted by high temperature, poor
distribution in a reactor favors local high temperatures and coke build up.
Coke deposit on the catalyst reduces the active surface area and greatly reduces catalyst
activity.
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6.3.2.2 Kinetic analysis of the chemical reactions

The effect of the main operating conditions on the rate velocity of the reactions involved in
the reforming process using the selected catalyst is summarized below.
A) Effect of hydrogen partial pressure
Figure 1, shows, with a semi-logarithmic scale, the relative rate velocity of the various
reactions as a function of hydrogen partial pressure. The dehydrogenation rate is used as
reference and taken at 100 (Log 100 = 2). Other reaction rates are measured against this
reference.
At 10 barg hydrogen partial pressure, the dehydrogenation of naphthene is about 10 times,
faster than isomerization, 30 times faster than dehydrocyclization and 50-60 times faster than
cracking (hydrocracking and hydrogenolysis).
At relatively high pressure (above 20 barg) the rate of coking is low compared to the other
reactions but it increases noticeably at lower pressure.
To sum up, figure 1 shows that there is an incentive to operate at low pressure:
cracking rate will be reduced and dehydrocyclization rate increased as well as the
coking rate.
On another hand thermodynamics also favors low pressure for dehydrogenation and
dehydrocyclization. The only drawback of low pressure is the high coking rate.
B) Effect of temperature
Temperature influences the rate of the various reactions as shown in figure 2. Energy of
activation is calculated from the slope of the curves. Dehydrogenation has a moderate
energy of activation (~ 20 Kcal. mole -1) as does isomerization (~ 25 Kcal. mole -1) and
consequently temperature only slightly increases the rate of these reactions.
Dehydrocyclisation has an higher activation energy 35 Kcal/mole-1 and consequently
temperature increases the rate of reaction.
Cracking and coking have higher energy of activation (45 and 35 Kcal. mole -1 respectively).
The rate of these undesirable reactions is more significantly increased by temperature.
To sum up, a higher temperature clearly favors the undesirable reactions more than
the desirable one. However a moderate temperature rise is required during the
catalyst life to maintain catalyst activity and therefore to produce octane.
C) 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 it is the case for thermodynamic equilibria, it appears that the rates of the reactions are
affected by the length of the chain of the reactant. Figure 3, presents the rates of
dehydrocyclization and cracking of C6 to C10 paraffins related to that of n-heptane, as a
function of the number of carbon atoms of reactant.
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Figure 3, shows that the cracking reaction rate, (the cracking curve represents in fact the
sum of hydrocracking and hydrogenolysis), increases regularly with the number of carbon
atoms, whereas dehydrocyclization rate exhibits a sudden increase between hexane and
heptane as well as between heptane and octane, while the variation between the higher
homologues remains relatively slight.
To sum up, 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 fraction to feed a reforming process is the
C6- C10 fraction.
CONCLUSIONS:
From the above analysis it can be concluded:
(a) Dehydrogenation reactions are very fast, about one order of magnitude faster than the
other reactions.
(b) Low pressure favors all desirable reactions and reduces cracking. To compensate the
detrimental effect of low pressure on coking, low pressure reformer requires continuous
catalyst regeneration. For semi regenerative reformer the recommended lowest
operating pressure to have acceptable cycle length is about 12 kg/cm2g.
(c) An increase in temperature favors the kinetics of dehydrogenation, isomerization,
dehydrocyclization, but accelerates the degradation reactions (cracking, coking) even
more. Consequently an increase in temperature leads to an increased octane associated
with a decrease in reformate yield.
(d) The reaction rates of such important reactions 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 suitable feed.
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FIGURE 1:
RELATIVE RATE OF REACTION vs HYDROGEN PARTIAL PRESSURE
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FIGURE 2:
RELATIVE RATE OF REACTION (V) vs TEMPERATURE
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FIGURE 3:
RELATIVE RATE OF REACTION vs NUMBER OF CARBON ATOMS
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6.3.2.3 Catalyst distribution in reactors

Thermodynamics and kinetics have shown that there is an optimum operating temperature
range, approximately 450deg.C- 520deg.C in order to simultaneously favor the rate of the
desirable reactions and limit the undesirable ones to an acceptable level. For each specific
case, the most appropriate operating temperature is selected taking into account the feed
quality (PNA, distillation range ...) and product requirement (octane).
Owing to the great endothermicity of the most important and desirable reactions (naphthenes
dehydrogenation and paraffins dehydrocyclization) this optimum temperature cannot be
sustained through out the whole catalyst volume. In addition, dehydrogenation is also, by far,
the fastest reaction, which means that the temperature drops very sharply over the first part
of the catalyst. In order to restore the catalyst activity, when temperature has dropped to a
certain level which depends upon the reactions involved, the reactor feed is reheated. To
achieve this, the catalyst is distributed in 3 reactors and intermediate heaters are provided.
Figures 4 and 5, illustrate this aspect, Figure 4 shows for a given feed (Paraffins: 45% LV,
Naphthenes 45% LV, Aromatics 10% LV) the profile of the amount of P.N.A along the
catalyst volume. In this case there is no need for more than 20% of the catalyst in the first
reactor because the naphthenes dehydrogenation results in a temperature too low to sustain
the reaction any longer. The reactor effluent is reheated to allow for the naphthenes
dehydrogenation to continue and the paraffin dehydrocyclization to start. Over the next 30%
of catalyst, distributed in the 2nd reactor, temperature drops again to a level where reheating
is required to enable the paraffin dehydrocyclization to proceed.
In this unit (3 reactors) the catalyst distribution is:

• R1 = 20 %
• R2 = 30 %
• R3 = 50 %
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Each specific case, obviously, requires a specific catalyst distribution.

In a somewhat simplified but practical way, for operational guidance, the main reactions
which take place in the various reactors can be represented in the following order:
• 1st reactor:
– Dehydrogenation
– Isomerization
• 2nd reactor:
– Dehydrogenation
– Isomerization
– Cracking
– Dehydrocyclization
• 3rd reactor:
– Cracking
– Dehydrocyclization
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CATALYST DISTRIBUTION IN THE 3 REACTORS

FIGURES 4 AND 5
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6.3.3 Catalyst
6.3.3.1 Catalyst characteristics
The Reforming catalysts RG 682A is a bimetallic catalyst consisting of platinum plus rhenium
promotor on an alumina support.
See paragraph 6.8 for the technical specifications.
The main features of these catalysts are:

• High purity alumina support having a strong mechanical resistance.
• High stability and selectivity due to the platinum associated with rhenium.
• High regenerability.
The combination of these qualities give the following advantages:
• High reformate yield.
• High hydrogen yield.
• High on-stream factor (long cycle duration).
• Low catalyst inventory.
6.3.3.2 Catalyst mechanism

A) Activity: metallic and acidic functions
The catalyst affects reaction rates through its two different functions: metallic and acidic,
which promote different type of reactions.
Dehydrogenation and hydrogenation reactions are enhanced by the metal activity.
Structural rearrangements of the molecules (from linear to cyclic for instance) which involve a
reorganization of the carbon bonds are primarily catalyzed by the acidic function of the
support.
Because of its high activity in dehydrogenation and dehydrocyclization, platinum has been
selected for the base catalytic metal. Promotor has been added to improve catalyst
selectivity and stability.
The support is a high purity alumina (acidic function) which is chiefly active for the cyclization
of paraffins to aromatics and for isomerization reactions.
In short, the main reactions involved in reforming processes are catalyzed essentially either
by the acid support or the metal functions, as indicated below:
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Dehydrogenation Metallic function

Dehydrocyclization Metallic + acidic functions
Isomerization Metallic + acidic functions
Hydrogenolysis Metallic function
Hydrocracking Metallic + acidic function
B) Metallic function
For a maximum catalyst activity the metal must be highly dispersed on the alumina support
and under the minimum possible particle size (actual figure is in the range of 1.10-6 mm).
This high dispersion and micrometric particle size which results from the special
manufacturing process must be maintained during the catalyst life by the use of proper
operating conditions and restored after regeneration.
In fact catalyst ageing and coke deposit require a temperature increase which favors metal
agglomeration and particle growth. The coke burning during the regeneration results in
further chlorine elution owing to combustion water, as explained in paragraph C hereunder.
Therefore an oxychlorination step is required to restore the chlorine level but also to favor the
re-dispersion of the metal.
A wet reduction leads to sintering of the metallic phase.
The poisoning of the metallic function is covered in detail in chapter “Catalyst contaminants”.
C) Acidic function
A certain level of acidity of the catalyst support is required to promote some of the desired
reactions (isomerization, dehydrocyclization). The optimum level of acidity changes
somewhat with the desired performance (maximization of gasoline and hydrogen yields or
gasoline and LPG production).
The acidity of the catalyst is dependant on the amount of chlorine which is fixed on the
catalyst at the manufacturing stage, then added in the oxychlorination stage of the
regeneration.
During operation chlorine elution (leaching) from the catalyst is a function of the recycle gas
moisture. The chlorine content of the catalyst is kept constant by injecting a chlorinated agent
into the reformer feed. To be noted, chlorine favours the bonding of metals/support.
Consequently low chlorine levels are promoting metals sintering or agglomeration.
The chlorine content of the catalyst must be in the range 0.9 % to 1.1 wt%. Moreover it is
known that alumina based catalysts require some moisture to activate the acidic
function.
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A simplified representation of the catalyst support chemical structure, after chlorination is as

follows:
OH Cl OH
Al Al Al
O O
The simplified theory, generally accepted today, suggests that the optimum acidity level
(which varies with the requested performance) is a function of concentration of the -OH
groups and the -Cl groups.
The relative concentrations, in turn are a function of the water and HCl content in the recycle
gas, because of the equilibrium which exists, between water and HCl in the recycle and -OH
and -Cl groups on the catalyst.
For the purpose of Reforming, this optimum acidity level is obtained for water content in the
recycle in the range 15 - 25 ppm vol. The associated HCl content should be approximately
0.5 ppm vol or less.
The basic recommendation is then to operate with 0.9 to 1.1 wt % of chloride on the
catalyst.
Starting from the optimum catalyst structure (the right balance of -OH vs. -Cl), an excess of
water in the recycle gas will shift the balance towards excess of -OH and reduces the
activity.
This is referred to as chloride elution or leaching by water and can be represented

schematically as follows:
OH Cl OH OH
Al Al +H O Al Al + HCl
2
O O
Conversely, if the amount of water in the recycle is too low the catalyst is rendered too dry,
and the -OH to -Cl balance is shifted towards -Cl. In other words, the catalyst is over
chlorinated, which means its acidic function is exacerbated (trend to hydrocracking and
increasing coking rate).
Of course, over-chlorination of the catalyst may result merely from the accidental presence of
chlorine, or uncontrolled addition, in the feed.
There are a couple of other occurrences worth mentioning:
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• If a catalyst is excessively dry (i.e. it has been operated with a deficiency of water for
some time) it will exhibit a very high acidic function indicated by an increased
hydrocracking activity.
• If a catalyst excessively dry undergoes a water upset (amount of water in the recycle over
50 ppm vol.) a situation may occur where the water displaces the chlorine from the first
reactors towards the last reactor with a subsequent temporary increase of the acidic
function and hydrocracking activity in the last reactor.
To conclude, for an optimum operation of the Reforming Unit:
• The chloride content of the catalyst must be maintained between 0.9 to 1.1 wt %.
Operators can adjust the chloride injection rate based on catalyst analysis.
• The water content in the recycle gas must be maintained between 15 to 25 volume
ppm.
D) Alteration of catalyst activity

The causes and consequences of catalyst activity loss (due to an unbalance of either the
acidic or metallic function) are listed in Table 2.
TABLE 2
Decrease of metallic
Decrease of acidic function Increase of acidic function
function
• Elution of chloride due to • Over chlorinated catalyst • Temporary reversible
Causes
high water content in the due to: poisoning by sulfur.

recycle gas.
– chlorine in the feed • Permanent poisoning by
• Nitrogen compounds (loss of metals.
– or too low water in recycle
Cl through NH4Cl) in the
gas.
feed.
• High water content in the
recycle gas (upset) on a
very dry catalyst (the acidic
function increase is
temporary).
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Initial consequences
• Decreased octane. • Slight increase in octane. • Large decrease in octane.

• Decreased LPG production. • Decrease in liquid product • Decreased delta T in first
and H2 yields. reactor.
• Increased Cl production
related to C1-C4 cut. • Increased LPG production. • Decreased C1 + C2
production.
• Increased recycle gas H2 • Decreased C1 production
purity. related to C1-C4 cut. • Increased liquid production.
• Increased liquid product • Decreased recycle gas H2 • Large decrease of H2
yield. purity. production.
• Decreased T in last • Decreased recycle gas H2
reactor. purity.
6.3.3.3 Catalyst contaminants

Catalyst contaminants are classified in two categories: temporary poisons (sometimes called
inhibitors) and permanent poisons.
Temporary poisons are those which can be removed from the catalyst without a shutdown
and for which the catalyst proper activity and selectivity is restored once the contaminant
disappears.
The effect of temporary poisons, if the operator maintains the operating conditions prevailing
before the poisoning, is a temporary decrease of performance.
The most common temporary poisons (inhibitors) of reforming catalysts are sulfur,
organic nitrogen, water, oxygenated organics and halogens.
Permanents poisons are those which induce a loss of activity 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, nickel, chromium, mercury,
sodium, potassium.
In order to ensure the optimum use of the catalyst, a proper design shall include:
• The removal of poisons from the feed prior to its introduction to the unit.
• The necessary procedures to remove, as far as possible, the temporary poisons from the
contaminated catalyst.
Impurities from the feed are removed by pretreating feed in adequately designed units.
However their efficiency is never complete and generally limited depending upon the type of
impurities to be removed. In addition a poor adjustment of the operating conditions of the
pretreating unit results in a decreased efficiency.
A smooth and successful operation of the reforming unit requires the proper
adjustment and control of the operating conditions of the pretreating unit.
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A) Temporary poisons
• Sulfur
Sulfur is the most common impurity found in the feed of any reforming unit. The maximum
allowable concentration is 0.5 ppm wt expressed as S. Whenever possible, operation at
lower sulfur content will provide additional catalyst stability and selectivity.
– Mechanism:
Poisoning is caused by H2S, either contained in the unit feed, or resulting from the
decomposition, on the catalyst, of sulfur compounds contained in the feed.
H2S reacts with platinum according to the equilibrium reaction:
Pt + H2S PtS + H2
and with rhenium according to the equilibrium reaction:
Re + H2S ReS + H2
and consequently it reduces the activity of the catalyst while decreasing the metallic contact
area.
The same type of reaction occurs with H2S towards the rhenium, and further reduces the
catalyst activity.
– Effect of sulfur contamination:
Sulfur contamination inhibits the metal function of the catalyst. This is indicated by:
• A decrease in hydrogen yield.
• A decrease in recycle gas purity.
• An increase in hydrocracking (LPG yield increase).
• An increased coking rate.
• A reduced temperature drop in the reactors, especially first one and sometimes an
increase T across the second reactor.
– Prevention and causes of contamination:
Sulfur removal is achieved by pretreating the naphtha feed, which results in H2S production.
Poor operation of the pretreater is generally the cause of sulfur poisoning of the reforming
catalyst:
• Either low activity of the hydrotreater catalyst.
• Sudden change of feed characteristics (EBP, total sulfur).
• Or too low hydrotreater reactor temperature or hydrogen partial pressure.
which leads to an insufficient sulfur removal. Unsatisfactory operation of the hydrotreater
stripper can also result in dissolved H2S being fed to the reforming unit. In such a case water
content of the reforming feed also increases.
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– Detection:
Analytical methods are available to detect sulfur in the unit feed. A very easy way, however,
is to check sulfur content in the recycle gas using Draëger tubes. The H2S content in the
recycle which corresponds to the 0.5 ppm wt in the feed, is approximately 1 ppm volume.
H2S detection can also be performed on the stabilizer column off-gas (about 5 ppm volume
corresponding to 1 ppm volume in the recycle gas).
– Remedies:
When the sulfur content in the recycle gas increases, the reactor inlet temperature must be
reduced.
Typically for an H2S level of 5 ppm vol in the recycle the reactor inlet temperature must be
lowered to 480deg.C; the reformer feed must be reduced accordingly to maintain product
quality (octane number). These conditions must be maintained until the cause of the upset
has been found and corrected. Temporary by chloride injection shall be increased by about 1
ppm wt.
The high severity operating conditions can only be resumed when the H2S content in the
recycle gas is lower than 1 ppm vol.
In no instance shall the lost activity due to sulfur poisoning be compensated with
temperature.
• Nitrogen:
Nitrogen is less frequently present in the reforming feed than sulfur. Scarcely present in
straight run naphtha, nitrogen is a usual impurity of cracked naphtha and may also result
from injection of amine based corrosion inhibitors.
The maximum allowable concentration in the feed is 0.5 ppm wt expressed as organic
nitrogen.
Organic compounds containing nitrogen are responsible for inhibition but nitrogen gas itself
(N2) has no detrimental effect.
– Mechanism:
Contamination is due to NH3 formed by decomposition of compounds containing organic
nitrogen, on the catalyst. Then NH3 which is alkaline, reacts with chlorine decreasing the
acidic function of the catalyst and producing ammonium chloride NH4Cl. This compound is
volatile in the conditions of the reactors and is eliminated inducing a loss of chlorine.
The reaction can be represented schematically as follows:
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Cl OH Cl Cl OH OH
NH3 + H O + Al Al Al
2 Al Al Al + HCl + NH
3
O O O O
and HCl + NH NH Cl
3 4
– Effect of nitrogen contamination:

Nitrogen contamination reduces the acidic function and is indicated by:
• A decrease in octane.
• A slightly increased hydrogen production.
• A reduced reactor temperature drop.
On top of this, ammonium chloride in the recycle gas can deposit in coolers, separators,
stabilizer cold trays, creating problems of corrosion (under deposit).
It is worth remembering that 0.5 ppm wt of organic nitrogen in the feed leads to
approximately 2 T/year of NH4 Cl for a 1 106 T/y unit.
Organic nitrogen removal is also achieved by naphtha pretreating of the feed. But it shall be
emphasized that nitrogen removal is more difficult than sulfur. Efficient nitrogen removal
often requires the use of a specific catalyst, also active for desulfurization, but generally
operating at higher hydrogen partial pressure. Naphtha, with high nitrogen content must not
be fed to a pretreater not designed for it.
Cracked naphthas are generally characterized by high organic nitrogen content,
consequently cracked naphthas shall never be introduced to a pretreater designed to
process straight-run feeds without getting technical advice from the licensor and/or
the catalyst manufacturer.
In the pretreating unit, decomposition of nitrogen compounds originates NH3. However the
amount is generally limited and easy to remove by stripping. The corrosion inhibitor (amine
based), usually injected in the pretreatment stripper shall be selected to be decomposed at
the condition of the stripper overhead line to avoid contamination of the stripper bottom
product (Reforming feed). In fact, the presence of nitrogen compounds in the feed is typically
due to a low activity of the pretreatment catalyst towards denitrification.
– Detection:
There is no available method for ammonia detection in the recycle gas. Thus laboratory
analysis need to be performed on the feed to detect nitrogen compounds.
– Remedies:
When nitrogen contamination is detected operators must:
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• Increase the chlorination agent injection.

• Not try to make up for the drop in octane number of the reformate by an increase of
the reactor inlet temperature. This will only increase the loss of chlorine.
• Take the necessary actions to lower the nitrogen content down to the acceptable
figure of 0.5 ppm wt.
• Water and oxygenated organic compounds:
Oxygenated organic compounds (methanol, MTBE, TAME, phenol...) are converted into
water at reactor conditions.
Water is not exactly a poison since some water is necessary to activate the acidic function of
the catalyst. However, in usual practice, elimination of water from reforming feed is a major
concern of operators, because an excess of water leads to a decrease in catalyst activity.
Water is often present in naphtha feeds, moreover water is frequently injected in reforming
feed hydrotreaters to remove formed salts in the cold part of the reaction section. The
maximum allowable content in feed is set to achieve approximately 20 ppm volume in the
recycle gas for conditions: P = 12 kg/cm2 g; T = 38deg.C at the separator drum. When
feeding a reformer unit from storage, route the sweet naphtha (ex-storage) through the HDS
unit stripper or splitter.
– Mechanism:
Water affects the acidic function of the catalyst and decreases the dehydrocyclization of
paraffins.
Water removal is usually achieved in the stripper of the feed hydrotreater. Generally
contamination by water results from a poor operation of this equipment.
– Detection:
Since water contamination is a major concern for the operator, on line analyzer is provided in
the recycle gas line.
Operating experience shows that the optimum water content in the recycle gas must be
within a range of 15 to 25 ppm (vol.). The associated chlorine level will then be about
0.5 ppm vol.
Above 50 ppm vol. of water, the reactor inlet temperature must be lowered to reduce the
chlorine elution (leaching) from the catalyst. The following figures are generally accepted:
• > 50 ppm water Temperature  480deg.C
• > 100 ppm water Temperature  460deg.C
Below 10 ppm of water in the recycle gas, the catalyst acidic function is enhanced. Water
injection must be used: 1 ppm wt in the feed results in an increment of 2 to 5 ppm vol. in the
recycle.
– Remedies:
In case of water upset,
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• Adjust chlorine injection to make up for the increased chlorine loss.

• Decrease reactor inlet temperature as indicated above.
• Restore operating conditions upstream of the unit to reduce water contamination.
• Check the amount of oxygenated compounds in the feed.
• If it is known that large ingress of moisture cannot be prevented, consider shutdown
of the unit until the situation is remedied.
• Halogens (chlorine, fluorine):
The maximum allowable amount in the unit feed is 0.5 ppm wt for each of them.
– Mechanism:
The presence of chlorine as chloride in the feed modifies the acidic function of the catalyst
and promotes the hydrocracking reaction. Once chloride is eliminated, the proper chloride
balance of the catalyst can be restored.
The effect of fluorine as fluoride is similar but it is more difficult to remove from the catalyst. It
is very seldom to find fluoride in the reformer feed.
– Effect of chlorine, fluorine contamination:
Hydrocracking reactions are enhanced:
• Lower liquid product yield.
• Higher LPG and C1 yields.
• Slightly higher octane.
• Decrease of hydrogen production.
Chlorine and fluorine are sometimes present in crude as organic halides owing to the field
production techniques. They are normally eliminated in the pretreatment stage. Note that if
present in pretreatment feed in notable quantity (several wt ppm) they provoke a huge
corrosion in the cold part of the pretreatment reaction section.
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B) Permanent poisons
Permanent poisons have been defined as contaminants which irreversibly damage the
catalyst.
Table 3 hereunder lists the main permanent poisons as well as their acceptable level in
reformer feed and their most likely source.
TABLE 3
Poisons Max. level (wt) Source
Arsenic 5 ppb max S.R. or cracked Naphthas
or gas condensates
Lead 5 ppb max Recycled slops
Copper < detection limit Corrosion
Mercury 5 ppb max Naphtha - condensates
Iron < detection limit Corrosion
Sodium < detection limit Crude
Silicon < detection limit Additives (foaming)
Calcium < detection limit Crude
Nickel < detection limit Corrosion
Magnesium < detection limit Crude
Chromium < detection limit Corrosion
Manganese < detection limit Crude
– Mechanism:
Most metals poison the metal function of the catalyst. Metal poisons tend to affect the first
reactor, then to break through and affect the 2nd reactor. The first reactor is typically the
reactor where the poisoning is first detected.
– Effect of metal contamination:
Metal contamination is characterized by:
• A dramatic decrease of the T in the first reactor associated with an increased T in
the second reactor, then if poisoning follows through, decrease of second reactor T with
an increase T in the third reactor etc.
• A decrease in octane number.
• An increase in liquid product yield.
• A decrease of hydrogen production.
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In addition, mechanical problems may result from the collection of corrosion products (scale,
rust...) in the first layer of the first catalyst bed.
The contaminants and the source of contamination are listed in Table 3 above. Prevention
consists of adequate hydrotreating and appropriate material selection to limit corrosion.
Metal poisons are generally partially retained on the upstream hydrotreating catalysts.
However the 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 check periodically the metal content of the hydrotreater feed and
product. It enables to monitor the performance of the hydrotreater with regard to
demetallization and also to be warned of a possible metal breakthrough of the
hydrotreatment catalyst, providing the maximum metal retention of the hydrotreatment
catalyst is known. When the metal loading of the hydrotreater catalyst is nearing the
maximum metal retention, the hydrotreatment catalyst needs be replaced.
C) Coke
The coke which deposits on the catalyst is a temporary poison since its detrimental effect is
reversible through regeneration. Owing to its paramount importance in catalytic reformers,
coke formation is treated separately.
– Mechanism:
Indane derivatives polynuclear aromatics or naphthenes are the assumed precursors of coke
formation. They result either from slight amounts of polynuclear aromatics in the feed
(depending upon the nature of the crude and the end point of the feed) or from the aromatics
producing reactions of the reforming process itself. Some diolefin intermediates of reforming
reactions are also potential coke precursors.
Coke deposit affects the catalyst activity by reducing the contact area between catalyst and
the reactants.
Since coke formation is inherently associated with the reforming reactions, there is no real
way to avoid it. One can only minimize it.
Coke will be reduced by a decrease in reactor temperature (i.e. if severity is reduced) and an
increase in hydrogen circulation. Low system pressure, to the contrary, favors coke
formation.
Another parameter to watch to minimize coke is the feed end point, in order to limit heavy
polyaromatics amount. In European countries the maximum allowable feed end point must
not exceed 180deg.C (ASTM D86) as the marketed gasoline end boiling point is limited at
205deg.C. But in USA were the marketed gasoline and boiling point can reach 215deg.C the
feed end boiling point can go up to 205deg.C (400°F). When the feed results from a mixture
of different streams, each stream must comply with the 180 deg.C end point.
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Note that in case of mixed feeds (use of imported naphtha, SR + cracked naphtha, etc…) the
final boiling point of the mixture does not give sufficient information. Each feed shall be
analyzed separatly as to know the final boiling point of each stream.
Very often mixed feeds are responsible of short catalyst cycle duration, even though the final
boiling point of the mixture stays within acceptable values.
RG SERIES CATALYSTS - CUMULATIVE POISONS LIMIT
(Beyond these limits catalyst performances start to deteriorate)
S ppm wt = ~ 700
Pb ppm wt = ~ 200
As ppm wt = ~ 200
Zn ppm wt = ~ 400
Co ppm wt = ~ 400
Cr ppm wt = ~ 400
Mo ppm wt = ~ 400
Cd ppm wt = ~ 400
Cu ppm wt = ~ 400
Fe ppm wt = ~ 5000
Si ppm wt = ~ 400
Na ppm wt = ~ 500
Ca ppm wt = ~ 100
K ppm wt = ~ 500
Mg ppm wt = ~ 100
6.3.4 Process variables

6.3.4.1 Independent variables
The process variables are:
• Pressure.
• Temperature.
• Space velocity.
• Hydrogen partial pressure or H2/HC recycle ratio.
• Quality of the feed.
The above are independent variables: each of them can be fixed by the operator - within
the operating range of the equipment - independently from the others.
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For one set of independent variables, for same feed characteristics, there is only one
performance of the unit i.e. one set of values for:
• Product yields.
• Product quality (octane).
• Catalyst stability (coke make).
In this chapter we examine the effect on the unit performance of each independent variable
taken separately.
6.3.4.2 Pressure
Hydrogen partial pressure is the basic variable because of its inherent effect on reaction
rates. But for the ease of understanding total reactor pressure can be used. Reactor
pressure is most accurately defined as the average catalyst pressure. Due to catalyst
distribution in the reactors, it is usually close to the last reactor inlet pressure.
All the hydrogen producing reactions i.e. dehydrogenation, dehydrocyclization are enhanced
by low pressure.
The lower the pressure the higher the yields of both reformate and hydrogen for a given
octane number. This is the reason for minimizing unit pressure drop and operating at the
lowest practical pressure. Low pressure however increases the production of coke.
Operator action on pressure is limited:
• Operating pressure rise is limited by equipment design pressure.
• Operating pressure lowering is limited by recycle compressor design power and
intake volume.
6.3.4.3 Temperature
Catalyst activity is directly related to reactor temperature. Thus the most direct operating
variable available for the operator, to control product quality and yields, is the reactor inlet
temperature.
In a conventional semi- regenerative unit when all independent variables are steady, the loss
of activity of the catalyst caused by the coke deposit results in a decrease of the product
octane as well as the reformate yield and recycle gas purity A slight modification in reactor
inlet temperature is used to compensate and maintain product octane number, or:
• To process a different feed quantity.
• To process a different feed quality.
• To balance catalyst ageing which occurs slowly over several years.
An increase of the reactor inlet temperature results in :
• An increased conversion of the non aromatic compounds of the feed mainly the
paraffins. But since the hydrocracking reaction is more favored than the cyclization of
paraffins, the end result is:
– An increased octane but a decrease in reformate yield.
– – An increase of the coke deposit.
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6.3.4.4 Space velocity

The space velocity is the amount of liquid feed, expressed in weight (or in volume) which is
processed in one hour, divided by the amount of catalyst, expressed in weight (or in volume).
Weight (volume) of feed and catalyst must be expressed with the same unit.
Weight of feed (per hour)
Weight Hourly Space Velocity: WHSV =
Weight of catalyst
Volume of feed at 15 C (per hour)
LHSV =
Liquid Hourly Space Velocity: Volume of catalyst
The inverse of the liquid hourly space velocity i.e. (LHSV)-1 is linked with the residence time
of the feed in the reactor. The space velocity then affects directly the kinetics of the
reforming reactions.
A decrease in the space velocity means an increased residence time, hence a higher
severity which results in increased octane, lower reformate yield, higher coke deposit.
When changing feed rate, an important recommendation derives from the above:
• Always decrease reactor inlet temperature first and decrease feed flow rate
afterwards.
• Always increase feed flow rate first and increase temperature afterwards.
6.3.4.5 Hydrogen to hydrocarbon ratio and hydrogen partial pressure
The H2/HC ratio is the ratio of pure hydrogen in the recycle gas (mole/hour) to the feed flow
rate (mole/hour), at first reactor inlet.
H2 Pure hydrogen (mole/hour) in recycle
=
HC Naphtha flow rate (mole/hour)
Hydrogen partial pressure is linked to the H2/HC ratio and total system pressure. Since there
is, in practice, little flexibility in the total pressure, hydrogen partial pressure is mainly
adjusted through recycle flow.
Recycle hydrogen is necessary in the reformer operation for purposes of catalyst stability. It
has the effect of sweeping the reaction products and condensable materials from the catalyst
and supplying the catalyst with readily available hydrogen. An increase in H2/HC ratio will
move the naphtha through the reactors at a faster rate and supply a greater heat sink for the
endothermic heat of reaction. The end result is an increased stability.
A lower H2/HC ratio decreases the hydrogen partial pressure and increases coke formation.
Within the typical operating range, the H2/HC ratio has little influence on product quality or
yields. It is not a variable that the operator typically adjusts, it is set by design based on an
economic balance between equipment sizing i.e. recycle compressors, fired heaters and the
cycle duration.
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Moreover, for a given unit, the amount of recycle is limited by the recycle compressor
characteristics (power, suction flow).
6.3.4.6 Feed quality

A) Distillation range
Light fractions have a poor naphthenic and aromatic content and consequently a high C6
paraffinic content. Cyclization of C6 paraffins to aromatics is more difficult than cyclization of
C7 or C8 paraffins, as discussed in paragraph “Kinetics analysis of the chemical reactions”
(point C).
Hence, for a required octane number, the lighter the feed the higher the required severity or,
conversely, at constant severity, low initial boiling point results in lower aromatic and
hydrogen yields.
In recent years, the restriction of benzene content in gasoline has resulted in selecting feed
with IBP above 82deg.C (180°F) to eliminate cyclohexane (benzene precursor).
Heavy fractions have a high naphthenic and aromatic hydrocarbons content, thus they need
a lower severity to obtain good yields. But these fractions contain also polycyclic compounds
which produce a high coke deposit on the catalyst. High final boiling point of the feed is
favourable up to a certain level, however detrimental if above specified limits. An end boiling
point above 180deg.C (350°F) is generally not recommended (see also paragraph 6.3.3.4 C).
B) Chemical composition
The detailed chemical composition of the feed is determined by gas chromatography
analysis. This analysis is necessary to predict the aromatics and hydrogen production as
well as the severity of the operation.
Even if not sufficient for a complete prediction, an index of characterization of the feedstocks
related to the actual and potential aromatics content of the feed, proves very useful. N + 2A
has long been used (N and A volume % of naphthenes and aromatics in the feed). Axens
now uses 0.85 N + A which is found to be more representative.
The higher this index, the lower the severity of operation to meet the same product
specifications. The lower this index (i.e. the higher the paraffins content), the higher the
severity of operation to meet the same product specifications as the dehydrocyclization of
paraffins becomes important.
Note that cracked naphthas have a ratio naphthenes C6 nucleus / naphthenes C5 nucleus
much lower than SR naphthas.
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Ratio NNC6 / NNC5

Number Coker Hydrocracking
SR naphtha FCC naphtha
of carbon Naphtha Naphtha
6 1.4 to 1.5 0.5 to 0.6 ~ 0.1 ~ 0.1
7 1.6 to 1.7 0.9 to 1.0 ~ 0.5 ~ 0.7
8 ~ 2.0 ~ 1.0 ~ 2.4 ~ 0.8
9+ * * * *
*: Starting with 9 carbon atoms analysis cannot allow to segregate NNC5 from NNC6.
Remember that aromatisation of NNC5 requires first an isomerisation in NNC6. If this
process is rather good for C7+ naphthenes it is only ~60% for the methylcyclopentane while
the cyclohexane is completly converted in benzene.
C) Impurities in the feed
The catalyst activity can be reduced, either temporarily or permanently by poisons contained
in the feed. Table 5 specifies the maximum allowable amount of each contaminant.
D) Summary
Table 4 summarizes the theoretical effect on the unit performance of each independent
process variable taken separately.
TABLE 4
Effect of process variables
Increased RONC Reformate yield H2 yield Coke deposit
Pressure
Temperature
Space velocity
H2/HC ratio
A + 0.85 N
Naphtha End boiling point
Quality Initial boiling point
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TABLE 5
Maximum allowable impurities (wt) in the feed
Component Max. allowable (wt)
Sulfur (as sulfur) 0.5 ppm max
Organic nitrogen (as nitrogen) 0.5 ppm max
Water or oxygenated products 5.0 ppm max
Chlorine as chloride 0.5 ppm max
Fluorine as fluoride 0.5 ppm max
Arsenic 5.0 ppb max
Lead 5.0 ppb max
Mercury 5.0 ppb max
Copper  detection limit
Iron < detection limit
Silicon < detection limit
Nickel < detection limit
Chromium < detection limit
Sodium < detection limit
Cadmium < detection limit
Potassium < detection limit
Manganese < detection limit
Magnesium < detection limit
Note that ASTM D86 distillation shall be similar to design and End Boiling point must be
lower than 180deg.C.
Also diolefins shall be absent from the feed and olefins content kept at the lowest, possibly
less than 0.1 wt %, as these are coke precursors. This value of 0.1 wt % corresponds to a
bromine index equal to approximately 150 (according to ASTM D 2710).
Operating with a feed having a content of impurities higher than the allowance will
lead either to the shortening of the cycle duration or to the decrease of the catalyst
life.
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6.4 Preparation for start-up

6.4.1 Chronology of operations
A typical bar chart sequence of events for the first start-up is attached. It includes the
phases of start-up preparation in which Axens representatives are involved. No time scale
has been given since the completion of these tasks depends on site manpower, local
facilities and contractual provisions between the Unit Owner and his Contractors.
The equipment inspection (reactors, vessels, columns...) takes place prior to the succession
of tasks which constitutes the start-up sequence itself, and a variable time gap separates the
equipment inspection from the completion on site of the Axens's start-up team.
The key milestone which enables the Engineering Contractor or the Unit Owner to insert the
Reforming schedule within his overall schedule is the availability of the recycle
compressor and fired heaters which allows to initiate the dry out of the reaction section.
This milestone has been selected as time zero.
It is recommended that the Axens' representative(s) is (are) present on site at least a week
earlier to enable them:
 To inspect the unit (mandatory attendance from the first day of unit check-out and
vessel inspection)
 To witness the leak test (optional for the 1st leak test and mandatory attendance for the
2nd leak test)
For the Detail Engineering schedule, the above period should coincide with the end of the
commissioning of the utilities (utilities systems available) and the completion of the
commissioning of the unit (water wash, hydro-tests and so on).
Then a typical chronology of operations is as follows (starting from Axens's team arrival on
site)
• Unit inspection
– (note that instrument checks will extend almost until the oil in).
• Initial leak test
• Once the recycle compressor and the fired heaters are available the dry out of the
reaction section can start. The hydrogen rich gas compressor can be started
simultaneously or subsequently.
• After a cooling down period and a last inspection of the internals the catalyst loading
takes place.
• A second leak test and partial inerting of the reaction section is performed.
• Catalyst is dried.
• Final inerting
• Stabilization is started at total reflux.
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• The reaction section is pressurized with hydrogen and catalyst reduction takes
place, followed by sulphiding.
• Oil-in: feed is introduced at reduced throughput:
– first at low severity.
– then at high severity.
• The hydrotreatment section is started-up.
• Throughput is increased to its nominal figure and the unit is lined out at design
conditions.
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FIGURE 6 :
TYPICAL START-UP SCHEDULE
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6.4.2 Equipment and unit inspection

The first inspection activity takes place towards the end of the construction work. As soon as
erection is advanced enough (equipment, piping and instrumentation) and when found
convenient to both Unit Owner and Axens, Axens will send representative(s) to carry out the
Equipment inspection (reactor, vessels, general lay out). The sooner is the better since it
will allow time for corrective work, if any. For this task one (two) engineer(s) is (are) required
for a period of two (one) week(s).
A Unit inspection which deals mainly with conformity of the unit to the approved PID's,
operability, instrument checks, will be carried out prior to the mechanical completion. It
requires typically two engineer-weeks. The full start-up team is mobilized somewhat later.
6.4.2.1 Equipment inspection

Prior to Axens's inspection the equipment involved must have been freed from debris, rust,
welding rods... temporary supports. The inner surface must be cleaned and brushed if
needed, and the equipment vacuum cleaned.
Axens's requirements are expressed essentially in Section 2, Equipment specifications of the
Process book. They will also be expressed in due time through the contractual review of
the critical equipment as listed in Section 2.
A) General
 Equipment inspection by Axens' representatives may be carried out in several phases.
- At the manufacturer's workshops.
- On site prior to the catalyst loading to reactors or prior to the mechanical completion
(other vessels).
- During and at the end of the catalyst loading for inspection of internals, etc.
 The workshop inspection is optional depending upon the complexity of the internals and
the critical nature of the items to be inspected. (e.g. for the reactors R-301/302/303).
 The site inspections prior to and during catalyst loading are mandatory, even if the
workshop inspection has been witnessed by Axens' representative and proved
satisfactory.
B) Scope of the inspection
The equipments to be inspected are as follows:
- Reactors
- Columns
- Drums/Vessels
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Equipment is inspected for compliance with Axens' specifications and drawings, and Axens'
recommendations for construction, as expressed in Section 2 (Equipment specifications) of
the Process Book. Axens' start-up advisor will issue, if needed, a list of remedial works to be
carried out.
A typical, but not complete list of items to be checked is given hereafter. The list needs to be
adapted according to the specific requirements of the unit as expressed in Section 2 of the
Process Book.
- Vessel temperature and pressure rating
- Vessel metallurgy
- Vessel elevation
- Vessel lining, internals
- Trays: number, type, spacing, levelness, liquid seal, weir height, valve number and type,
metallurgy, weep holes, supports
- Distributors: location, levelness, size and number of holes and chimneys, correct
installation with gaskets
- Quench devices: location, size and number of holes for quench pipe, size of quench box
- Ability to reinstall manways covers and associate elements after catalyst loading
- Nozzles
- Vortex breakers
- Demisters: size, materials, support
- Pressure instruments: location, range
- Thermowells: location and length
- Level instruments: location, level, range
- Fireproofing, insulation
- Presence of names plates
- Cleanness
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C) Inspection preparation works

Here below is the description of the preparation work to be carried out by the Engineering
Company or Unit Owner to allow access for Axens' representatives to the internals.
- Reactor Isolated by blinds, from any potentially dangerous source
(flare, fuel gas, hydrogen, N2, chemicals, HC...). Manways
open and atmosphere breathable to allow 1st inspection
for reactor wall state and a 2nd inspection after assembly
of the internals (without internal manways).
- Columns, Drums and Vessels Isolated by blinds from any potentially dangerous source
(flare, fuel gas, hydrogen, N2, chemicals, HC...).
Manways and vents open, atmosphere breathable.
Internals assembled.
D) Vessels internals assembly and inspection

It is advised to assemble the internals and have them inspected as early as possible, in order
to perform any adjustment without delaying the start-up planning. For the inspection of the
various items listed below, refer to the reactors detail drawings, in section 2 (Volume 1) of the
Semi-Reg Reforming unit Process Book: Equipment process specification R-301/302/303.
This description applies to a downflow reactor (R-301/302/303):
 Install the outlet collector at the reactor bottom. As applicable check the size of the wire
mesh, seal welding and the fastening of the various parts. In case of a screen, check its
fastening and the slot opening. Refer to the relevant drawings 2RE671 sheets 1 and 2
(page 11/13 & 12/13 of documents 04653 300 R-301 Rev0 / 04653 300 R-302 Rev0 /
04653 300 R-303 Rev0).
 Close the catalyst draw-off pipe. The wool plug will be inserted later prior to the catalyst
loading. Refer to the relevant drawing 2RE681M sheets 1 and 2. (page 12/13 & 13/13 of
documents 04653 300 R-301 Rev0 / 04653 300 R-302 Rev0 / 04653 300 R-303 Rev0).
 Check the feed diffuser. Perform a blank assembly on the reactor top flange. Refer to the
relevant drawing 2RE611 (page 9/13 of documents 04653 300 R-301 Rev0 / 04653 300
R-302 Rev0 / 04653 300 R-303 Rev0).
Once this blank assembly has been carefully performed, the internals are dismantled to
prepare for the catalyst loading. Each piece must be clearly identified.
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6.4.2.2 Unit inspection

This inspection is the first task of Axens' team upon its arrival on site. It shall take place prior
to the mechanical completion of the unit.
A) PID check
During the phases of the detailed Engineering work, the last issue of the Engineering PID's
must have been checked against the last issue of Axens's PID's.
Upon their arrival, the Axens team will carry out a check of the "as built" unit against the
requirements expressed by Axens. This check is primarily for construction conformity, piping,
instruments, safety devices and fittings.
Location of instruments, valves, fittings (including drip rings, special shut-off valves, tie-ins
etc...), wherever Axens issued a special recommendation, will be checked for compliance
with this recommendation.
Remedial work will be carried out, if necessary.
B) Operability check
This consists of an assessment of the possibility to carry out all the operations required for
commissioning, start-up and shutdown. It focuses mainly on access to instruments and
valves (including vents, drains), to manholes, to spectacle blinds, and to parts of equipment
that need to be dismantled. The presence of the required start-up and pressurization lines is
checked as well as the impact of safety devices on start-up operations.
C) Instrument check
This task is within the Engineering Company or Unit Owner responsibilities. The following is
only a reminder:
a) Prior to unit start-up, all instruments must have been checked with regard to:
 Proper tagging,
 Proper location in the process,
 Correctness of assembly,
 Operating range consistent with the operating conditions,
 Calibration,
 Flow orifice size, coefficients, orientation versus flow,
 Level instruments will be calibrated using the design liquid density,
 Instrument wiring integrity, polarity, grounding.
b) Alarm checking
Make sure that the released mechanism on the unit actuates the corresponding light or
audible alarm in the control room.
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c) Valves
The control valves are removed during cleaning operations. They will be checked for
cleanness of the seats and free movement of the plug or ball.
Check the valves motion and their response to the controller signal.
When all the single instruments have been individually checked, when all their addresses
have been verified in the DCS, then the loop checking can take place for each loop or group
of control loops.
Each automatic action, either linked to the process or to equipment, shall also be individually
tested.
d) Safety devices check
The process includes a number of specific safety devices referred to Interlocks Safety (IS)
which are implemented in the Emergency Shutdown System (ESD). These devices are
designed either to protect the unit against misoperation or to fulfill safety actions.
The Interlocks Safety (IS) is composed of independent systems which in the occurrence of
pre-defined potentially harmful events, initialize various actions such as:
- Valve(s) are set to their failure position (FC, FO or FL)
- Shutdown of equipment (pumps, compressors, furnace, electrical heater, etc.) to alleviate
the risk.
The details of the Interlocks Safety are given in the document "SHUTDOWN LOGIC IS" in
the section 4 of the Process Book. They must be thoroughly read and understood by
operators.
This Interlocks Safety, in accordance with this document, will be updated and agreed upon
by the representatives of the Engineering Company, Unit Owner, and Axens. The tests of
these devices must be witnessed by Axens representatives and remedial work must be
carried out until the operation is fully satisfactory.
The principles of these checks are as follows:
- A simulated default signal from the primary sensor will be fed into the system and the
resulting signal output to valves or equipment will be checked.
- Whenever possible, the end result of the signal output such as actual valve failure or
machine shutdown will be observed.
- Ultimately, a real test which requires running machines must be performed during the
forthcoming operation procedures.
Throughout this exercise, the actual physical position of the valves or status of machines will
be checked against the indications shown in the control room.
The check of the motorized valves is part of the same task. It includes:
- A site test of the opening/closing of the valve upon the input signal.
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- A check of the reported information in the control room and a check of the control room
command.
6.4.3 Preliminary operations

6.4.3.1 Definitions
The following definitions are used throughout this chapter:
 Precommissioning is the period during which non-operating checks and verifications that
the installation conforms to specifications, and drawings, are carried out. It includes the
unit cleaning, calibration of instruments, cold-alignment checks, testing of safety devices,
etc. This phase leads to the mechanical completion or ready for commissioning.
 Commissioning is the period during which the dynamic verification of the functioning of
equipment, the simulation of control loops and safety systems, and the operational tests
are carried out. Commissioning includes also a variety of activities such as cleaning and
drying-out of piping systems, tightness tests, loading of chemicals, desiccants and
catalysts, running-in of pumps, turbines and compressors and unit final inerting.
These operations are conducted before feed introduction into the plant and end up at a point
called ready for start-up meaning that the plant is ready to be operated for the first time.
6.4.3.2 Axens' involvement (responsibilities)
Typically, Axens' start-up team arrives towards the end of the unit precommissioning.
Enough time must be allowed to the start-up team for the unit inspection prior to the
mechanical completion of the unit.
It is not within Process Licensor responsibilities to issue instructions related to the
precommissioning activities.
Regarding commissioning activities Axens' involvement is defined in the following
paragraphs of this chapter. In some instances Axens is only a witness that the activity is
carried out in accordance with the state of the art and does not hamper the satisfactory
execution of the forthcoming start-up operations. In other instances Axens either checks the
results of tests or issues instructions that must be strictly followed (special requirement, unit
dry out, catalyst loading).
Both precommissioning and commissioning operations must be carried out in accordance
with equipment manufacturer's instructions and relevant standard codes and procedures
(API).
Well planned and carefully executed precommissioning and commissioning activities
generally result in a quick and successful start-up.
6.4.3.3 Utility systems commissioning
Here is a non restrictive list of these systems and the status under which they are expected
to be:
• In service means the system is operational: main header and user feeder lined up. Each
individual user only is isolated either by block valves, if available, or blinds.
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• Ready to use means the system (main header, individual user feeder) have been
cleaned, dried if required, leak and pressure tested and left under the appropriate
atmosphere. The main header has been subsequently shut off with block valves and
blinds.
Instrument air : In service

Utility air : In service
Cooling water system : In service
Individual user isolated, drain open
Nitrogen system : In service
Checked for proper oxygen content
Steam : In service
Drains and traps have been checked
Fire water : In service
Fuel gas : Ready to use
Inside the unit battery limit the system is blanketed with
nitrogen, oxygen content has been checked.
Flare system : Ready to use
The main header flare of the unit is kept open to atmosphere
and isolated with a blind from the flare collector at the battery
limit.
Hydrocarbon closed sewer : Ready to use
Process water : Ready to use
Electrical equipment : Ready to use
All wiring, junction boxes, breakers, switches have been checked for integrity, operability and
compliance with specifications. Electrical motors have been run in for 4 hours (disconnected
from the driven machine) if no mechanical objection arises.
6.4.3.4 Unit commissioning
The following operations related to process unit equipment are completed in accordance with
Unit Owner regulations and the equipment manufacturer's instructions:
• Equipment washing.
• Hydrostatic test of piping.
• Rotating machine alignment.
• Pump running in.
• Heater refractory drying (refer also to 6.3.4).
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It is worth mentioning that water wash should be avoided, if possible, for equipment which
will be subjected to a forthcoming drying.
6.4.3.5 Initial leak tests
Initial leak tests will be performed under Unit Owner or Engineering company responsibility
and the general instructions below shall only be used as a reminder.
The initial leak tests can be performed using air or nitrogen depending upon local facilities.
The test pressure will be the air or nitrogen system pressure or the unit (or section of unit)
design pressure, whichever is the lower. For equipment on low alloyed steel, the test
pressure shall remain below the quarter of the design pressure of the equipment to avoid
detrimental effect of temper embrittlement.
The unit is isolated with blinds from adjacent sections containing hydrocarbons (liquid or
gaseous), and from utilities systems where pressure is lower than air (or nitrogen) pressure.
The pressure decrease must be checked on several pressure gauges and possibly checked
on a pressure recorder. Leaks must be carefully located and tightened. Their location must
be recorded. The leak test is satisfactory when the pressure decrease is lower
than 0.05 kg/cm2/hour over a period of 4 consecutive hours (at approximately constant
temperature).
The air (nitrogen) used for leak tests should be purged out of the unit using low points drains
to remove free water, if any.
For the purpose of leak tests the unit will be divided into sections of approximately the same
design pressure. Air (nitrogen) will be injected at different locations depending on check
valves locations.
Note: "Always", during initial leak test make sure, that all pumps/compressors are
isolated with vents/drains open to atmosphere to prevent accidental pressurization
and as such possible seal damage by effect of “reverse pressure”. Pumps and
compressors are only to be leak tested when seal systems are cleaned and properly
commissioned by Vendor/Suppliers representatives and/or Rotating Equipment
specialists.
During the "Construction Phase", all seals and all rotating equipment must be
carefully isolated, must never be pressurized and should always be kept in a
protective clean environment with conservation oil in the seals, if lubricated by oil, or
nitrogen in the seals operated by gas (compressors).
6.4.3.6 Recommended sections for leak tests (see drawings here after)
For the purpose of leak testing, Axens recommends to split the unit into several sections. All
sections have to be isolated from the other sections by blinds, or valves.
A) Reaction section
The following equipments with their connections are included:
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• The reactors.
• The heaters.
• The reactor feed/effluent exchanger.
• The reactor effluent air cooler.
• The separator drum.
• H2 rich gas compressor KO drum.
 The feed filters
• In addition, all utilities lines, especially the ones connected to the flare and fuel gas
networks (including safety valves) will be fitted with blind flanges.
The points of isolation are indicative only and must be reviewed on-site, to take into account
actual piping arrangement.
B) Absorption section
• The HP absorber feed cooler.
• The HP absorber drum.
 The hydrogen rich gas chloride adsorbers
• In addition, all utilities will be fitted with blind flanges, including connections to the
flare and fuel gas and all PSV's will be blinded.
C) Stabilization section
• The LPG absorber drum.
• The stabilizer feed / bottom exchanger.
• The stabilizer column.
• The stabilizer reboiler.
• The stabilizer overhead cooler.
• The reformate trim cooler.
• The stabilizer reflux drum.
• The deethanizer reboiler
• In addition all utilities will be fitted with blind flanges, including flare and fuel gas lines
and all safety valves isolated with blind flanges.
D) Deethanizer section
• The deethanizer reboiler
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• The deethanizer feed / bottom exchanger.

• The deethanizer column.
• The deethanizer condenser.
• The LPG product trim cooler.
• The deethanizer reflux drum.
• In addition all utilities will be fitted with blind flanges, including flare and fuel gas lines
and all safety valves isolated with blind flanges.
When the leak tests are completed, the reaction section and recycle gas dryer must be dried
prior to catalyst loading.
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PFD Leak test N°1/4
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6.4.4 Drying out of the unit

6.4.4.1 Introduction
The reaction section must be dried prior to catalyst loading, firstly to avoid damaging the
catalyst with water, secondly to shorten the duration of the low severity operation after first oil
in.
Unit dry out is conducted simultaneously with the heater refractory drying. The Axens
representative will consult with the heater manufacturer representative to agree on a
procedure (chiefly rate of temperature rise and duration of steps) which is mutually
acceptable.
The description of the unit dry out, below, reflects Axens's requirements only.
The dry out operation uses a nitrogen circulation loop through all of the equipment in the
reaction section. The recycle compressor is used to circulate the nitrogen at the maximum
rate and the fired heaters provide the heat. These sections must be isolated from the other
sections during this step.
6.4.4.2 Preparation and lining-up
All TI’s (in the firing box, in the process fluid, tube skin) have been checked. The burners,
dampers, control and safety systems have been checked. All safety measures and controls
normally involved in the firing of heaters must be followed in agreement with Unit Owner or
heater manufacturer procedures.
Make a list of required instruments and check that they are connected and in service.
Check that orifices plates are installed where required and correctly calibrated (coefficient
adjusted for nitrogen) check that all safety valves are installed and connected to atmosphere.
The recycle compressor must be commissioned prior to start (blinds to be removed and left
in open position):
• commission the reactor effluent air cooler.
6.4.4.3 Reaction section
Refer to Drawings (see drawings here after):
• Reaction section pressurization (reaction section as defined in paragraph
“Recommended sections for leak tests”). Check that:
– The reaction section is blocked in at the feed.
– The separator bottoms pumps are isolated.
– The H2 rich gas compressor and spillback are blocked in.
– The off-gas line to fuel gas / flare is blinded and the line to atmosphere is open.
Nitrogen is introduced at the recycle compressor discharge and the reaction section is
pressured to 5 to 9 bar g. The pressure controller on the separator drum is commissioned at
the set pressure with the off-gas discharged to atmosphere.
• Nitrogen circulation and dry-out
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– Open suction and discharge valves of the recycle compressor and start the
machine according to the manufacturer's instructions. This initiates nitrogen
circulation through the reaction section. Once maximum flow rate has been
established start draining free water from all the low points.
– Light small fires in the preheater and interheaters according to the manufacturer's
instructions and increase the reactor inlet temperature up to 200deg.C at a rate of
40deg.C per hour.
• Follow-up and end of drying
Purge water from the separator drain and all low points (air cooler outlet, separators,
compressors K.O. drums etc....). Keep record of all the water drained to follow the drying
rate, showing the total amount of water drained at regular intervals.
Purge from the loops to ensure no pockets of water are held up.
The system is considered dry, at this temperature (200deg.C), when the water draw-off is
less than 10 liters per hour.
Then the temperatures are increased to 400deg.C at a rate of 20deg.C per hour. When the
amount of water drained is lower than 5 liters per hour, the temperature is increased to
500deg.C at a rate of 20deg.C per hour and maintained until the total water draw-off is less
than 1 liter per hour.
The 50deg.C temperature must be reached in the reaction section of the reformer in order to
check if any problems occur, due to the thermal expansion of the reactor internals.
When the system is dry (water drained becomes lower than liter per hour), lower the
temperature to 200deg.C (50deg.C/h). Then stop firing and circulate nitrogen until the
reactors are cooled down to 40deg.C. The doors of the heater boxes could be opened in
order to speed-up the cooling process.
Stop then the recycle, and H2 Rich Gas Compressor, and close the block valves at suction
and discharge. Depressure and repressure the unit with air, to remove nitrogen. Check that
the atmosphere is suitable for entry into the vessels.
Note:
During the temperature rise, watch the skin temperatures of the heater tubes and vaporized
LPG / fuel gas temperature to avoid any overheating of the tubes. Check also the
temperature of each equipment in order not to exceed the design figures.
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PFD Drying out N°1/2
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PFD Drying out N°2/2
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6.4.5 Catalyst loading

Catalyst loading shall be performed under air atmosphere.
When the reaction section drying out is complete and nitrogen has been replaced by air, the
reactors can be opened for inspection of the internals.
If needed, the reactors will be brushed and vacuum cleaned before catalyst loading starts.
The catalyst loading period must be as short as possible to minimize the risk of moisture
entering the reaction system. If necessary the job will be done in shifts. Covers must be
installed at the top of each reactor on temporary structures to protect against rain.
6.4.5.1 Preliminary checkings
 Check that the reactor is properly isolated.

 Open the top manhole. Aerate and check that the atmosphere inside the reactor is
suitable for entering (21% O2). Respect the refinery vessel entry permit system at all
times. Supply air hose connections to reactor top as necessary.
 Make sure that the catalyst and inert balls drum are gathered in a sheltered place,
close to the reactor.
 Check the quality of inert balls. If they are broken, they must be sorted and fines
removed.
 Check that all the internal parts to be installed during loading are available. Check
their conformity to the drawings and the quality of the materials.
 All the reactor internals are made of parts which can be dismantled in order to allow
their introduction through the manhole. Their assembly has already been checked.
 Ensure that all the necessary safety and personnel protection equipment is available
(gloves, dust masks, respirators, safety harnesses, etc.) as well as means of
communication (walky-talkies).
 Before loading, the catalyst drums must be stored in a safe place and protected from
rain.
6.4.5.2 Specific recommendations
 Do not roll the drums of catalyst to avoid breakage of the extrudates. Big bag shall be
handled very carefully.
 Whenever possible in case of sock loading a person shall be inside the reactor to
level the catalyst bed and move the loading sleeve. Another person must be in
attendance outside with equipment and instructions in case of emergency.
 Catalyst must be loaded carefully to minimize free fall. Maximum permissible free fall
height is 1 meter. Do not walk directly on catalyst. Use wooden walking boards.
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 In case of heavy rains stop loading. If prolonged rainy weather is forecast, provision
for a weatherproof cover must be made. If loading operations are not to continue for
an extended period, then the inlet flanges must be covered in a weather tight fashion
whilst unattended.
 Working in a dusty catalyst atmosphere is not physically harmful, provided that dust
masks are worn. Make sure that no foreign material is left in the reactor (pieces of
sleeve, walking boards, tools, etc.).
6.4.5.3 Catalyst loading duration
Catalyst loading period by itself lasts between 2 and 5 days according to the amount of
catalyst to be loaded, the number of reactors and their type, the work force and, last but not
least, the weather. This figure does not take into account the reactors opening neither their
boxing-up, but includes internals installation. In this period of time there is no provision for
internals repair (scallops, center pipe, etc.).
Note also that dense loading does not make the overall loading any faster or longer. On the
contrary, the use of Texicap instead of conventional steel covering system can save up to
20 % of the time.
6.4.5.4 Equipment and personnel
The list below is based on the following assumption: catalyst loading will be carried out with 1
crane.
• 1 telescopic crane capable of lifting approximately 3 tons, 5 meters above the reactor
upper manhole (See following drawings).
• 1 forklift to handle the catalyst drum pallets.
• Stationary hopper equipped with Ø 8 to 10" nozzles to be installed on the reactor
upper manhole.
• 2 mobile hoppers, each with a capacity of about 5 to 6 catalyst drums (See following
drawings).
• 1 structure (scaffolding and timbers) to unload the drums into the mobile hoppers
(See following drawings).
• 1 safety harness, rope ladders, portable oxygen analyzer, low voltage lighting, dust
masks, air masks, goggles, plastic sheets to protect drums and reactor in case of
rain.
To serve the above mentioned equipment the following personnel is necessary:
• 1 foreman,
• 1 crane operator,
• 1 fork lift operator,
• 1 team of 4 riggers at ground level for catalyst handling and loading into the mobile
hoppers.
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• 1 team of 6 fitters for vessels opening, closing and for catalyst loading.
Note: This personnel shall be permanently present during the loading operation. The total
number of personnel will be obtained by multiplying by the number of shifts, if the
loading takes place on 24 hours basis.
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APPENDICES TO CATALYST LOADING
Appendix 1 Catalyst handling with drums

Appendix 2 Catalyst handling with big bags
Appendix 3 Filling-up the hopper at ground level from drum
Appendix 4 Ground level preparation for big bag lifting
Appendix 5 Mobile hopper
Appendix 6 Stationary hopper
Appendix 7 Slide valve
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APPENDIX 1
CATALYST HANDLING WITH DRUMS
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APPENDIX 2
CATALYST HANDLING WITH BIG BAG
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APPENDIX 3
FILLING-UP THE HOPPER AT GROUND LEVEL FROM DRUMS
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APPENDIX 4
GROUND LEVEL PREPARATION FOR BIG BAG LIFTING
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APPENDIX 5
CATALYST LOADING - MOBILE HOPPER
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APPENDIX 6
CATALYST LOADING - STATIONARY HOPPER
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APPENDIX 7
CATALYST LOADING - SLIDE VALVE
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6.4.6 Chloride adsorbers loading

The adsorbent loading procedure of the chloride adsorbers is the same than the catalyst
loading procedure of the reactors.
6.4.7 Second leak test
The procedure for the second leak test is the same than the initial leak test procedure.
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6.5 First start-up

The following describes the very first start-up of a newly built unit. Any subsequent start-up
of the same unit will very likely not include all the following steps, depending upon the status
of the unit after the shutdown. For instance the catalyst reduction procedure need not be
performed again, except in the case of catalyst renewal.
6.5.1 Status of the unit
The status of the unit prior to its initial start-up is a follows:
• Each section as defined in chapter “Recommended sections for leak tests” has been
leak tested (initial leak tests).
• All the sections (except the Adsorption, stabilization and deethanizer sections) have
been dried.
• Catalyst has been loaded in the reactors and the relevant sections leak tested again
and partially inerted (residual content of O2 between 2 and 5% volume).
• The adsorption, stabilization and deethanizer sections have not been inerted.
• The unit is isolated with blinds at the battery limits:
– on the feed and products lines,
– on the flare and fuel gas headers.
• Pressure relief valves in the reaction and adsorber sections are blanked off, except
those to atmosphere.
• The 300-PV-0601 A/B on the separator drum discharge to atmosphere.
6.5.2 Chronology of start-up operations
The sequence of first start-up is as follows:
• Drying of the catalyst under an atmosphere with a residual O2 content.
• Complete inerting of the adsorption, stabilization and deethanizer sections.
• Stabilization section start-up on total reflux.
• Pressurization with hydrogen of the reaction section and the adsorption section.
• Heating up, reduction of catalyst, sulfiding and chloriding.
• Oil in.
• Operation of the unit at low capacity and low severity with desulfurized naphtha.
• Operation of the unit at low capacity and high severity.
• Start-up of the hydrotreater unit.
• Operation of the unit at nominal capacity and high severity.
The chronology of the various start-up tasks is shown on the attached schedule.
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The durations shown are those required to perform the tasks. The time gap between two
consecutive operations has not been taken into consideration.
START-UP SCHEDULE
TIME (DAYS) 0 1 2 3 4
TASKS
- H2 PRESSURIZATION OF THE
REACTION SECTION (1)
- COLD NAPHTHA
CIRCULATION
(BY-PASSING HDS REACTION
SECTION)
- SULFIDING & START-UP OF

THE UNIT
- PRODUCT TO STORAGE
Notes: 1 - H2 leak tests are carried out simultaneously with the pressurization.
6.5.3 Stabilizer start-up on total reflux

During the catalyst heat-up, the stabilizer can be put on total reflux, using the dedicated
heater for reboiling.
If the stabilization section was inerted with steam it has been subsequently pressured with
nitrogen and then H2.If the stabilization section was inerted with nitrogen, purge nitrogen to
vent or to flare, then pressure with H2.
Establish a level in the bottom of the stabilizer with desulfurized naphtha from storage or
from the upstream hydrotreater (NHT) through:
• The hydrotreater stripper (NHT).
• The start-up line to the suction of the separator bottom pumps.
• Start the separator bottom pump.
• Through the HP absorber drum.
• Through the stabilizer feed/bottom exchangers.
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• To the stabilizer.
When the level 300-LIC-1202 of the stabilizer bottom indicates 80%, stop the naphtha make-
up and:
• Establish a circulating loop through the stabilizer reboiler bypass using the stabilizer
reboiler pumps.
• Set the flow to design conditions.
• Start the stabilizer condenser.
• Slowly warm up the column by means of the reboiler bypass.
Maintain column pressure around 6 to 7 kg/cm2 gauge by setting the 300-PIC-1001 (PIC on
the LPG absorber drum). When the level of the stabilizer reflux drum indicates 50%, start the
stabilizer reflux pump and send reflux to the column.
Operate the stabilizer on total reflux.
6.5.4 Deethanizer start-up on total reflux
If the section was inerted with steam it has been subsequently pressurized with H2.
If the section was inerted with nitrogen, purge nitrogen to vent or to flare, then pressurize
with H2.
The purpose of this procedure is to fill up the unit with LPG from the Stabilizer, to circulate
this fluid around the bottom of Deethanizer and to remove water accumulation.
The start-up circulation flow rate is fixed at 60% design throughput.
Start bringing in LPG feed to the Deethanizer.
When the level 300-LIC-1602 of Deethanizer indicates 80%, stop the LPG feed and:
• Commission water to the overhead condenser.
• Start the reboiler of the Deethanizer and slowly warm up the column.
When the level of the reflux drum indicates 50%, start pumps and send reflux to the column.
Operate the deethanizer on total reflux.
6.5.5 Catalyst drying
This procedure, which must be applied before the catalyst reduction, ensures a good
elimination of water that has been reabsorbed by the catalyst during handling and loading. It
is carried out in the presence of chlorine and of oxygen. The catalyst drying does not replace
the phase of oxychlorination which is part of the catalyst regeneration procedure described in
this document. It is only applicable to a brand new catalyst.
After catalyst loading, the reaction circuit is established and placed under a 5 to 9 kg/cm2
gauge pressure of nitrogen. After start-up of the recycle compressor, the oxygen
concentration in nitrogen is adjusted and maintained around 2 to 5 volume % during the
whole drying step.
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This oxygen concentration is followed regularly by an on-line analyzer.

Injection of air could become necessary to keep the oxygen concentration at the required
level.
Furnaces are fired and temperature of all catalytic beds is increased at a rate of 40deg.C per
hour up to 485deg.C (the average temperature between reactor inlet and outlet temperatures
because there are no thermocouples inside the reactors).
When the catalyst temperature reaches 350deg.C, an injection of a suitable chlorinated
compound is carried out (for example methane tetrachloride), for about four hours, so as to
introduce chlorine (as Cl) equivalent to 0.1 wt % of the total mass of catalyst. This injection is
done at the first reactor inlet while progressing normally with the temperature rise.
During the whole operation of drying, the water which has condensed and accumulated in
the separator drum and at all low and cold parts of the unit is drained every hour. The
quantity of water collected is recorded precisely. Separator temperature is kept as low as
possible.
The catalyst bed temperature is maintained at 485deg.C for two hours minimum, or until the
total quantity of water drained at low points is lower than 10 liter per hour. Then temperature
is reduced to 350deg.C at a rate of 50deg.C per hour.
At this temperature level, furnaces and recycle compressor are shutdown simultaneously.
By using sampling devices of the first and third reactors, catalyst must be sampled at the end
of the drying step. The analyses of chlorine on the catalyst shall be used to eventually
proceed with a final rechlorination before feed injection.
If some repairs had to be performed at this stage, the catalyst would be kept under
chlorine/oxygen atmosphere, the nitrogen purge being accomplished only at the beginning of
the reduction step.
(See figure 8).
6.5.6 Catalyst reduction
The reaction section is purged with a nitrogen containing less than 100 ppm vol of
CO + CO2 in order to eliminate oxygen to a concentration of no more than 0.3 vol. % and to
decrease CO + CO2 concentration also under 100 ppm vol. If the nitrogen purge follows a
regeneration purge the section until the SO2 content is lower than 50 ppm vol. Swing open
the isolation blinds (except the one on the feed) as soon as possible.
Electrolytic hydrogen shall be used for the reduction of the metal oxides.
Note that about 15 times the volume of the reaction section is needed. This quantity takes
into account the quantity needed to maintain the pressure in reaction section up to oil in.
As an alternative, hydrogen produced by a steam reforming + PSA unit (99.9 vol.% of H 2 and
CO + CO2 < 20 vol. ppm) can also be used. Both of them being dry and hydrocarbon free
will allow to reduce the metals oxides in a proper way. If none of the above mentioned
hydrogen gas are available it is possible to use hydrogen rich gas from a reformer unit,
mixed with nitrogen.
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Hydrogen purity must stay higher than 75 vol.% and C2+ content shall be limited to 2 % vol.
Due to the presence of hydrocarbons, catalyst coking will take place during the
reduction stage and lead to a shorter cycle duration, in addition catalyst activity and
stability will also be affected as well as product yields.
Nitrogen is displaced by hydrogen from recycle gas compressor discharge to separator drum
(compressor is isolated and purged separately). Increase then the pressure to 1.0 kg/cm2 g
and depressurize to flare at separator drum. Repeat once this operation, and then increase
the pressure up to 7 kg/cm2 g minimum at separator and start-up the recycle gas
compressor.
Furnaces are fired again immediately after start-up of the recycle compressor in order to
avoid any natural cooling of the catalyst.
Beds temperature is progressively increased to 510deg.C at a rate of 40deg.C per hour. As
there are no thermocouples inside reactors, the beds temperature is calculated as the
average between inlet and outlet temperatures. The reduction step starts when this average
temperature is 500deg.C.
This temperature is maintained at least during 4 hours or until the quantity of water drained is
lower than 0.05 % of the catalyst weight per hour. Check every hour H2S in recycle gas.
During this whole step, water formed by reduction is drained every hour from the separator
drum and at the various low and cold parts. The quantity of water collected is recorded
precisely. Separator temperature is kept as low as possible.
Hydrogen make-up may be necessary to maintain the pressure inside the reaction section.
Under no circumstances should a neutralizing solution be used to protect cold parts of the
loop as this will lead to water saturated conditions and chloride removal which will adversely
affect metals dispersion.
If for any reason the reduction is stopped for more than 24 hours another short calcination
step -about 3 hours- shall be performed as during the shutdown the catalyst will cool down
and adsorb water. If re-started in these conditions the reduction will be done under too wet
atmosphere and this will lead to metals agglomeration and consequent short cycle duration.
Note 1: Oxygen removal before catalyst reduction.
• In case of leak in the section, oxygen will be introduced.
• In case of lack of blinds, hydrocarbons can be introduced.
• In the particular case of cold wall reactor (internal insulation), contaminants (sulfur,
heavy hydrocarbons) will enter the section.
6.5.7 Catalyst sulfiding
Sulfiding is performed to reduce temporarily the extra activity of the catalyst, especially the
hydrogenolysis function of the freshly reduced metallic phase which could lead to cracking
reactions with production of methane. This procedure (See figure 9) is based on a reversible
formation of sulfides.
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This operation also allows the sulfiding of iron metal which could lay down in the reactor
during the catalyst regeneration.
The sulfiding step is carried out after reduction, when the catalyst beds temperature has
been reduced from 500deg.C down to 400deg.C at a rate of 50deg.C per hour.
The sulfiding step lasts for at least 3 hours at 400deg.C. The recommended sulfiding
agent is dimethyldisulfide (DMDS) which is an odorous liquid with a low vapor pressure.
The sulfur injection is carried out reactor by reactor starting with reactor n°2, then reactor n°3
and finally with reactor n°1. This allow either to let more time for the sulfur to disperse in the
last reactor and to oil-in the unit immediately after reactor n°1 sulfiding.
For fresh catalyst, the quantity of DMDS to be introduced corresponds to 0.15 wt. % sulfur on
catalyst (i.e. 150 kg of sulfur for 100 tons of catalyst equivalent to about 225 kg of DMDS).
After regeneration this quantity can be reduced to 0.10 wt % sulfur on catalyst.
Every 30 minutes, the concentration of hydrogen sulfide at reactors outlet must be
determined using the usual method of Dräger tubes or equivalent. Such analysis are used to
make sure that each catalyst bed is well sulfided (~ 20 ppm vol.) and that the excess of H2S
is transferred from one reactor to the following one.
If, in the course of the sulfiding step, an injection pipe happens to be plugged and it becomes
impossible to sulfide one given reactor, then the required quantity of DMDS for this given
reactor will be introduced at the inlet of the upstream reactor.
For the first reactor, another injection point should be found to introduce the required quantity
of sulfur.
During this step, remaining water is drained from the separator drum and at the various low
and cold parts.
Note: - DMDS is the selected sulfiding agent.
- DMDS “evolution”, less odorous, can also be used.
- Mercaptans can also be used but their handling is difficult.
- H2S, too dangerous to handle shall be avoided.
- CS2, too dangerous and responsible for catalyst coking is banned.
- Polysulfides, responsible for catalyst coking are also banned.
6.5.8 Oil-in
The catalyst bed temperature being stabilized at 400deg.C, the reaction section pressure is
increased to a minimum of 8 kg/cm2 g at the separator drum by injection of start-up
hydrogen. Swing open the blind on feed.
The hydrotreated feed from NHT unit is introduced to the reactors at 60% of the design rate
in about 10 minutes. The furnaces are controlled to maintain 400deg.C at the inlet of each
catalytic bed (around 405deg.C at furnace outlet). If exothermal phenomenon is not observed
(temperature increase higher than 5deg.C), the inlet reactor temperature can be increased
by 10deg.C during the first hour, then pushed to 460deg.C at a rate of 25deg.C per hour.
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During this period, a continuous injection of chlorinated agent is carried out. The quantity to
be introduced amounts to 10 ppm wt calculated as Cl concentration in the feed rate to the
unit. Check with catalyst samplers that the chlorine content of the catalyst is lower than
0.8wt%. The Cl concentration in feed can be increased-up to 20 ppm wt. The chlorinated
agent can be used as pure component, or diluted in naphtha feed.
The production of gas brings an automatic increase of pressure which is adjusted at its
operating value. The excess of gas is fed to the feed pretreater.
The temperature increase profile in function of the water content of the recycle gas is
described in the following paragraph “Start-up phase”.
If the feed pretreater unit cannot be in operation before the reformer start-up, it is necessary
to use a dry and low sulfur content naphtha for this phase of start-up. Route the feed from
storage to the NHT stripper to eliminate the water before entering the reformer unit.
6.5.9 Start-up phase

After feed injection, a phase of water removal develops for a period of 3 to 5 days during
which special precautions must be taken for temperature increase profile in function of water
and hydrogen sulfide concentrations in the recycle gas (See figure 10).
If the naphtha feed is already dry and desulfurized (from NHT), the operator has advantage
to bring the feed rate to its maximum value in order to reduce the dehydration time and, in
consequence, to minimize the period necessary to reach the desired octane level (for
information, it is recommended to decrease as fast as possible the water content in the
reformer feed below 5 ppm wt).
Please also note that a high feed rate brings a good repartition of flow through the catalytic
beds and an improved distribution of chlorine on the catalyst. Hence, the exothermal
reactions are minimized.
6.5.9.1 First temperature level: 460deg.C

This temperature level is maintained as long as the water content in the recycle gas is over
200 ppm vol and the hydrogen sulfide content higher than 10 ppm vol.
The injection of chlorinated agent is maintained at a rate of 10 ppm wt chloride to feed during
this phase. As the unit is equipped with catalyst samplers, the chloride level of the catalyst
known, it is possible in case of low chloride content to increase the chlorinated agent
injection as to have up to 20 ppm wt chloride to feed.
6.5.9.2 Second temperature level: 470deg.C

The reactor inlet temperature is increased to 470deg.C and maintained at this level as long
as the water content in the recycle gas is above 100 ppm vol and the hydrogen sulfide
concentration is higher than 5 ppm vol. The injection of chlorinated agent is decreased to
5 ppm wt during this phase.
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However, the rate of chloride injection and the place of introduction might be modified in
function of the chloride concentrations determined by analysis on the catalyst samples which
are collected from the reactor bottoms using the sampling systems.
6.5.9.3 Third temperature level: 480deg.C
The temperature is finally increased at inlet of each reactor to 480deg.C and maintained at
this level while keeping the water content in the recycle gas between 100 and 50 ppm vol
and the hydrogen sulfide concentration between 5 and 2 ppm vol. The chloride injection is
reduced to 3 ppm wt in the naphtha feed.
6.5.9.4 High severity operation:  480deg.C
The reactor inlet temperature is then progressively increased to the required value to reach
the reformate octane number as soon as the recycle gas water content is below 50 ppm vol
and the hydrogen sulfide concentration is lower than 2 ppm vol. It is recommended to wait
30 ppm vol moisture in the recycle gas before increasing the reactor inlet temperatures
above 500deg.C.
The chloride injection rate as a function of the recycle gas water content is defined in more
detail under the "normal operation" chapter. When catalyst sampling devices are installed the
catalyst of first and last reactor is analyzed for chloride content.
6.5.9.5 WAIT increase summary
RI Tdeg.C 460 max 470 max 480 max > 480 > 500
H2O in R/G ppm > 200 < 200 < 100 < 50 < 30
H2S in R/G ppm > 10 < 10 <5 <2 <1
Chloride injection rate ppm wt 10 – 5 5 3 2 0.2 - 1
During this period an increase of reactor inlet temperature, RI TºC, implies a temporary rise
of moisture in the recycle gas, as at the new WAIT conditions more water is removed from
the catalyst.
Consequently maintain anyway the new WAIT even though the moisture in the recycle gas
exceeds the allowance.
6.5.10 Figures and drawings attached to putting the unit into service
FIGURE 7 : REACTION SECTION DRY OUT DIAGRAM
FIGURE 8 : CATALYST DRY OUT DIAGRAM
FIGURE 9: CATALYST HEATING REDUCTION AND SULFIDING
FIGURE 10 : TYPICAL REFORMING START-UP
FIGURE 11 : HYDROTREATER, REFORMER, START-UP (FOR YOUR INFORMATION)
FIGURE 12 : HYDROTREATER, REFORMER, START-UP (FOR YOUR INFORMATION)
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REACTION SECTION DRY OUT DIAGRAM

FIGURE 7
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CATALYST DRY OUT DIAGRAM

FIGURE 8
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CATALYST HEATING REDUCTION AND SULFIDING

FIGURE 9
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TYPICAL REFORMING START-UP

FIGURE 10
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HYDROTREATER, REFORMER, START-UP

FIGURE 11
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HYDROTREATER, REFORMER, START-UP

FIGURE 12
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6.6 Operation of the unit

6.6.1 Summary of operating conditions
Chapter 6.3.4 listed the process variables, i.e. the variables (pressure, temperature, space
velocity, H2/HC ratio) which according to the thermodynamics and the kinetics have an
impact on the reactions involved in the process. This rather theoretical approach did not
outline whether the operator could actually change the particular variable. In the present
chapter we will look at these variables again from a more practical standpoint as operating
parameters and how the operators can actually use them to adjust the performance of the
unit.
6.6.2 Control philosophy of the Process
To assure the unit’s performance, there are several controlled operating parameters on
which operators can act on:
- flow rate of the naphtha feed from NHT unit;
- control of reactors inlet temperatures, by adjusting the heaters duty, with impact on final
reformate quality (octane number) and quantity;
- H2/HC ratio controlling the hydrogen flowrate of recycle compressor;
- reaction section pressure controlling the hydrogen flow rate sent to absorption section;
- stabilization section pressure by adjusting the fuel gas quantity send to network;
- reformate and LPG specifications acting on the column operating parameters: reflux flow
rate control reset by stabilizer’s top temperature and reboiler return temperature reset by
stabilizer’s sensitive tray temperature;
6.6.3 Operating parameters
6.6.3.1 Change of feed rate
The modification of the feed rate, while maintaining a constant reformate octane level,
requires an adjustment of the reactor inlet temperature.
According to experience, it appears easier to monitor the temperature at each reactor inlet at
the same value ("horizontal" profile). "Ascending" or "Descending" profiles can be used (to
handle very high naphtenic feed, heater skin temperature problem, etc...).
6.6.3.1.1 Increase of feed rate
The increase of feed rate must be followed by an increase of reactor inlet temperature using
the indications given in the figure attached in following appendices.
The simplified following rules can apply:
• increase of feed rate by 10%  increase of temperature by 2deg.C.
• increase of feed rate by 20%  increase of temperature by 3.5deg.C.
• increase of feed rate by 50%  increase of temperature by 8deg.C.
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6.6.3.1.2 Decrease of feed rate

The reactor inlet temperature must be reduced at first. This operation is then followed by a
decrease of the feed rate according to information shown on the figure given in following
appendices.
The simplified following guidelines can apply:
• decrease of feed rate by 10%  decrease of temperature by 2deg.C.
The changes in feed rate and temperatures are accomplished in such a way that cracking
reactions and coke deposit on the catalyst are avoided.
Following such adjustments, it is necessary to check the reformate octane number after
stabilization of the operating conditions and to correct the eventual injections of water and
chlorine. The recycle ratio must be recalculated and possibly adjusted by varying on the
recycle compressor speed.
6.6.3.2 Change of reformate octane number
With a constant feed rate, the modifications of the reformate octane number are obtained by
changing the reactor inlet temperature.
The temperature increase per point of octane number depends on several factors: operating
pressure, recycle ratio, feedstock quality in terms of naphthenes and aromatics content and
mostly the state of catalyst activity.
Nevertheless, the operator can follow the indications given in following appendices, or follow
the « rules-of-thumb » listed here below:
• RON (clear): 85 to 90  temperature increase of ~ 1.8deg.C per octane point.
6.6.3.3 Recycle gas water content. Water and chloride injection
The adjustment of water content in the recycle gas at the high pressure separator is a
determining factor for a good operation of the reforming unit.
The recommended water concentration in the recycle gas must be between 15 and 25 ppm
vol. This corresponds to a water content in feed of about 5 ppm wt. Note also that
decomposition of oxygenate compounds increases this value.
Normally a well operated NHT stripper provides a feed containing 1 to 5 ppm wt of water.
An increase of concentration can indicate:
• A misoperation of the stripping column at the pretreater.
• The feeding of the reformer from a storage having not been water drained.
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• The utilization of lines or equipments which have been either water washed or pressure
tested with water.
In such cases, an additional injection of chlorine agent must be performed
(tetrachloroethylene, trichloroethylene or tetrachloromethane are preferred) agent at a rate
indicated in the following table. If necessary, the reactor temperature shall be decreased.
Conversely if the unit is fed with a feedstock properly treated, an injection of water can be
carried out at a rate of 2 to 4 ppm wt calculated on the feed rate expressed in weight.
Anyway never let the moisture in the recycle gas fall under 10 ppm vol. Start water injection
when reaching this value.
Note: As a thumb rule, it can be said that at 1 ppm wt of water in feed corresponds to ~ 3 to
5 ppm vol moisture in recycle gas. Never forget this rule when injecting water to feed.
About 1 hour after water injection the recycle gas moisture analyzer shall start to
increase. On the contrary this analyzer shall be controlled and the water injection
reduced or water packages checked for leaks.
The water concentration is monitored by an on-line analyzer placed on the recycle gas.
The most common are of the "Beckmann" type with a phosphoric acid cell. These analyzers,
which are normally resistant when the water concentration is below 700 ppm, show partial
degradation in function with time and their indications correspond to values getting lower and
lower. Note that online analyzers can be crosschecked with a portable analyzer (Mitsubishi
or Shaw).
Before adjusting the water injection rate, it is recommended to check the analyzer cell as per
the methods given by the manufacturer.
Chloride level of the catalyst is maintained by injecting a chlorinated agent to the feed. As to
have an accurate control of the injection the chlorinated agent is diluted with reformate.
Table indicating the approximate chloride content of the feed

in function of the water content in the recycle gas
Recycle gas Chloride content, (Cl),

content, ppm weight in feed
ppm volume
15 - 25 0.2 to 1.0
25 - 35 1.0 to 1.5
35 - 50 1.5 to 2.0
 50 3.0 (Decrease reactor inlet temperature to 480deg.C).
 100 5.0 (Decrease reactor inlet temperature to 460deg.C).
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When the recycle gas contains more than 35 ppm vol water, such situation must be
temporary and no short term effects occur. In the range of 50 ppm, an increasing production
of LPG can be noticed against a decrease of the reformate yield, as the water increase
enhances temporarily the last reactor catalyst acidity.
The chloride concentration on the catalyst must stay in the following range:
• 0.9 wt % to 1.1 wt %
With sampling device it is recommended to collect a sample from reactors twice a month and
eventually at a higher frequency during the temporary changes of operation.
The normal analyses to be carried out on such samples are: chloride, coke, sulfur and
occasionally, metals, surfaces area and platinum dispersion.
If the unit is not equipped with sampling device, the following figures 13 to 15 can be used to
monitor the H2O/Cl equilibrium with a better accuracy than the figures given in the table
(Chloride content of the feed function of the water in the recycle gas).
Using figure 15, H2O/Cl molar ratio required to maintain 1 wt % chloride on the catalyst at
actual conditions can be determined.
Catalyst surface area is obtained by using the following rule:
- As already mentioned in paragraph “catalyst mechanism”, the normal range of water
content in recycle gas is about 15 to 25 ppm vol, and the associated HCl should be
approximately 0.1 to 0.2 ppm vol (i.e. 0.5 ppm vol or less).
- HCl content in recycle gas is measured by dedicated Dräger tubes, scale 0 to 10 ppm vol.
Sampling point shall be drained until the temperature is equal to the one of the recycle gas at
compressor discharge.
- Typically chloride injection in normal operating conditions shall be between 0.2 and 1.0 ppm
wt related to feed. In the case of presence of nitrogen compounds in feed, chloride injection
shall be increased (~ 0.25 ppm wt of chloride for 0.1 ppm wt nitrogen above 0.5 ppm wt in
feed)
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The specific area varies as follows:

Brand new catalyst = base
st
After 1 regeneration = base x 0.92
After 2nd regeneration = base x 0.87
After 3rd regeneration = base x 0.85
th
After 5th regeneration = base x 0.81
th
th
Chlorine injection estimation

PH2O / Cl MR
RFCC = PFCC x
RH2O / Cl MR
With:
RFCC = Required feed chloride content in ppm wt.
PFCC = Present feed chloride content in ppm wt.
PH2O/Cl MR = Present H2O/Cl molar ratio calculated as follows:
H 2 O ppm wt
(Feed Kg/h x ) + (RGNm 3 h/22.4 x H 2 O ppm vol)
18
Cl ppm wt
(Feed Kg/h x ) + (RGNm 3 h/22.4 x Cl ppm vol)
35.5
RH2O/Cl MR = Required H2O/Cl molar ratio obtained from figure 15.

Example:
Feed = 50000 Kg/h - H2O = 4 ppm wt
Cl = 1.5 ppm wt
Recycle gas = 70000 Nm3/h - H2O = 26 ppm mol
Cl = 0.4 ppm mol
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Required H2O/Cl molar ratio = 20

 50000 x 4 ppm  + 70000
 18  
22.4 x 26 ppm 
RFCC = 1.5 wt ppm x = 2.0 wt ppm
 50000 x 1.5 ppm

 + 70000
35.5   
22.4 x 0.4 ppm  x 20 
Notes: Cl in feed is the chloride coming from the feed (if any) plus the Cl from chloriding
agent injection. Cl injection shall be the difference between required chloride content
and Cl contained in feed (if any).
As surface area decreases with the regenerations, catalyst ability to fix chloride is
also decreasing. This is well evidenced in figure 15. Consequently chloride content
of the feed shall be increased.
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MONITORING OF EQUILIBRIUM CHLORIDE ON CATALYST

FIGURE 13
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« CHLORIDE ON CATALYST »
TEMPERATURE CORRECTION FACTOR
FIGURE 14
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MOLAR WATER / CHLORIDE RATIO DETERMINATION

TO OBTAIN 1 WT% CHLORIDE ON CATALYST
FIGURE 15
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6.6.3.4 Sulfur content - hydrogen sulfide concentration

A properly hydrotreated feedstock must contain less than 0.5 ppm wt sulfur.
If the accuracy of the analytical methods is not sufficient to monitor the content of sulfur in
feed, it is practical to measure the hydrogen sulfide in the recycle gas and in the stabilizer
off-gas.
H2S content in the recycle gas should not be more than 1.0 ppm vol. and should normally be
less than 0.5 ppm vol.
As already said in paragraph 6.3.3.4 for low values of H2S in the recycle gas, a more
accurate approach can be made by checking the H2S content of the stabilizer off gas. For
instance 5ppm vol. in stabilizer off-gas corresponds to about 1 ppm vol in the recycle gas.
For instance 5 vol. ppm in stabilizer off gas corresponds to about 1 vol. ppm in the recycle
gas.
6.6.4 Adjustment of operating conditions

Chapter 6.3.4 listed the process variables, i.e. the variables (pressure, temperature, space
velocity, H2/HC ratio) which according to the thermodynamics and the kinetics have an
impact on the reactions involved in the process. This rather theoretical approach did not
outline whether the operator could actually change the particular variable. In the present
chapter we will look at these variables again from a more practical standpoint as operating
parameters and how the operators can actually use them to adjust the performance of the
unit.
6.6.4.1 Pressure
Theoretically, the lower the pressure, the higher are the reformate yield and hydrogen purity -
for a given space velocity - and feed characteristics.
The pressure at the last reactor inlet is generally considered as the most representative for
the purpose of this discussion.
However there is little flexibility since the unit and the recycle compressor are designed for a
given pressure. Lowering the operating pressure below the design pressure results in higher
pressure drop and is limited by the recycle compressor design driver power.
The low pressure which favors high yields, favors also coke build up.
6.6.4.2 Temperature
Temperature, together with space velocity (see hereafter) is the most important and most
used operating parameter.
By simply raising or lowering reactor inlet temperatures, operators can increase or decrease
the octane number of the product.
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Since all reactor inlet temperatures are not necessarily identical it is commonly accepted to
consider the weight average inlet temperature (WAIT) as representative of the reactor
temperatures.
Nevertheless, a WAIT flat profile is recommended for fixed bed reformer operation.
The WAIT is defined as follows:
WAIT =
wt of catalyst R1 x Ti1 + wt of catalyst R 2 x Ti2  + wt of catalyst R3 x Ti3
Total wt of catalyst
Ti1, Ti2, Ti3 are inlet temperatures to reactors R1, R2, R3

(wt of catalyst R) is the weight of catalyst in reactors R1, R2, R3,
Assuming the space velocity (i.e. the feed rate) and feed characteristics stay unchanged, an
increase of temperature (i.e. WAIT) has the following effects:
• Increases octane number.
• Decreases the yield (of C5+ fraction).
• Decreases the H2 purity.
• Increases the coke deposit.
At constant WAIT, the coke deposit and the ageing of the catalyst (caused by the
regenerations, the possible metal deposit and the unavoidable upsets) result in a slight but
steady loss of activity (i.e. of octane). An increase of temperature (WAIT) through the cycle
compensates this activity loss.
Larger and temporary changes in temperature are required:
• To change octane - at constant feed quality and quantity.
• To change feed quantity and still maintain octane (see space velocity hereunder).
• To change feed quality and still maintain octane (see feed quality).
The set of curves given in the appendix allow an estimate of the increment in the WAIT which
would result from increment in the selected parameter:
• Space velocity (WHSV) figure 16
• Pressure figure 17
• RON clear figure 18
• Feed quality (A + 0.85N and MABP) figures 19 and 20
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Example: one wants to increase RON from 96 to 100. Refer figure 18 in appendix.
RON 96  WAIT = -4.5
RON 100  WAIT = 5.5
Result  WAIT = 5.5 - (-4.5) = 10deg.C
CONCLUSION: WAIT must be raised by 10deg.C.
WABT, weight average bed temperature, is defined as follows:
 Ti1 + Ti1 '  +  catalyst wt R x Ti2 + Ti2 '  +  catalyst wt R x Ti3 + Ti3 ' 
 catalyst wt R1 x     
 2   2 2   3 2 
WABT =
Total weight of catalyst
Ti1, Ti2, Ti3 are inlet temperatures for reactors R1, R2, R3
Ti1', Ti2', Ti3' are outlet temperatures for reactors R1, R2, R3
catalyst wt R1, R2, R3 are the weight of catalyst for reactors R1, R2, R3
6.6.4.3 Space velocity

Space velocity has already been defined as the amount of liquid (expressed in weight or in
volume) which is processed per hour divided by the amount of catalyst (in weight or in
volume). The inverse of the space velocity is linked to the residence time (or contact time) in
the reactors.
Knowing the liquid flow rate (or the space velocity), plus the recycle flow and the reactors
operating conditions enables to calculate the actual flow in the reactor, hence the contact
time.
The lower the space velocity is (i.e. the higher the contact time), the higher the severity,
assuming that all other conditions stay unchanged.
Lowering the space velocity has, then, the same effects as increasing the temperature i.e., it:
• Increases the octane number.
• Decreases the product yields.
• Decreases H2 purity.
• Increases coke deposit.
If temperature increase is limited (by heater design duty or anything else) lowering space
velocity (i.e. decreasing flow rate) can give an additional boost to octane.
Operators must bear in mind that each time liquid feed rate is changed, a temperature
correction must be applied if octane is to be maintained. When feed is increased,
temperature must be raised and conversely, when feed is reduced temperature must be
lowered.
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When changing feed rate, an important rule is:

• For feed increase: Increase feed first, then adjust temperature increase to meet
octane.
• For feed reduction: Lower temperature first, then adjust feed reduction to meet
octane.
Example of temperature adjustment with space velocity (see figure 16 in Appendix).
Original conditions Increased feed

Feed vol. bbl/h 800 1000
m3/h 127.19 158.99
Sp gr (API) lb/bbl (55) 265.3 no change
Kg/m3 756.9 no change
Feed wt lb/h 212,240. 265,300.
t/h 96.270 120.340
Catalyst wt (lb) 117,910. no change
(t) 53.480 no change
WHSV 1.8 2.25
WAIT reading -2 + 2.5
(deg.C)
WAIT change Base + 4.5
(deg.C)
CONCLUSION: For an increase of WHSV from 1.8 to 2.25 the WAIT must be
increased by 4.5deg.C.
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6.6.4.4 Hydrogen to hydrocarbon ratio

The H2/HC ratio is the ratio of pure H2 in the recycle (mole/h) to the feed flow rate (mole/h).
The H2/HC ratio is calculated as follows:
R
H2 M xY
HC = F
m
Where R is the recycle flow in kg/h
M is the recycle gas molecular weight
F is the feed rate in kg/h
m is the feed molecular weight
Y vol. fraction of H2 in the recycle gas
R
H2
= 22.4 x Y
HC F
m
3
Where R is the recycle flow in Nm /h
22.4 is the recycle gas molecular volume
F is the feed rate in kg/h
m is the feed molecular weight
Y vol. fraction of H2 in the recycle gas
The recycle gas molecular weight (M) is obtained by chromatographic analysis, as well as
the H2 vol. fraction (Y).
The feed molecular weight (m) is obtained by chromatographic analysis or by correlation
from its distillation range and specific gravity.
Operators can change the H2/HC ratio by lowering or increasing the recycle compressor
flow.
The H2/HC ratio has no obvious impact on the product quality (octane) or yield, but a high
H2/HC ratio reduces the coke build up.
It is strictly recommended to operate with a H2/HC ratio equal to (or higher than) the
design figure.
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6.6.4.5 Feed quality

The feed has always been hydrotreated with the object of removing sulfur, nitrogen, metals
and in case of cracked naphthas the olefins and diolefins. It is assumed the pretreated feed
meets the specifications given in the paragraph “Feed quality” 6.3.4.6.
The feed quality, once hydrotreated, is mainly expressed by its chemical analysis and its
distillation range.
A) Chemical analysis
The chemical analysis of the feed will give for each carbon number (C6, C7, ... to C10) the
breakdown into Paraffins, Naphthenes, Aromatics (or PNA).
As the fastest reaction is the dehydrogenation of naphthenes into aromatics, the quality index
of a specific feed can be characterized by its initial concentration in naphthenes and
aromatics.
An index (A + 0.85N) where N and A are the volume percent of naphthenes and aromatics in
the feed, is used by Axens to characterize the process feed.
A feed with a high (A + 0.85N) index will be easier to process than one with a lower one, i.e.:
• The same octane will be obtained at a lower severity (temperature) and the product yield
will be higher.
• Or for the same severity (temperature), the octane will be higher.
Typically, with a feed having a higher reforming index, the naphthenic hydrocarbon content is
generally higher, the endothermic reaction heat is increased and the feed flow rate will be
limited by the heater design duty. In the opposite case, with a paraffinic feed the hydrogen
purity of the recycle gas decreases and operation will be limited by the recycle compressor
capacity.
Figure 19 in appendix gives an estimate of the relationship between PNA and severity. As
with the other figures it is used to determine increments related to an existing base case (see
example), versus a new case.
B) Distillation range
One feed property that Refiners can control is the distillation range. The naphtha end point is
controlled in the upstream unit distillation. The initial boiling point is controlled at the naphtha
hydrotreater splitter.
The feed distillation range in European countries where the end boiling point of the marketed
gasoline shall be lower than 205deg.C is generally as follows:
(deg.C) (°F)
IBP (Initial Boiling Point) 70 - 100 158 - 212
EBP (End Boiling Point) 140 - 180 284 - 356
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Lower IBP enables to include in the feed, components such as methylcyclopentane (BP
72deg.C) and cyclohexane (BP 80.7deg.C) which are benzene precursors.
In some cases however the benzene content in the gasoline is to be strictly limited. In these
cases the IBP must be raised to 82deg.C (180°F) or above.
A feed with a low IBP generally contains more C6 and lighter paraffins and requires a higher
severity to obtain the same octane number than a feed with a higher IBP.
One must also consider the distillation end boiling point (EBP). High EBP means heavier
fractions which are richer in aromatics and naphthenes and thus are easier to process.
However the high boiling point fractions are potential sources of polynuclear aromatics which
are coke precursors. In addition high EBP of the feed leads to obtain a reformate EBP higher
than 200deg.C (problem with gasoline pool). EBP higher than 180deg.C (356°F) are
generally not recommended in European countries.
Figure 20 in appendix gives an estimate of the change in severity associated with a change
in the distillation range. The distillation range is expressed by the mean average boiling point
(MABP) defined as follows:
MABP =
T 10% + 2 x T 50% + T 90%
4
Example of temperature adjustment for A + 0.85 N and MABP changes

(See figures 16 and 17 in appendix)
Base case Alternate case

(A + 0.85 N) LV% 42 35
MABP (deg.C) 130 122
 WAIT Figure 16 - 4.8 + 0.7
 WAIT Figure 17 - 1.2 + 0.8
 WAIT from Figure 16 (A + 0.85 N) Base + 5.5
 WAIT from Figure 17 (MABP) Base +2
CONCLUSION: WAIT must be increased by 7.5deg.C.
6.6.4.6 Butane content of the reformate

In the case of a gas chromatography is not available the butane content of the reformate can
be estimated using figure 21.
6.6.4.7 Start of run WAIT calculation
S.O.R. WAIT is not really an operating parameter but an indication of the catalyst activity.
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Figure 22 gives the expected SOR WAIT versus RONC for different qualities of feedstock.
(0.85 N + A) using a fresh catalyst in the following operating conditions:
WHSV = 2 - reactor average pressure = 13.5 barg.
It is supposed that chloride level of the catalyst is between 0.9 to 1.1 wt %, that recycle gas
moisture, chloride and H2S contents are according to the recommendations.
After correction for pressure, WHSV and MABP the SOR WAIT can be compared to the
present WAIT. The  between both WAIT’s gives an idea of the catalyst activity.
Plotting on a graph the  WAIT allows to follow the loss of activity of the catalyst.
6.6.4.8 Cycle length

The cycle length is defined:
• either as the number of months of operation.
• or the number of cubic meters of feed treated per kilogram of catalyst or barrels per
pound.
It depends on:
• the operation severity:
– WHSV,
– RONC,
– H2/HC,
– Operating pressure.
• the nature of the feedstock:
– Feed composition (0.85N+A vol%),
– End Boiling Point deg.C.
The influence of these parameters on the cycle length is given in the following figures:
Figure 23 : WHSV
Figure 24 : RONC
Figure 25 : H2/HC
Figure 26 : Operating pressure
Figure 27 : Feed composition (A + 0.85N vol%)
Figure 28 : End Boiling Point deg.C
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Application
The cycle length is equal to 10 months in the base case conditions. What will be the cycle
length in the new case ?
Base case New case

WHSV 1.5 2
RONC 94 96
H2/HC 6 5
Operating pressure 15 18
Feed composition (A + 0.85N vol%) 30 40
End Boiling Point deg.C 160 170
Figure 23 Figure 24 Figure 25 Figure 26 Figure 27 Figure 28

WHSV RONC H2/HC PRESS. A+ EBP
0.85N
Base case 1.78 1.62 1.28 1.0 0.64 1.1
New case 1.3 1.34 1.0 1.22 1.0 1.0
The cycle length for new case will be equal to:

 1.30   1.34   1.0   1.22   1.0   1.0 
10 x   x  x  x  x  x   = 8.2 months
 1.78   1.62   1.28   1.0   0.64   1.1
6.6.4.9 Delta C5+ yield (wt %) for different feedstocks/versus RONC

Figure 29, allows you to forecast, for different feedstocks, the change in C5+ yield which will
result from a variation of the reformate octane number.
The curves were plotted for an average reactor pressure of 13.5 bar g. Other operating
pressures can be approximated by using similar trends as plotted in figure 29.
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APPENDICES ATTACHED TO
PARAGRAPH OPERATING PARAMETERS
FIGURE 16 WAIT correction for WHSV

FIGURE 17 WAIT correction for pressure
FIGURE 18 WAIT correction for RON Clear
FIGURE 19 WAIT correction for (A + 0.85N)
FIGURE 20 WAIT correction for MABP
FIGURE 21 Reformate RVP versus Butane content
FIGURE 22 SOR WAIT requirement versus feed composition
(A + 0.85N vol %)
FIGURE 23 Relative coking rate versus WHSV
FIGURE 24 Relative coking rate versus RON Clear
FIGURE 25 Relative coking rate versus recycle molal ratio H2/HC
FIGURE 26 Relative coking rate versus reactors pressure
FIGURE 27 Relative coking rate versus feed composition
(0.85N+A vol%)
FIGURE 28 Relative coking rate versus feed end boiling point
deg.C
FIGURE 29 Delta C5+ yield (wt %) for different feedstocks/versus
RON Clear
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WAIT CORRECTION FOR WHSV

TYPICAL HYDROTREATED STRAIGHT RUN NAPHTHA
FIGURE 16
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WAIT CORRECTION FOR PRESSURE

(TYPICAL HYDROTREATED STRAIGHT RUN NAPHTHA)
FIGURE 17
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WAIT CORRECTION FOR TYPICAL

HYDROTREATED STRAIGHT RUN NAPHTHA
FIGURE 18
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FIGURE 19
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FIGURE 20
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REFORMATE RVP VERSUS BUTANE CONTENT

FIGURE 21
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SOR WAIT REQUIREMENT VERSUS FEED COMPOSITION

(A + 0.85N Vol.%)
FIGURE 22
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RELATIVE CYCLE LENGTH VERSUS WHSV

FIGURE 23
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RELATIVE CYCLE LENGTH VERSUS RON C

FIGURE 24
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RELATIVE CYCLE LENGTH VERSUS

H2/HC MOLAR RATIO
FIGURE 25
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REACTOR AVERAGE PRESSURE
FIGURE 26
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RELATIVE CYCLE LENGTH VERSUS FEED COMPOSITION

(A + 0.85N Vol.%)
FIGURE 27
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FEED END BOILING POINT
FIGURE 28
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DELTA C5 + YIELD (WT%) FOR DIFFERENT

FEEDSTOCKS / VERSUS RON C
FIGURE 29
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6.6.5 Troubleshooting
6.6.5.1 General
The main causes of Refiners’ concern related to process can be one or more of the following:
• Unexpected decrease of octane number.
• Loss of reformate yield.
• Unexpected T reduction in the first catalytic bed.
• High hydrocracking rate.
6.6.5.2 Unexpected decrease of the octane number

We are not considering here the cases where the octane number decreases which are easily
related to:
• A change in feedstock quality (more paraffins).
• A lowering of the reactor inlet temperature.
• An increased feed flow rate.
An unexpected decrease of the octane number may be caused by one or several of the
following points:
• Leak in the feed/effluent exchangers.
• Presence of nitrogen in the feed.
• Presence of sulfur in the feed.
• Presence of metals in the feed.
• Low chloride content of the catalyst.
• Partial by-pass of the catalyst.
A) Leak in the feed/effluent exchanger

Since the feed is at higher pressure than the effluent, it may leak through the exchanger.
Relatively small leaks can lower the product octane number significantly.
Exchanger leaks can be detected by injecting tracers in the feed. An easy natural tracer is
dimethylcyclohexane which is present in the feed and not in the product. Another method is
measuring the octane number on the product side, upstream and downstream the
exchangers.
How to detect feed / effluent exchanger leak:
- Presence of sulfur in the reformate allows you to suspect a leak at feed/effluent exchanger
(the small amount of sulfur present in feed 0.1 to 0.5 ppm wt is transformed in H2S in the
reactors and is mainly found in the recycle gas).
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To ascertain a leak on this exchanger the following methods can be followed:

TEST WITH PHENOL
Small quantity of phenol is injected in the reformer feed. Phenol is dissociated in the reactors
(hydrocarbon and H2O) and shall not be found in the reformate if the exchanger is not
leaking. Phenol in feed and separator liquid is dosed by UV detection (method IFP-9860).
Procedure is as follows:
1. Decrease the liquid level in separator down to the lowest acceptable level. Analyse feed
before injection of phenol.
2. Inject 100 ppm phenol in reformer feed. Analyse feed 10 minutes after phenol injection.
Phenol concentration should be approximately 100 wt ppm.
3. After 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, take a
sample at separator drum bottom.
4. Stop phenol injection when the last sample at separator bottom has been taken.
In case of exchanger leak, phenol will be detected in separator product. As the method
forecast use of 25 ml samples by safety each sample will be equal to 50 ml.
In the case you cannot perform by yourselves the analysis, send well sealed sample bottles
to an independent laboratory or to Axens’ laboratory.
TEST WITH HYDROCARBON TRACERS
Ratio cyclohexane / methyl-cyclopentane in reformate.
cC6
 0.1
McC5
Above this ratio you can consider that the reactor feed / effluent exchanger is leaking.
For instance a ratio of 0.3 means approximately 5% feed leak to effluent.
Ratio methylcyclohexane + 1Cis2 Dimethyl cyclopentane / 1 trans2
Dimethylcyclopentane in reformate.
McC6  1 cis2DMcC5
 1.7
1 trans2 DMcC5
Above this ratio you can consider that the CRU feed / effluent exchanger is leaking. For
instance a ratio of 2.0 means approximately 5% leak feed to effluent.
Note: These ratios are valid if the components used for calculation are present in feed for
more than 1% each. Also they are valid for a reformate having a RON between 94 and
102.
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B) Presence of nitrogen in the feed

The maximum allowable nitrogen content in the feed is 0.5 ppm wt expressed as NH 3. Its
effects to the catalyst, the causes and remedies have been described in chapter “Catalyst
contaminants”.
C) Presence of sulfur in the feed

The maximum allowable sulfur content in the feed is 0.5 ppm wt expressed as sulfur.
It is worth nothing that sulfur affects primarily the octane number.
The effect, the causes and remedies have been covered in chapter “Catalyst contaminants”.
D) Presence of metals in the feed

The presence of metal induces a permanent catalyst poisoning which results in a quick and
noticeable drop in the octane number. It shows mainly through a shift in the T across the
reactors.
E) Low chloride content of the catalyst

If the chloride content is too low, the catalyst activity is reduced and the octane is lower than
expected.
It is possible with catalyst sampling devices to check and optimize the chloride levels.
The optimum content lies between 0.9 to 1.1 wt %.
Any shortfall in chloride level can be rectified by increasing the continuous injection level. It is
recommended to do this correction slowly as short large doses can create large chloride
gradients through the reactors, especially in dry units. It may take several weeks to re-
equilibrate the catalyst chloride levels following a large deviation.
F) Partial by-pass of the catalyst

If for any reason, part of the catalyst is by-passed, the actual space velocity is higher than
expected and the octane will drop. A higher temperature would be required to make-up for
the octane loss.
The causes of by-passing can be multiple: damaged internals, build-up of fines or scales at
various places in the catalyst bed, catalyst slumping, etc...
A hazardous situation may occur because of channeling, due to the risk of exothermic
hydrocracking reactions taking place in the area where space velocity is very low.
By-passing and channeling are generally identified by increased pressure drop or uneven
and odd temperature profiles.
In such a case the reactor should be dumped, screened and reloaded.
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6.6.5.3 Loss of product yield

A loss in product yield may be caused by one or several of the following points:
• Presence of metals in the feed.
• Too high chloride content of the catalyst.
A) Presence of sulfur in the feed

The sulfur affects primarily the hydrogen rich gas production. Any increase in sulfur above
0.5 ppm wt reflects immediately in a lower H2 yield and a reduced deltaT across the first
reactor. Refer to chapter “Catalyst contaminants” for the causes, effects and remedies.
B) Presence of metals in the feed

This will be discussed later in the item related to decreased T in the first reactor.
C) Too high chloride content of the catalyst

A too high chloride content (above 1.1 wt % as Cl) promotes hydrocracking reactions which
result in a lower products yield, a lower hydrogen purity, a lower hydrogen yield, but a higher
octane.
A too high chloride content will be detected through an increased yield of stabilizer overhead
liquid and gas and lower hydrogen recycle purity.
To correct it, chloride injection must be reduced, but not stopped unless severe over
chloriding occurs. It may take several weeks to re balance the chloride levels on the catalyst.
6.6.5.4 Unexpected T reduction

The temperature difference T (inlet - outlet) in the various reactors is a very good indication
of the catalyst condition.
Obvious reasons for a T decrease are:
• Feedstock quality: naphthene dehydrogenation is highly endothermic. A lower
naphthene content shows up immediately on the T in the first reactor.
• H2/HC ratio increase (increased recycle). An increased recycle acts as a larger heat
sink for the heat of the reaction.
Other reasons of a T decrease are the consequence of upsets, mentioned earlier, such as:
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• Presence of nitrogen in the feed.

• Too high chloride content (which favors hydrocracking - exothermic reaction).
A loss of T in the first reactor generally results from a sulfur upset in the unit feed. Poor
operation of the pre-treatment reactor or of the stripper can then be suspected. Severity must
be reduced, according to the H2S content in the recycle (for H2S > 5 ppm vol, reduce
temperature to 480deg.C).
In case of low T in reactors 2 and 3, hydrocracking can be suspected. If such is the case,
H2 purity drops and LPG production increases.
Generally hydrocracking does not occur in the first reactor because the average temperature
is lower.
But the most worrying aspect of a decreased T, when it cannot be related to one of the
above grounds, is that it may be result of a permanent poisoning with metals.
Lead, arsenic and other metals mentioned in chapter “Catalyst contaminants” are very
severe catalyst poisons. The maximum allowable contents are shown in table 3 of chapter
“Catalyst contaminants”.
Due to the very high poisoning activity of the metals, the catalyst in the first reactor is
affected first, and the deltaT through this reactor decreases. The endothermic reactions
(naphthenes dehydrogenation) move then to the 2nd reactor which exhibits an unexpected
high T.
Heavy metals generally result either from the crude processed or from a poor operation of
the upstream hydrotreating unit. Reprocessing of leaded gasoline (not a common occurrence
to day) can also cause catalyst poisoning.
Metals poisoning requires the dumping and replacement of the catalyst load.
6.6.5.5 High hydrocracking rate and risk of temperature runaway

Hydrocracking will be suspected when H2 purity drops, the amount of LPG and stabilization
off-gas increases with a simultaneous decrease of product yield.
Hydrocracking can be caused by:
• A fresh catalyst (too active) or an excessive acid function of the catalyst (i.e. high
chloride).
• A too high severity (either a too high temperature at the reactor inlet or a too low
space velocity).
• Poor distribution (channeling) in the reactor which results in local high severity
conditions.
The precautions to avoid hydrocracking are:
• Not to operate at capacity below the design turn-down ratio (50%).
• Not to introduce feed on a fresh or regenerated catalyst before sulfiding.
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• Not to introduce feed for the first time on a fresh or regenerated catalyst, at
temperature higher than 400deg.C. For a subsequent restart the temperature limit
can be increased to 430deg.C.
• When raising throughput, to raise flow first and increase temperature afterwards.
• When lowering throughput, to lower temperature first and throughput afterwards.
• To raise temperature always cautiously: proceed by increment of 2deg.C/h.
• To monitor the differential pressure in the reactors. An increased differential pressure
is the sign of poor distribution.
If hydrocracking is suspected:
• Lower the reactor inlet temperature down to 400deg.C.
• Increase the feed rate to full capacity (to increase space velocity).
• Keep (or set) the recycle gas flow to the maximum.
• Consider catalyst dumping after next regeneration.
Note: Excessive hydrocracking will cause the reformate to become deep yellow. This colour
is due to the formation of polynuclear aromatics.
6.6.5.6 Stabilizer high pressure drop/bad fractionation

Ammonium chloride salts deposits on the upper cold trays of the column are generally
responsible for this bad behaviour.
Washing requirement can be decided when column becomes unstable, with considerable
fluctuations in the column top pressure and temperature as well as reflux drum and column
bottom levels. Consequently either reformate RVP or LPG C5+ content are affected.
The following procedure for on-line washing of the stabilizer column can be adopted:
1- Line-up an empty reformate tank to receive reformate during stabilizer washing period.
Note that the reformate will be badly stabilized and will contain chlorinated water.
2- Reduce the stabilizer bottom column down to 140deg.C. Stop the reflux pump when
reflux drum level is lower than 20%.
3- Reduce the pressure down to 10 kg/cm2g.
4- Connect treated water injection line to the reflux line upstream the 300-FV-1302. Drain
the treated water line to remove iron oxide scales and other debris until the water is
clear.
5- Close the reflux 300-FV-1302 block valves and by-pass valve. At 140deg.C on
stabilizer bottom start to introduce the treated water to the column. Introduction of
water shall be very gradual to avoid pressure upsets. Then increase the water flow rate
up to 20 wt. % of the feed rate.
6- Collect water sample from reformate to storage line, downstream the reformate trim
cooler,every half hour and check for chlorides and conductivity.
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7- Continue the washing until the chloride level in water is lower than 100 wt ppm in two
consecutive samples.
8- Then discontinue the treated water injection and drain the reflux line for any hold-up
water.
9- Wait for 2 hours for the water in the stabilizer to drain and check the reformate which
must be free of water before starting the bottom temperature increase.
10- Drain the stabilizer reflux drum, bottom, reflux pumps suction for any water.
11- Slowly increase bottom temperature and pressure, gradually, establish the reflux and
normalize the column conditions.
12- Check for reformate RVP and switch the reformate to rundown tank.
Alternatively, the column can be water washed or steamed at the next convenient shutdown.
6.6.5.7 High pressure drop in the reactors

This problem is caused by broken catalyst particles, being trapped between the vertical wires
of the central pipe obstructing the open area. Fines and dust accumulate building a cake
around the centre pipe. At this point the pressure drop will start to increase depending on the
size of area obstructed. For semi-regenerative units, this is generally not a problem. After
catalyst loading, if the catalyst has been mishandled then excess of particles fines will start to
accumulate quickly on the centre pipe and the pressure drop increase will be observed within
several days of operation. If this pressure drop is excessive, then the unit would have to be
shutdown for catalyst screening and cleaning of the centre pipe. If the pressure drop is not
excessive, then the unit can be operated until a shutdown is convenient.
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6.7 Shutdown and restart of the unit

6.7.1 General
Normal shutdown applies to a shutdown planned in advance for preventive maintenance or
to unexpected events which are not of an emergency nature.
Before initiating any planned shutdown, review all records to determine what inspections and
repair work must be accomplished during the shutdown. Prepare a shutdown schedule,
including plans for pre-arranging feed and product inventories during turnaround time. Notify
all services and other dependent operating units of the schedule so that all activities can be
properly coordinated. Arrange for all required parts, tools and services in advance, in
particular adequate nitrogen for purging.
When shutting down, steps should be taken to prevent catalyst or equipment damage from
expansion, contraction, thermal shock or unusual pressure surges. Purge with care all
vessels, using inert gas and steam until all equipment is free of hydrocarbon liquids and
gases. Purge thoroughly and check the atmosphere in the vessels before entering or starting
repairs. Rigorously observe all safety precautions.
The procedure consists of switching-off the feedstock under hydrogen rich atmosphere in
order to reduce the cracking of heavy components in contact with a too hot catalyst.
• Reduce reactor inlet temperature to 460deg.C at a rate of 25deg.C per hour.
• Simultaneously, decrease the feed rate to 60% of its design value.
• Stop chlorinated agent and/or water injection to feed.
• Cut-off the feed and maintain the recycle gas circulation during two hours at 460deg.C at
reactor inlet.
• Cool down the catalytic beds to 350deg.C at a rate of 50deg.C per hour, then switch-off
furnaces.
Several shutdown cases are considered:

 Short duration shutdown (i.e. less than 24 hours).
 Long duration shutdown followed by inspection of equipment.
 Long duration shutdown followed by maintenance, inspection or catalyst unloading
 Shutdown for regeneration
6.7.1.1 Short period shutdown

This shutdown is typically less than 24 hours to carry out minor repairs without opening any
major equipment.
In this case, shutdown the compressor and leave the reaction section under pressure.
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6.7.1.2 Long period shutdown

This shutdown is required for major repair of some equipment or some sections of the unit.
The procedure described above for short period shutdown is followed and completed with full
cooling of equipment to ambient temperature. When required for entering the equipment, the
whole unit is drained and inerted.
If the shutdown is planned for a longer period the procedure is the same for short period
shutdowns but this time, the recycle gas circulation must be maintained until the catalyst
beds are totally cooled down. The recycle compressor is then shutdown and the reaction
section depressurized.
A nitrogen purge is then carried-out in the case maintenance work demands such precaution.
6.7.1.3 Shutdown followed by maintenance, inspection or catalyst unloading

Shutdown for this purpose requires the complete removal of hydrogen and hydrocarbons
from the equipment. The equipment of reaction section must be purged with nitrogen before
admission of air. Other equipments must be steamed out. The first steps of shutdown are the
same as used for long period shutdown described above.
Important notes
1 Entry of personnel into vessels needs particular safety precautions. Vessels operating
in presence of H2S may contain sulfides adhered to the surface of metal. These
sulfides are pyrophoric and may release H2S. The forced ventilation and permanent
supervision is required on vessels subject to work of personnel inside these vessels.
2 The nitrogen purge does not mean that vessel is ready for entering of personnel.
Nitrogen is suffocating gas leading to death. The vessels must be fully vented and
tested for oxygen content before admission of personnel entry. The "dead" spaces in
vessels such as downcomers, separation weirs, etc. must be considered.
6.7.1.4 Shutdown for regeneration

The procedure starts as for a normal shutdown:
• Reduce reactor inlet temperature to 460deg.C at a rate of 25deg.C per hour.
• Simultaneously, decrease the feed rate to 60% of its design value.
• Stop chlorinated agent and/or water injection.
• Switch-off the feed.
The subsequent operation consists of ensuring a maximum elimination of hydrocarbons:
• Under circulation of recycle gas, increase the temperature at reactor inlet to 510deg.C
in one hour.
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• Maintain this temperature during 2 hours and drain all liquid hydrocarbons which have
accumulated in the different cold low parts of the unit and at the separator drum
bottom. Keep same conditions until there is no more purge of liquid.
• Decrease the reactor inlet temperature to 350deg.C at a rate of 50deg.C per hour.
Switch-off the furnaces and stop the recycle compressor.
• Decrease the reaction section pressure and purge with nitrogen in order to eliminate
hydrogen and hydrocarbons (sweeping, pressurization / depressurization, or any
other method). Purge the catalyst sampling device to drain all liquid hydrocarbons
they may have retained. The residual content of hydrogen and of hydrocarbons must
be below 0.3 volume % at the end of the nitrogen purge operations. Isolate the
reaction section with blinds and proceed with the regeneration operation (see chapter
“Special procedure for catalyst”).
6.7.1.4.1 Sulfur removal procedure

Due to the low sulfur of reformer feed when multimetallic catalysts are used, the sulfur
removal should not be necessary.
Anyway, if due to a malfunction of the NHT unit, the reformer feed contained  1 ppm wt total
sulfur for a long period this procedure can be used. As the unit is equiped with sampling
devices, a total sulfur of more than 1000 wt ppm on the catalyst, means than the sulfur
removal shall be performed.
Contamination by sulfur can be reduced by circulating high purity hydrogen at high
temperature transforming sulfur compounds in H2S later on removed by a caustic solution
washing.
As chloride and sulfur occupy concurrently the catalyst sites, addition of chloriding agent
during sulfur removal will help sulfur elimination.
As sulfur is transformed in sulfate during regeneration it is wise, especially with catalyst at
start of life, to remove the sulfur before the regeneration. Sulfates fixed on the catalyst
support are very difficult or impossible to remove.
It is very important to perform the sulfur removal before coke combustion when the unit
suffered an important sulfur poisoning as to avoid an important formation of sulfates during
combustion. But it is to be considered that more coked the catalyst, more difficult the sulfur
removal.
After the feed has been switched off at 460deg.C, reactors inlet temperature is increased up
to 510deg.C and maintained at this value during two hours to strip the hydrocarbons
adsorbed on the catalyst and drain all hydrocarbons which have accumulated in the different
cold parts of the unit. Then reduce reactors inlet temperature to 40deg.C.
• Decrease the pressure of the reaction section to the minimum the recycle gas
compressor can accept.
• By injecting electrolytic hydrogen increase the pressure of the reaction section to a
pressure which can allow a smooth operation of the recycle gas compressor with low
MW gas. Repeat this operation if necessary as to have a hydrogen rich gas
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containing less than 5 vol.% of C3+, then increase the pressure up to aproximately 10
kg/cm2 g at separator drum.
• Start the neutralization solution circulation.
• Start chlorinated agent injection to have a 20/1 H2O/Cl mole ratio (See Table 1).
• Increase reactors inlet temperature to  530deg.C at a rate of 40deg.C/hour.
 inlet T  + outlet T  
  = 525 C
 2 
• Maintain the pressure of the reactor by injecting electrolytic hydrogen.
• Check H2S content at the outlet of each reactor. Plot the results on a graph.
• When H2S content at the outlet of all reactors is lower than 2 vol. ppm sulfur removal
is considered as complete.
• Stop chlorination agent injection and neutralizing circulation. Drain the neutralizing
solution, rinse the circuit with fresh water and drain the cold parts of the reaction
section.
• Cool down the reaction section to 350deg.C at a rate of 50deg.C /hour. Switch-off the
furnaces and stop the recycle gas compressor.
• Depressurize the reaction section to flare and purge with nitrogen in order to eliminate
any remaining H2S, until residual hydrogen results lower than 0.1 vol. %. Isolate reaction
section with blinds and proceed with the regeneration procedure.
6.7.1.4.2 Sulfate removal procedure

If the sulfur removal is unsuccessful, either checked by sulfur analysis with catalyst samplers
or if the H2S in recycle gas stayed very low during the sulfur removal phase, sulfate removal
shall be carried-out after the combustion phase.
Basically sulfate removal procedure is identical to sulfur removal one. To be noted that
during coke combustion part of the sulfur is eliminated under the form of SO 2 while the rest is
transformed in sulfates and sulfur oxides.
The reaction section has the following conditions at the end of combustion:
• Recycle compressors in service, RiT’s = 510deg.C, O2 content in the recycle gas  1
vol. %, all reactors T’s negative, neutralization circulation in service.
The sequence is as follows:
• Stop chlorinated agent injection and neutralisation solution circulation.
• Rinse the circuit with fresh water, then drain carefully all cold low points.
• Decrease RiT’s from 510deg.C to 350deg.C.
• Cut combustible to fired heaters and stop the recycle gas compressor.
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• Depressurize the section. Purge the section with nitrogen until O2 < 0.3 vol. %.
• Set blinds in reduction position.
• Introduce electrolytic hydrogen and follow exactly the sulfur removal procedure, the
only difference being that RiT’s are decreased to 480deg.C, in one hour instead of
350deg.C before switching-off the heaters and stopping the recycle gas compressor.
• Pressurize the section with nitrogen up to the regeneration pressure.
• Start the recycle gas compressor and cut-on fire to the heaters.
• Slowly inject air until obtaining 1 vol. %. Note that residual combustion can be
expected due to the carbon content of the chlorinating agent used during the sulfate
removal.
• Resume neutralisation solution circulation and chloriding agent injection.
• Increase RiT’s up to 510deg.C.
When no more sign of post combustion follow the oxychlorination, calcination and drying
procedure as described before.
6.7.2 Unit restart

The start-up can then be carried out according to the following procedure:
• Increase the unit pressure to 8-12 kg/cm2 g, using reformer hydrogen rich gas or
electrolytic hydrogen. In case of hydrogen shortage the pressure can be increased to
the lowest pressure which permits a start of the recycle gas compressor. A nitrogen
make-up is also possible, but hydrogen concentration shall stay above 60 vol%.
• Start-up recycle gas compressor.
• Light all furnaces and increase the reactor temperature to 430deg.C at a rate of
40deg.C per hour.
• After temperature stabilization, inject feed at 60% of design capacity.
• Adjust reactor inlet temperature at a rate of 30deg.C per hour up to 460deg.C then
20deg.C per hour up to 480deg.C and finally by steps of 10deg.C per hour in order to
obtain the desired reformate octane number, under the condition that moisture in the
recycle gas stays under 30 ppm vol.. On the contrary refer to section “Start-up
phase”.
• Adjust the required feed rate.
• Resume chlorinated agent and/or water injection to feed.
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6.7.3 Emergency shutdown

6.7.3.1 General
This unit is equipped with certain emergency shutdown controls which will automatically
place the unit in a non-hazardous status should a major failure occur. The actions of the
emergency shutdowns are aimed at protecting (a) the personnel and (b) the catalyst and
equipment from heavy coking or serious damage.
Personnel and equipment protection also results from the following:
 Personnel having a thorough knowledge of the safe operating and shutdown
procedures.
 A compliance with the safety rules in plant construction i.e. safety distances,
adequate orientation, etc.
 The installation of adequate fire and gas detection devices and fire fighting
equipment.
 Thorough operator safety awareness and procedures training.
The role of the process licensor is to provide safe operating and shutdown procedures based
on his knowledge of the chemical reactions involved, the unit design and past experience.
Concerning the catalyst preservation, operators must avoid:
 Catalyst bed temperatures exceeding 540deg.C, to keep grain temperature under
700deg.C as over this temperature there is a change of alumina structure. Note that
the design temperature of the reactor (under design pressure) is much lower.
 The presence of hydrocarbons without a sufficient hydrogen quantity which would
result in a rapid coke deposit and the possible formation of « catalyst cakes » which
favour channeling.
 Quick depressurization of the reaction section which can damage the alumina support
and induce the formation of catalyst fines.
The refinery safety regulations shall apply and have a priority and precedence over any other
considerations.
Note that reformer emergency shutdown provokes a pretreating unit shutdown if no
alternative supply of hydrogen is available.
The following sections cover most situations operators may have to face according to
Axens' operating experience. All operating personnel must study and fully understand the
steps to be taken in such situations prior to the unit start-up.
Many of these situations are handled by automatic shutdown trips. These trips must always
be operational, by-passing must be kept to a minimum e.g. during start-up, transient periods
only. Refer to "shutdown logic IS" in section 4 of the Process Book.
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The following procedures include all the actions to be taken by the operator assuming no
action by the automatic devices.
Some of the following situations may happen in an emergency shutdown. If the right and
prompt action is taken, an orderly normal shutdown is possible.
6.7.3.2 Recycle compressor failure
Immediately:
• Switch-off all furnaces and stop the feed pump. Stop also chlorinated agent and/or
water injection pump. Close and isolate the feed valves and the pressure regulation
valve with the associated block valves.
If necessary, open the dampers in order to avoid overheating of the tubes.
• Keep the stabilizer at total reflux conditions.
• If the unit pressure level is sufficient to use again the compressor, start-up this recycle
compressor. When healthy increase the reaction section pressure to 8 kg/cm2 g by
hydrogen make-up.
• If the pressure level is too low, carry out an injection of hydrogen to reach the proper
and minimum value necessary for the compressor operation. Start-up the
compressor, then increase the reaction section pressure to 8 kg/cm2 g by hydrogen
make-up.
6.7.3.3 Loss of feed
Either both pumps failure or more likely upstream units upset.
• Maintain the recycle gas flow rate and the pressure of the reaction section.
• Stop chlorinated agent and/or water injection pump
• If the shutdown is expected to be short, decrease the reactor inlet temperature to
430deg.C and maintain this temperature level.
• Keep the stabilizer at total reflux conditions.
• Feedstock will be again injected at this temperature (proceed with normal start-up
procedure).
6.7.3.4 Other pumps failure
• Separator bottom pumps
• Stabilizer reflux pumps
• LPG absorber bottom pumps
• etc...
This situation requires to stop the unit feed. Refer to paragraph « Loss of feed ».
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6.7.3.5 Utilities failure: fuel gas

All burners of all heaters will be shutdown.
Cut-off feed immediately and proceed as per loss of feed with however the following
difference: in order to insure the highest possible temperature for hydrocarbons sweeping
with the recycle gas, air to reaction heaters (primary and secondary) must be closed.
6.7.3.6 Utilities failure: cooling water
In case of total failure the unit must be shutdown:
• Cut-off fire to all reactor heaters and cut-off feed.
• Keep the recycle gas compressor in service as long as possible without risk for the
machine, in order to cool down the heaters tubes and the catalyst.
• Cut-off fire to stabilizer reboiler.
6.7.3.7 Utilities failure: instrument/power or air
Both instrument air or instrument power failure will have the same effect:
• All control valves will fail to their safe position.
• Emergency safety valves (ESDV), if any, will close.
• Recycle compressor will stop.
• Cut-off fuel gas to all burners.
• Stop all pumps.
• Close feed valves and separator valves.
• Maintain pressure in reaction section and stabilizer.
6.7.3.8 Major leak - fire
The following are only guidelines which must be reviewed and complemented by the refiner.
They are considering the process view point.
In case of major leak the following actions must be taken:
• Cut-off fire to all heaters. Close the stack damper of all heaters, stop draft fan units, if
any, and inject snuffing steam.
• Shut off the feed pumps.
• Depressurize the stabilizer and adsorber section.
• If possible keep the recycle compressor running for few more minutes to cool down
the heaters coils and sweep the catalyst from hydrocarbons, then shut-it down.
• Depressurize the reaction section to flare.
• Decrease to a minimum the level in the vessels then stop all the pumps.
• When depressurized vessels cool down watch the pressure and inject nitrogen to
avoid vacuum.
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In case of fire.
Generally speaking, all precautions to be taken and operations to be carried-out, are the
same as above and the fire fighting can take place.
Note: If leak occurs in one of the heaters, the hydrocarbons will ignite immediatly. In such a
case let the fire develop in the heater box.
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6.8 Catalyst specifications and special procedures

6.8.1 Manufacter
Catalyst is manufactured by Axens in their facilities located at SALINDRES 30340 FRANCE.
Head office address:
Axens
89, boulevard Franklin Roosevelt
B.P. 50802
92508 RUEIL MALMAISON CEDEX – FRANCE
Phone: 33 (0) 1 47.14.21.00 Fax: 33 (0) 1 47.14.25.00
6.8.2 Catalyst specifications

A) Catalyst RG 682A
See hereafter Technical Data Sheet for chemical and physical properties (at the time of
operating instructions issue). An updated version is available on the web side:
www.axens.net.
B) Adsorbent AxTrap 857 (for chloride removal)
See hereafter Technical Data Sheet for chemical and physical properties (at the time of
operating instructions issue). An updated version is available on the web side:
www.axens.net.
6.8.3 Packaging, handling and storage
Drums must be handled with care to avoid catalyst breakage. The drums must not be rolled
and must not be allowed to fall.
Rain, snow, sand can damage the catalyst and its containers. Therefore adequate shelter for
the catalyst during storage, transport and loading must be arranged.
Before loading operation, the catalyst loading equipment must be safely installed and checked
ready for operation. Reactors and internals must be previously inspected for dimension
conformity and cleanliness.
Catalyst can be delivered either in steel drums or in big bags.
Adsorbent for HCl can be delivered either in fiber drums or in big bags.
Catalyst must be handled with care to avoid breakage of the catalyst extrudates. During the
loading, the loading sleeve shall be adjusted to allow a free fall no higher than 1 meter above
the catalyst level. Catalyst drums must not be rolled and big bags must be carefully handled
to avoid catalyst attrition.
Catalyst delivered in sealed still drums shall be stored in an enclosed and ventilated
warehouse. Storage time under such a condition is two years without any damage for the
catalyst and for the packaging.
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When necessary outdoor storage is possible.
For the drums provided:

- Installation on their pallet located on a dry ground.
- They must be protected under a plastic cover carefully tied-up.
Catalyst delivered in big bag shall normally be loaded in the reactor as soon as it arrives on
site. Short duration storage can be envisaged provided it is in a covered and dry warehouse.
PACKAGING
RG 682 A
DRUM
Description Steel drum (UN standard) with internal plastic bag - Air tight cover
Thickness: 0.8 mm – Tare : 145 kg
Dimensions Diameter: 0.6 m – Height = 0.9 m
Standard capacity : 217 liters
Net weight 105 kg
BIG BAG
Description External skin: Fiber glass spliced propylene
Internal skin: 80 micron polyethylene
Dimensions Square section: 80 x 89 cm
Cylinder diameter: 110 cm
Height: empty 160 cm
full 120 to 150 cm
Net weight 700 kg
AxTrap 857
DRUM
Description Fiber drum
Dimensions Standard capacity : 217 liters
Net weight 150 kg
BIG BAG
Dimensions Standard capacity : 1500 liters
Net weight 1000 kg
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Before the loading operation, the loading equipment must be safely installed and checked
ready for operation. Reactors and internals must be previously inspected for dimension
conformity and cleanliness.
During loading and unloading operations personnel must take the following precautions:
• Outside the reactors, wear dust mask, protective clothing, goggles, gloves and
helmet.
• For a short period inside the reactors, a safety harness must be worn and a second
man must be in attendance.
As a general rule nobody is allowed to enter a vessel before the atmosphere has been
proven suitable and all vessel nozzles are blinded.
In addition, personnel working inside a vessel during the loading must wear air mask
covering the entire face.
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6.8.4 Special procedures

6.8.4.1 Regeneration (See Drawings here after)
For bimetallic platinum and rhenium catalysts the coke accumulation on the first reactor is
around 3 to 8 weight % at the end of a normal cycle. The end of a normal cycle is defined as
a C5+ yield decline higher than 2 wt. %.
The coke deposit increases in the successive reactors with a maximum in the last reactor
which can vary from 14 to 22 weight % at the end of a normal cycle.
Deviation of these coke deposit levels is an indication of mechanical and/or operating
problem. Flow bypassing in one reactor can displace the reactions to the next one, resulting
in an unusual coke deposit.
Excessive seal oil leak from the recycle gas compressor will result in a too high coke deposit
on the first reactor catalyst.
Poisoning of the first reactor catalyst will also shift the reactions to the following ones.
The following procedure applies for a normal regeneration carried out after the end of a
normal cycle of operation. It can be adapted if the catalyst has suffered from a contamination
by sulfur or in case of poor performance of the catalyst during the cycle.
As a general rule, it is advised to start coke combustion after an increased chlorination of the
catalyst. The chloride injection must be increased during the two last weeks of operation at
the end of cycle to a value of 2 wt. ppm calculated on the basis of the feed rate measured in
weight. This is in order to reach / keep a minimum of 1 wt. % chlorine in all catalyst beds.
The unit is shutdown and hydrocarbons are purged as described in the procedure "Shutdown
for regeneration".
During the whole regeneration, temperature at the separator shall be kept as low as possible:
chloriding agent requirement will be lower.
Catalyst regeneration is done in 2 phases:
• Coke combustion: which reduces the coke content of the catalyst to less than
0.1 wt %.
• Catalyst reactivation aimed to restore both metal and acid functions of the catalyst.
6.8.4.2 Preparation of the unit

The reaction section is hydrocarbon free and put under slight positive nitrogen pressure.
The unit is then prepared for regeneration as follows:
• Turn all necessary blinds and isolate the unit from all pipe systems containing
hydrocarbons.
• Install gas sampling systems at reactor outlet and at high pressure separator.
• Install an O2 and CO2 analyzers and connect to the different gas sampling systems.
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• Prepare all lines for air injection and check the recording / reading of air flows. Purge
and flush those pipes to eliminate water and various debris.
• Check the pump and the pipes used for chlorinated agent injection as well as the
storage tank. Check the individual lines to each reactor. The chloride injection
device shall be installed as per figure 34.
• Wash with demineralized water from upstream air coolers to separator (flow
about 30% of design feed flow rate). Drain at separator bottom until there are
no more traces of ammonium chloride salts and iron scales. Afterwards isolate
the recycle gas compressor by blinds, then wash with demineralized water the
separator, the compressor suction and discharge line. This will avoid recycle
gas vibration problem and subsequent spurious shutdown due to the carry-
over of salts to the compressor due to the high moisture content of the recycle
gas during the coke combustion. It is also wise to wash the effluent/feed
exchanger with hot water.
• Certain refiners wash the recycle gas compressor with condensates additioned with
sodium carbonates every regeneration after coke condensation (see with the
compressor manufacturer for exact procedure). Others prefer to dismantle the
compressor with same frequency.
• Before establishing a caustic solution level in the separator circulate clear water in the
washing circuit and drain carefully this initial inventory.
• Prepare a caustic soda/demineralized water solution with a 4 wt. % concentration of
NaOH in the separator drum. Check and prepare the circulation pump and its flow
controller. The required flow is 25 to 35% of the design feed flow rate to the unit, is
controlled carefully in order to obtain a good washing and a sufficient neutralization of
hydrochloric acid present in the effluent of combustion. The caustic solution is
injected upstream the effluent air coolers.
• Check the caustic solution injector which is installed on corresponding P and I
diagram.
• During the chloride injection monitor the concentration so as to have a pH of the
solution between 7.0 and 7.5.
• Alkalinity to be kept at 2 to 3 wt. % of NaOH equivalent.
• Prepare an analytical program with control laboratory to monitor the complete
elimination of sodium carbonates and to predict the soda make-up into the section
when the solution does not show a sufficient neutralization effect.
• Do not exceed 5 wt. % of solids in the solution.
• Set the unit under a nitrogen pressure at 1 bar below the pressure of the regeneration
air system while maintaining the normal flow direction through the reactors. The
reactor average pressure is adjusted between 5 and 15 barg depending on the air
supply pressure. Higher pressure will obviously reduce the combustion period.
• Commission all effluent air cooler fin fans and check that cooling water is in service at
trim coolers.
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6.8.4.3 Coke combustion – oxychlorination - calcination

The combustion air is introduced at recycle compressor suction. The combustion develops
from first reactor to last reactor.
For a reactor where coke burning develops, it is necessary to watch carefully the
temperature in order to avoid any run-away (see figure 32).
• Start the compressor.
• Make sure that the reactor effluent coolers are in their maximum service and that the
compressor flow rate is set at its maximum value compatible with the regeneration
operating conditions.
• Light the furnaces and increase the inlet reactor temperature to 400deg.C at a rate of
50deg.C per hour.
• At 350deg.C, start the anti-corrosion loop circulation and begin injecting the
chlorinated agent to the 1st reactor. The injection rate should be such that the molar
ratio H2O/Cl is 20/l. See the attached table at the end of this paragraph. The injection
rate is calculated according to separator drum pressure and temperature. This
injection is carried out until the end of the calcination step.
Note: If there exists an air line to the 3rd reactor equipped with a FI, parallel burning of 1st
and 3rd reactor can be undertaken. In such a case chloride injection is kept to first
reactor. Particular care will be taken at the end of second reactor catalyst coke burn
as to avoid excessive O2 concentration at last reactor inlet.
COKE COMBUSTION
FIRST COMBUSTION
• When all catalyst beds have reached a temperature of 400deg.C, introduce the
regeneration air at compressor suction and follow the evolution of temperature inside
the catalyst beds. If possible, all temperatures must be recorded.
• The regeneration air flow rate is controlled in such a way that the temperature
increase through the catalyst bed does not exceed 40deg.C, (outlet Rx temperature -
inlet Rx temperature).
The temperature of the combustion zone (flame front) shall not be higher than 450deg.C.
This can only be checked if bed thermocouples are available. This is achieved by
decreasing the air flow rate (the injection of air can be eventually stopped) in order to
maintain a temperature at reactor outlet not exceeding 440deg.C.
• In order to monitor the temperature increase, the oxygen concentration at reactor inlet
is controlled in the range of 0.5 volume % and under no circumstances must exceed
0.8 volume %.
The burning generally starts with an oxygen concentration of 0.1 volume % in the gas
entering the reactor. As long as combustion takes place, the air flow rate must be adjusted
in order to limit the temperature increase through the catalyst bed at 50deg.C or to maintain
the reactor outlet temperature at 440deg.C max.
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During the whole phase of combustion, the O2 and CO2 contents at reactor inlet and outlet
are regularly (every hour) monitored. Cooled sampling devices must be installed for that
purpose.
When T between inlet and outlet becomes negative (- 2 / - 3deg.C) in the last reactor and
when the oxygen concentration at last reactor outlet equals the oxygen concentration at
reactor inlet, the combustion phase is considered complete. In the case of first and third
reactor parallel burning, air to third reactor shall be cut-off at the end of second reactor
burning, so as to have all combustion air injected at compressor suction.
The combustion is achieved reactor by reactor, except in the case where air is injected into
two different reactors at the same time (parallel burn).
SECOND COMBUSTION
When the first combustion is completed and the reactor temperatures are stable at 400
deg.C, the inlet temperature is then progressively increased to 480deg.C in 4 hours with an
oxygen concentration of 0.5 to 1 volume % in the recycle gas. Watch for the second
combustion to take place.
A maximum temperature increase of 30deg.C through the catalyst bed is acceptable,
corresponding to a maximum temperature inside the reactors of 510deg.C. Where bed
thermocouples are available, individual point may not exceed 520deg.C.
PROOF BURNING
The maximum oxygen content in the gas at reactor inlet must be 1 volume %. When the
second combustion is completed, the reactor inlet temperatures are increased to 520deg.C
in one hour. Keep reactor inlet temperature at 520deg.C during 2 hours. No post
combustion shall be noted at this stage. On the contrary reduce inlet temperature to
480deg.C. Temperature increase can only be resumed when no temperature increase exists
in the reactors.
If no maintenance work is forecast proceed directly to oxychlorination step.
If maintenance work and/or catalyst unloading for screening is planned, it shall take place at
the end of carbon combustion. Catalyst unloading for screening should take place during 5 th
regeneration or after 5 years operation whichever comes first. If so, stop chlorinated agent
injection and caustic solution circulation. Drain the caustic solution, wash with clear water,
drain at all low point then start cooling down the unit with the recycle gas compressor running
to a temperature at which the unit can be inspected and the catalyst unloaded. During all the
cooling down period maintain at least 3.0 vol. % of O2 in the recycle gas.
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Injection rate of chloride

during the phases of combustion and calcination
related to conditions at separator drum
Molar ratio H2O/Cl = 20/1
Temperature 4 5 6 7 8 9 10 11 12 13 14 15
deg.C bar g bar g bar g bar g bar g bar g bar g bar g bar g bar g bar g bar g
10 1,92 1,60 1,37 1,20 1,07 0,96 0,87 0,80 0,74 0,69 0,64 0,60
15 2,67 2,22 1,90 1,67 1,48 1,33 1,21 1,11 1,03 0,95 0,89 0,83
20 3,66 3,05 2,61 2,29 2,03 1,83 1,66 1,52 1,41 1,31 1,22 1,14
25 4,95 4,13 3,54 3,10 2,75 2,48 2,25 2,06 1,91 1,77 1,65 1,55
30 6,64 5,53 4,74 4,15 3,69 3,32 3,02 2,77 2,55 2,37 2,21 2,07
35 8,79 7,33 6,28 5,50 4,89 4,40 4,00 3,66 3,38 3,14 2,93 2,75
Expressed in Kg of chloride Cl per 10,000 Nm3/h of recycle gas.
Note: 1 Kg of chloride Cl = 0.96 liter of trichloroethane
1.37 liter of dichloropropane
0.85 liter of trichloroethylene
0.72 liter of tetrachloroethylene
0.68 liter of carbon tetrachloride
1.19 liter of dichloroethane
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6.8.4.4 Catalyst sieving and reloading

Catalyst unloading for screening should take place after the combustion of the coke during
3th regeneration or after 5 years operation, whichever comes first.
Catalyst shall be unloaded from reactor bottom unloading nozzle. Unloading by “sucking”
(vacuum system) must be avoided as it leads to huge breakage of catalyst.
CATALYST SIEVING
Catalyst sieving machine is installed under the reactor to be unloaded. Sieved catalyst /
alumina balls / fines dust and broken extrudates are recovered in drums.
Two upper grids (mesh opening  16 mm and  4 mm) allow the segregation of  3/4" and
 1/4" alumina balls. The lower grid (mesh opening  1 mm) allows the elimination of fines,
dust and broken extrudates from the sieved catalyst.
Note that sieving a catalyst withdrawn from the bottom of the reactor leads to a
catalyst loss of ~ 5 %. On the contrary sieving catalyst unloaded by “sucking” can
lead to losses as high as 20 %.
In both cases fresh catalyst shall be available on site to compensate the losses.
CATALYST RELOADING
After sieving the catalyst is reloaded as follows:
• First reactor:
Fresh catalyst necessary to compensate the losses occuring during the sieving, plus
catalyst from the second reactor.
• Second reactor:
Catalyst from the first reactor, plus what remaining from second reactor itself.
• Third reactor:
Its own remaining catalyst plus excess catalyst from the second reactor.
6.8.4.5 Catalyst reactivation

OXYCHLORINATION
If the unit has been shut down after coke combustion for maintenance work the unit is first
swept with nitrogen to reduce the oxygen concentration down to ~ 1 vol% and then the
reaction section pressure increased to the regeneration pressure.
Then the recycle gas compressor is started-up, heaters are fired and reactor inlet
temperatures increased to 520deg.C (50deg.C/h). Bed average temperature: 510deg.C.
At 350deg.C the anticorrosion loop circulation is started up and the chloride injection
resumed (20/1 H2O/Cl molar ratio).
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• At 510 deg.C stable average bed temperature, the oxygen concentration in the gas is
increased to 5 volume % in 2 hours while observing carefully for any restart of the
combustion (see figure 33). If necessary, reduce or stop the air injection. Check that
CO2 concentration stays lower than 10 vol %.
• Maintain the conditions: bed temperature = 510deg.C and 5 vol. % O2- during 4
hours and check every hour that the HCl content in the gas at reactors outlet is higher
than 40 ppm vol. (Draëger tubes).
CALCINATION
• Increase the oxygen concentration up to 12 vol. % (for pressure < 5 kg/cm2g see
figure 31) in one hour. Then, maintain such conditions at 510deg.C for 6 hours
without exceeding an outlet reactor temperature of 520deg.C. Check that CO2
concentration stays lower than 5 vol %.
RINSING / DRYING
• At the end of the calcination phase at 510deg.C, stop the anti-corrosion loop
circulation and drain the caustic solution at all cold low points.
• The anti-corrosion loop will then be rinsed away with clear water then drained
carefully at all cold low points. Stop the chlorinated agent injection as soon as the
rinsing water make-up is stopped. The caustic solution purging, cleaning with clear
water and draining the clear water shall be done as quickly as possible.
During all these operations the temperature at reactors inlet is maintained at
520deg.C. Temperature shall only be decreased when the total clear water
drained at all cold low points is lower than 0.05 wt % of the catalyst per hour.
This drying period should be carried-out in about 4 hours and should not exceed
6 hours.
COOLING
While maintaining an oxygen concentration in the recycle gas higher than 3 vol. %, the
reactor inlet temperatures are decreased to 350deg.C at a rate of 50deg.C per hour.
At this temperature, furnaces and recycle compressor are shutdown and the reaction section
is depressurized and purged with nitrogen in order to obtain a residual content of oxygen not
higher than 0.3 volume % (See note 1 paragraph 6.6.3).
As soon as the O2 and CO + CO2 contents are lower than 0.3 volume %, nitrogen is displaced
by electrolytic hydrogen and the pressure of the reaction section increased to a minimum of
7 barg.
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Immediatly after, continue with catalyst reduction (see paragraph “Catalyst reduction”), then
catalyst sulfiding (see paragraph “Catalyst sulfiding”).
Note 1: When the unit is equipped with catalyst samplers, catalyst samples should be taken
at the end of combustion phase. This could allow to finely adjust the chlorine
injection.
Note 2: If for any reason reduction cannot take place immediatly after the post calcination
drying the catalyst shall be cooled down to 180deg.C while keeping an oxygen
concentration ~ 5 vol %. Nitrogen purge will take place only when the forecast for
reduction start-up is known.
6.8.4.6 Emergency handling procedure for regeneration

Following broad approach (modified suitably for each specific site) will be used as guideline.
1- If the caustic circulation fails and can not be restored immediately, block in the air
injection. Stop chloride injection. Maintain the recycle gas compressor operation and
maintain the catalyst beds hot. Caustic make-up to be stopped. If the duration is
forecast to be long, decrease the reactor inlet temperatures down to 400deg.C and
maintain O2 concentration between 0.5 and 0.8 vol %.
2- If the catalyst temperatures become excessive, delta > 50deg.C, block in the air injection
to all reactors. Discontinue chloride injection. Investigate the incident thoroughly before
the air is re-introduced.
3- If the recycle compressor fails or must be shutdown and if it is known that it can not be
restarted, then block in the air injection immediately. Stop chloride injection and caustic
circulation. Cut-off fire to heaters. Try to maintain the system pressure at 6 barg, with
N2.
If the recycle compressor fails when first burn is in progress ensure that the O 2 content is
in the range of 0.5 - 0.8 % never above 1%. Inject N2 to maintain O2 content in this range
if needed.
If the recycle compressor fails when final burn is in progress ensure that the O2 content
is in the range of 0.8 - 1.2 % never above 1.5%. Inject N2 to maintain O2 content in this
range if needed.
If the recycle compressor fails when calcination is in progress ensure that the O 2 content
is in the range of 8 - 10% never below 5%.
When recycle gas compressor is healthy, in each of the above cases ensure that the O 2
limits are not exceed before you increase the temperatures.
4- In all cases be sure that caustic does not find its way to the catalyst. Also do not inject
chloride when recycle compressor is stopped or when air is stopped for long duration.
5- If the proceedings are to be halted for long duration before reduction, a catalyst
preservation procedure shall be adopted. See the chapter “Shutdown for regeneration”
in this book.
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6.8.4.7 Miscellaneous
Flow meters reading correction:
A) Correction for gas given in volume
MW d x P op x T d
K 1
= R
1
x
MW op x P d x T op
B) Correction for gas given in weight

MW op x P op x T d
K 2
= R 2
x
MW d x P d x T op
Where:
K1 : Corrected flow at 0 deg.C and 1 ATM in Nm3/h.
K2 : Corrected flow in kg/h.
R1 : Instrument reading in Nm3/h.
R2 : Instrument reading in kg/h.
MW d : Design molecular weight.
MW op : Operating molecular weight.
Pd : Absolute design pressure in ATM.
P op : Absolute operating pressure in ATM.
Td : Design temperature in °K.
T op : Operating temperature in °K.
Note: A molecular weight ~ 30 can be taken into consideration for the recycle gas flow
calculation during the regeneration if you have not a more accurate analysis.
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Calculation of catalyst coke levels:

Assuming that coke molecular formula is CH1.3, the coke combustion can be represented by
the following equation:
2.65
CH1.3 + O2  CO2 + 0.65 H2 O
2
Thus 0.7547 mole of coke is burned for each mole of O2 consumed. This means that it
requires 2.23 Nm3 of oxygen to burn 1 kg of coke or 10.62 Nm3 of air to burn 1 kg of coke.
If the amount of air is known (air inlet minus losses) the quantity of coke burned can be
calculated directly.
On the contrary the following formula can apply:
 O2 inlet (vol. %) - O2 outlet (vol. %) 
O2 combustion rate =   x Recycle gas (Nm 3 / h)
 100 
Total O2 consumption = O2 consumption rate (Nm3/h) x combustion time (hours).
Total oxygen combustion (Nm 3 )
Coke combusted =
2.23 (Nm 3 / kg)
Example of coke calculation :

• Recycle gas = 30 000 Nm3/h.
• O2 concentration at 1st reactor inlet = 0.8 vol. %.
• O2 concentration at last reactor outlet = 0.1 vol. %.
• Combustion phase duration = 12 hours.
 0.8 - 0.1
Oxygen consumption : 30 000 x   x 12 = 2520 Nm 3
 100 
2520 Nm 3
Combusted coke : = 1130 kg
2.23
It can also be calculated as follows:

The total quantity of air injected during the combustion phase multiplied by a coefficient for
air losses (0.9) corresponds to the total quantity of coke.
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For instance 13 333 Nm3 of air corresponds to:

13333 x 0.9
= 1130 kg of coke
10.62
Repartition of the coke between the reactors can be calculated using the sum of hourly
positive delta T’s obtained in each reactor and the sum of hourly positive delta T’s for all
reactors during the combustion.
R1 T = 200deg. coke = 1130 x 200 = 75 kg % on catalyst = 75 = 5.65
C 3000 1327

C 3000 3000

C 3000 5838 0
All Rx = 3000deg. coke = 1130 % on catalyst = 1130 = 11.1

T C kg 10165 2
Eventhough these methods are not very accurate they give a good idea of the total coke
deposited during the cycle as well as the repartition of the coke.
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PFD Regeneration N°1/2
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PFD Regeneration N°2/2
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WATER DIAGRAM IN AIR - FIGURE 30
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OXYGEN REQUIREMENTS DURING CALCINATION

FIGURE 31
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REGENERATION : COKE COMBUSTION

FIGURE 32
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REGENERATION : OXYCHLORINATION / CALCINATION

FIGURE 33
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CHLORINE INJECTION DEVICE

FIGURE 34
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6.8.5 Chemicals
DMDS:
Dimethyldisulfide is a pale yellow liquid with a foul odor. It contains 68% of sulfur and its
molecular weight is 94.
1. Commercial specifications
Typical analysis
 Purity > 98% 99.5%
 Methylmercaptan < 1% 0.30%
 Moisture < 0.06%
 Cloud point < -5deg.C/- < -10deg.C/-14°F
23°F
2. General properties
 Freezing point = -84.7deg.C = -121°F
 Boiling point (1 atmosphere) = 109.6deg. = 229°F
C
 Specific gravity d 420CC = d 3968CC = 1.0625
 Refractive index nD20C = nD68C = 1.526
 Viscosity (20deg.C = 68°F) = 0.62 cP

 Surface tension (20deg.C = 68°F) = 33.6 dynes cm-1
= 0.0062 poundals per inch
 Cryoscopic constant = 0.030C-1 = 0.054 F-1
 Polar moment = 1.95 D
 Dielectric constant = 9.6
 Heat of vaporization = 9.6 mth mole-1
= 183.8 BTU/lb
 Heat of combustion = 665.8 mth mole-1
12 750 BTU/lb
 Flash point (open cup) = 16deg.C = 61°F
 Cubic expansion coefficient = 0.0011
(at 50deg.C = 122°F)
 Conductivity = 5.2 10-7 -1 cm-1
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= 13.2 10-7 -1 inche-1

 Compressibility coefficient = 0.45
(at 22.7deg.C = 72.9°F and 100 bars = 1 450
psi)
 Compressibility coefficient = 0.70
(at 100deg.C = 212°F and 100 bars = 1 450
psi)
 LEL = 1.1% in air
 UEL = 16.1% in air
 Auto ignition temperature = > 300deg.C (> 570°F)
 Sulfur content = 68 wt %
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6.9 Safety and health recommendations

Various hazardous and toxic substances are present in this process.
These substances are contained in the different streams and chemical products discussed in
section 1 of the Process Book.
Detailed data regarding the hazard and toxicity of these compounds can be found in the
following documents:
 OSHA Regulated Hazardous Substances published by the Occupational Safety and
Health Organization - US Department of Labor.
 « Fiches toxicologiques » published by :
Institut National de Recherche et de Sécurité
30, rue Olivier Noyer 75680 PARIS CEDEX
The unit owner is advised to request the relevant data sheets from the above organizations.
These sheets are regularly updated by these organizations.
Concerning catalysts and additives supplied under a trade mark, the relevant updated
Material Safety Data Sheets must be required from the manufacturer.
The European Directive instructs all companies supplying products, to provide product
Safety Data Sheets in a controlled manner.
In order to comply with this obligation, Axens has installed on the internet network an access
to Axens' Safety Data Sheets, with a record of customer names and e-mail addresses. This
mechanism enables the automatic dispatch of safety data sheets revisions related to each
customer's needs.
Consequently, we invite you to connect to the site "www.quickfds.com" to discover the
procedure to record your name and e-mail address and to obtain access to the Safety Data
Sheets that meet your needs.
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6.10 Analytical control

6.10.1 Recommended methods and frequency
The frequencies given below are routine related to a normal operation. During start-up and
test runs more analyses will be required. The following schedule is proposed for the
analyses.
ASTM methods are copyrighted by ASTM International, UOP methods are copyrighted by
UOP. All methods are available through ASTM International, 100 Barr Harbor Drive, West
Conshohocken, PA 19428-2959 USA. The methods may be obtained through ASTM
website www.astm.org.
Product Analysis Method Frequency

Feed Composition IFP 9301 2 per week
Specific gravity ASTM D 1298 / D 4052 1 per day
Distillation ASTM D 86 1 per day
Total sulfur content ASTM D 5453 (1) / D 4045 1 per day
Doctor test ASTM D 4952 As required
Oxygenated components ASTM D 4815 with FID As required
Total chlorine content ASTM D 7536 As required
Total nitrogen content ASTM D 4629 As required
Bromine index ASTM D 2710 As required
Arsenic content IFP 9312 As required
Copper content ASTM D 6732 As required
Lead content IFP 9406 As required
Mercury content UOP 938-10 As required
Iron content ICP-MS (2) As required
Silicon content HR ICP-MS (3) As required
Other metals contaminants (5) GFAAS (4) – ICP-MS (2) As required
(1) ASTM D 5453 is recommended on usual basis. Total sulfur by ASTM D 4045 could be used if
necessary for cross-checking.
(2) ICP - MS = Inductively Coupled Plasma with mass spectrometer detection
(3) HR ICP MS = High resolution ICP-MS, detection limit is 20 ppb. Si can be back calculated on the
basis of spent catalyst analysis
(4) GFAAS = graphite furnace electrothermal atomic absorption spectrometry
(5) Axens can provide support to help for external analysis in IFPEN laboratories or other specialised
laboratories. Specification below available methods quantification limit can be back calculated
based on the spent catalyst analysis.
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Stabilized Composition IFP 9302 2 per week
reformate
Distillation ASTM D 86 1 per day
Specific gravity ASTM D 1298 / D 4052 1 per day
RON clear ASTM D 2699 or Carburane 1 per day
(6)
MON clear ASTM D 2700 or Carburane As required
(6)
Reid Vapor Pressure ASTM D 323 1 per day
Bromine index ASTM D 2710 Required if to
storage
Existing gums ASTM D 381 Required if to
storage
Potential residue ASTM D 873 Required if to
storage
Feed/Effluent Leak research (cresols, IFP 9860 or IFP 9707 As required
exchanger phenols and thiophenols
content)
Recycle gas H2 purity Online analyzer
Composition IFP 9908 1 per day
Water Online analyzer (7)
Hydrogen sulfide Draeger tube 67 28041 1 per day
HCl Draeger tube CH 29501 1 per day
CO UOP 603 or infrared As required
or Dräger tube 67 33 051 +
pre-tube CH 24101
CO2 UOP 603 or infrared As required
Hydrogen Composition IFP 9908 1 per day
production
HCl Draeger tube 67 28041 1 per day
H2S Draeger tube CH 29501 As required
Fuel gas Composition IFP 9909 1 per day
(6) Carburane = Detailed Hydrocarbon Analysis Software licensed by Vinci technologies.
(7) Additional checking can be done with portable analyser.
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LPG LPG sampling method ASTM D 1265
Composition IFP 9909 1 per day
Density ASTM D 1657 1 per day
Copper strip ASTM D1838 As required
Total sulfur content ASTM D 6667 / D 4468 (8) As required
Total chlorine content ASTM D 4929 (9) / UOP 930 As required
H2S and RSH ASTM D 6228 As required
HCl Draeger tube CH 29501 As required
Regeneration O2 Portable / Online analyzer
gas IFP 9810 As required
(during or Refinery Gas Analyser (10)
regeneration) CO IFP 9810 As required
or Refinery Gas Analyser
or Draeger tube CH 19701
CO2 IFP 9810 As required
or Refinery Gas Analyser
or Draeger tube CH 25101
HCl Draeger tube 67 28181 As required
SO2 Refinery Gas Analyser As required
Reduction H2 purity IFP 9908
Hydrogen (inlet) CO UOP 603 or infrared
or Dräger tube 67 33 051 +
(during pre-tube CH 24101
regeneration) CO2 UOP 603 or infrared
Reduction H2 purity IFP 9908
Hydrogen CO UOP 603 or infrared
(outlet) or Dräger tube 67 33 051 +
pre-tube CH 24101
(during CO2 UOP 603 or infrared
regeneration) HCl Dräger tube CH 29501
H2O Portable analyzer
(8) ASTM D 6667 is recommended on usual basis. Total sulphur by ASTM D 4468 could be used if
necessary for cross-checking.
(9) ASTM D 4929 part B: Oxidative combustion and microcoulometry detection using LPG injection
loop.
(10) To check online analyzers
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SERVICE :

Caustic recycle Alcalinity UOP 209 1 per shift
(during Total solids ASTM D 5907 1 per day
regeneration)
pH pH paper / ASTM D1293 1 per shift
Catalyst (11) Carbon content 310 CA 220 1 per week
for spent
catalyst on
last reactor
As required
for
regenerated
catalyst
Chlorine content 310 CA 207 / IFP 9303 (12) 1 per week
for spent
catalyst on
last reactor
As required
for
regenerated
catalyst
Sulfur content 310 CA 220 / IFP 9303 (12) 1 per week
for spent
catalyst on
last reactor
and as
required on
1st reactor
As required
for
regenerated
catalyst
Other metal contaminants ASTM D 7260 or WDXRF As required
(13) for spent
catalyst on
1st reactor
Specific surface area ASTM D 3663 As required
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(11) From usual practice, only carbon, sulphur and chloride determination are performed in refinery
laboratory. Other determinations are seldom required and can be performed in Axens
laboratories or other specialised laboratories.
(12) 310 CA 207 and 310 CA 220 are to be used on usual basis. WDXRF method IFP 9303 could be
used if necessary for cross-checking. WDXRF = Wave-Length Dispersive X-Ray Fluorescence.
(13) Matrix matched calibration.
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6.10.2 Description of IFP/Axens analytical methods

The following analytical methods are attached in Appendix A:
IFP 9301 Petroleum naphtha

Detailed analysis
Capillary gas chromatography
IFP 9302 Stabilized reformate effluent
Detailed analysis
IFP 9303 Alumina-based catalysts
Determination of chlorine and sulfur
Wave length dispersive x-ray fluorescence
IFP 9312 Petroleum products analysis
Determination of arsenic
Graphite furnace electrothermal atomic absorption spectrometry
IFP 9406 Gasoline and naphtha analysis
Determination of trace amounts of lead
Graphite furnace electrothermal atomic absorption spectrometry
IFP 9707 Stabilized reformate effluent
Determination of naphthenes - Evaluation of naphtha traces
IFP 9810 Catalytic cracked gas
Analysis of hydrogen, nitrogen, oxygen, carbon oxides, hydrogen
sulphide, ammonia and hydrocarbons
Gas chromatography
IFP 9860 Petroleum products
P.Cresol, Phenols and thiophenols
UV Spectrophotometry
IFP 9908 Reforming gas analysis of hydrogen
and low hydrocarbons content gas chromatography
IFP 9909 Reforming gas analysis of hydrocarbons
and low hydrogen content gas chromatography
310 CA 207 Determination of chloride ions in used catalyst
Potentiometric titration
310 CA 220 Determination of total sulfur and carbon in used catalyst
Infra-red analysis of combustion products

300 IO Operating Instructions Rev0

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300 IO Operating Instructions Rev0

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August 2011

Job Number 04653/C-209

PT ISTANA KARANG LAUT

Rev. Date Prepared by Checked by Approved by Comments

6. OPERATING INSTRUCTIONS SECTION......................................... 4

6. OPERATING INSTRUCTIONS SECTION

6.1.2 Compulsory instructions and reference documents

Process Flow Diagrams: Reference number Rev.

Piping and Instrumentation Diagrams:

6.2 Purpose of the Process

6.3 Chemical reactions and catalysts

6.3.1.3 Catalyst activity, selectivity, stability

6.3.2 Chemical reactions

A) Desirable reactions with hydrogen production

The cyclohexane reaction, for instance, proceeds as follows:

Thermodynamically the reaction is highly endothermic and is favored by high temperature

c) Effect of parameters on naphthene dehydrogenation

Increase of Effect on dehydrogenation due

d) Effect of parameters on paraffin dehydrocyclization

Increase of Effect on dehydrocyclization due

B) Desirable reactions without hydrogen production

Iso-N paraffin equilibria

Theoretically, at the selected operating temperature (about 500deg.C) the thermodynamics

e) Transalkylation (Alkyl disproportionation)

6.3.2.2 Kinetic analysis of the chemical reactions

6.3.2.3 Catalyst distribution in reactors

In this unit (3 reactors) the catalyst distribution is:

Each specific case, obviously, requires a specific catalyst distribution.

CATALYST DISTRIBUTION IN THE 3 REACTORS

The main features of these catalysts are:

6.3.3.2 Catalyst mechanism

Dehydrogenation Metallic function

A simplified representation of the catalyst support chemical structure, after chlorination is as

This is referred to as chloride elution or leaching by water and can be represented

D) Alteration of catalyst activity

high water content in the due to: poisoning by sulfur.

• Decreased octane. • Slight increase in octane. • Large decrease in octane.

6.3.3.3 Catalyst contaminants

– Effect of nitrogen contamination:

• Increase the chlorination agent injection.

• Adjust chlorine injection to make up for the increased chlorine loss.

6.3.4 Process variables

6.3.4.4 Space velocity

6.3.4.6 Feed quality

Ratio NNC6 / NNC5

Naphtha End boiling point

Quality Initial boiling point

6.4 Preparation for start-up

6.4.2 Equipment and unit inspection

6.4.2.1 Equipment inspection

C) Inspection preparation works

D) Vessels internals assembly and inspection

6.4.2.2 Unit inspection

6.4.3 Preliminary operations

Instrument air : In service

• The deethanizer feed / bottom exchanger.

PFD Leak test N°1/4

PFD Leak test N°2/4

PFD Leak test N°3/4

PFD Leak test N°4/4

6.4.4 Drying out of the unit

PFD Drying out N°1/2

PFD Drying out N°2/2