Train Train Train Training ing ing ing Material Material Material Material

CATALYTIC REFORMING
II
Table of Contents
Ch.1 Basic Principles …………………………………………..…… 1
1.1 Introduction …………………………………..………………… 2
1.2 The Problem of Antiknock Quality ……………………..……… 2
1.3 Octane Number …………………………………...…………….. 2
1.4 Composition Effect on Octane Number ………………….…….. 3
1.5 Reforming ………………………………………………………. 6
1.5.1 Thermal Reforming …………………..…………………. 6
1.5.2 Catalytic Reforming ………………………..…………… 7
1.6 Feed Treatment By Hydrogen……………………………………. 11
1.6.1 Hydrofining ……………………………..………………. 12
Ch.2 The Catalytic Reforming Process …………………………... 14
2.1 Introduction ………………………………………………..….. 15
2.2 Feed to Catalytic Reforming ………………………………….. 16
2.3 Product from Catalytic Reforming ……………………………. 17
2.3.1 The Typical Yield …………………………………….... 18
2.3.2 Reformate Composition ………………………………... 19
2.3.3 Reformate Specification …………………….…………. 20
2.4 Catalytic Reforming Techniques ………………..…………….. 22
2.4.1 Fixed-Bed Technology ……………………………..….. 24
2.4.2 Moving-Bed Technology …………………………...….. 34
2.4.3 Fluid-Bed Technology ………………………………..... 41
Ch.3 Process Chemical Reactions and Thermodynamics ………. 43
3.1 Introduction ………………………………………………..….. 44
3.2 Process Reactions …………………………………………..…. 44
3.2.1 Dehydrogenation of Naphthenes …………………...….. 44
3.2.2 Isomerization of Paraffins and Naphthenes ………...….. 45
3.2.3 Dehydrocyclization of Paraffins ………………….……. 45
3.2.4 Hydrocracking and Dealkylation ………………….…… 45
3.3 Relative Reaction Rate ………………………………………... 47
3.4 Heats of Reaction …………………………………………..…. 50
CATALYTIC REFORMING
III
Ch.4 Catalytic Reforming Catalyst ………………………………. 51
4.1 Introduction …………………………………………...………. 52
4.1.1 Classification of Catalyst ………………………….….... 52
4.1.2 Main Types of Catalyst ……………………………..…. 54
4.1.3 General Catalyst Characterization and Properties ……... 54
4.2 Types of Catalytic Reforming Catalyst ……………………...... 57
4.2.1 Platinum on Chlorinated Alumina ……………………... 57
4.2.2 Bimetallic …………………………………………….... 58
4.3 Effect of Platinum content of Catalyst ………………………... 60
4.4 Catalyst Preparation ………………………………………….... 61
4.4.1 Optimization of the Formation …………………..…….. 61
4.4.2 Unit Operations ………………………………..………. 62
4.5 Reaction Mechanisms ……………………………………...….. 68
4.5.1 Hydrogen Action ……………………………….…….... 69
4.5.2 Sulfur Action ……………………..……………………. 71
4.6 Catalyst Deactivation ………………………………………….. 73
4.6.1 Characterization of Coke ……………………...……….. 73
4.6.2 Effects of Reaction Conditions on Coking Deactivation . 74
4.6.3 Mechanism of Coke Formation ………………...……… 78
4.6.4 Poisoning of Naphtha Reforming Catalyst …………….. 80
4.7 Catalyst Regeneration …………………………………………. 87
4.7.1 Effect of the Type of Process on Cycle length ………… 87
4.7.2 Catalyst Regeneration Steps ……………………..…….. 87
4.7.3 Factors Affecting Coked Catalyst Reactivity ………….. 87
4.7.4 Regeneration of coked Catalyst ………………….…….. 87
4.7.5 Regeneration of Sulfur-Contaminated Catalyst …….….. 91
4.8 Procedure of Regeneration ……………………………………. 92
4.8.1 Pre-Shutdown ………………………………………….. 92
4.8.2 Shutdown ………………………………………….…… 92
4.8.3 Carbon Burn ………………………………………….... 92
4.8.4 Oxidation ………………………………………………. 93
4.8.5 Cool Down ……………………………………..………. 93
4.8.6 Nitrogen Purge …………………………………………. 93
4.8.7 Reduction ………………………………………………. 93
4.8.8 Sulfate Removal ……………………………………….. 94
4.8.9 Start-Up ……………………………………………..…. 94
Ch.5 Catalyst Reforming Parameters ……………………...…….. 95
5.1 Introduction ……………………………………………...……. 96
5.2 Temperature …………………………………………...………. 96
CATALYTIC REFORMING
IV
5.3 Reaction Pressure ……………………………………...……… 98
5.4 Hydrogen to Hydrocarbon Ratio ………………………..…….. 99
5.5 Space Velocity ……………………………………………..… 101
5.6 Feedstock Properties …………………………………………. 102
Ch.6 Hazard Assessment ………………………………………… 105
Ch.7 Plant Design ………………………………………………... 118
Ch.8 Design ………………………………………………….…… 122
8.1 Material Balance ……………………………………………... 123
8.2 Heat Exchanger Design ………………………………...……. 126
8.3 Furnace Design ………………………………………………. 143
8.4 Reactor Design ………………………………………….…… 163
8.5 Stabilizer Design ………………………………………….…. 168
8.6 Pump Design ………………………………………………… 177
8.7 Compressor Design ………………………………………….. 182
8.8 Tank Design …………………………………………………. 187
References ………………………………………………………… 191
CATALYTIC REFORMING
1
CH.1
Basic Principles
Ch.1 BASIC PRINCIPLES
2
1.1 INTRODUCTION
The problem of low octane ratings of naphtha is solved by increasing the
contents of isomers and aromatics in its composition. Catalytic
Reforming involves some reactions such as Isomerization,
Dehydrogenation, and Dehydrocyclization which convert the low octane
number components in naphtha into very high octane number
components, consequently enhancing the antiknock quality of gasoline.
Two types of reactors are used in the catalytic reforming process: the
fixed-bed reactor and the moving-bed reactor. The used catalyst for
catalytic reforming processes is the platinum supported on a silica or
silica-aluminum base for fixed bed processes and non-precious metal
oxide catalysts for fluid and moving bed processes. Most of the catalytic
reforming reactions favor high temperatures, low pressures, and low
space velocities.
1.2 THE PROBLEM OF ANTIKNOCK QUALITY
A very important property of an automobile gasoline is its resistance to
knock, detonate or ping during service. Knocking occurs in the
combustion chamber in the cylinder of motor engines, this knocking is a
result of the sudden combustion of the gasoline-air mixture in the
cylinder. The more the fuel-air mixture is compressed, the more power
the engine can produce.
With the increase of loads and duties on engines over years and the
subsequent development of automobile engines, compression ratios of
engines are increased to deliver more power. But this increase in
performance goes together with an increase in knocking and detonation.
The gasoline which occurs in the crude oil is too poor in the antiknock
quality to be used alone as a fuel in the modern automobile engines that
are designed on using high compression ratios. Hence when straight-run
gasoline (Naphtha) is used directly in engines, it will knock causing
a lose in power and a loud noise.
1.3 OCTANE NUMBER
The antiknock property of a gasoline is generally expressed as its octane
number. This number is the percentage of iso-octane in a blend with n-
heptane that produces the same amount of knocking produced by the
CATALYTIC REFORMING
3
tested gasoline. ASTM has standardized octane number test methods into
Research Octane Number (RON), and Motor Octane Number (MON)
tests. (RON) is produced using normal road conditions, while (MON) is
produced using sever or high-speed conditions on the testing equipment.
The arithmetic average [(RON+MON)/2] is increasingly used nowadays.
Worth mentioning here is that when octane number is reported or
assigned to gasoline without definition, then research octane number is
the meant measurement, unless stated otherwise.
1.4 COMPOSITION EFFECT ON OCTANE
NUMBER
Extensive studies of octane numbers of individual compounds have
brought to light some general rules. Table (1.1) shows the octane
numbers of several hydrocarbons. Normal paraffins have the least
desirable knocking characteristics and they become progressively worse
as the molecular weight increase, while iso-paraffins and naphthenes have
higher octane numbers than the corresponding normal paraffins. The
octane number of the iso-paraffins increases with the increase of
branching of the chain. Olefins have markedly higher octane numbers
than the corresponding paraffins and aromatics usually have very high
octane numbers.
Comparing the different hydrocarbon series, aromatics – except for
Benzene – are the hydrocarbons with the highest octane numbers. Hence,
to increase the octane number of gasoline, the paraffinic and naphthenic
contents in gasoline should be transformed into aromatics and iso-
paraffins. Such a transformation process is called the Reforming Process.
Ch.1 BASIC PRINCIPLES
4
Table (1.1), RON for some pure hydrocarbons.
Another solution for the low antiknock problem of gasoline was used in
1922 which was the use of TEL (Tetra Ethyl Lead). TEL increases the
octane number greatly when added to gasoline in small quantities.
Pure Hydrocarbons RON
Paraffins
n-Butane 113
i-Butane 122
n-Hexane 19
2-Methylpentane 83
2,2-Dimethylbutane 89
2,3-Dimethylbutane 96
n-Heptane 0
2-Methylhexane 41
n-Octane -19
Olefins
1-Pentene 91
1-Octene 29
3-Octene 73
Naphthenes
Methylcyclopentane 107
Ethylcyclopentane 75
1,1-Dimethylcyclopentane 96
Aromatics
Benzene 99
Toluene 124
o-Xylene 120
m-Xylene 145
p-Xylene 146
Oxygenates
Methanol 106
Ethanol 99
2-Propanol 90
(MTBE) 117
CATALYTIC REFORMING
5
However, over years, in many countries the amount of added lead has
been decreased gradually by strict regulations in order to pave the way for
completely preventing its use for its harmful effect on man's health and
environment. Nowadays lead-free gasoline is used in most countries
around the world and as a substitute additive for TEL to the gasoline,
oxygenates such as alcohols, MTBE, and TAME are now used to increase
the octane number of gasoline. Table (1.2) shows the Maximum
allowable contents of some oxygenates.
The ethers may be produced at the refinery by reacting suitable alcohols
such as methanol and ethanol with branched olefins from the fluid
catalytic cracker, such as iso-butene and iso-pentene, under the influence
of acid catalysts. In the mid-1990s, methyl-t-butyl ether (MTBE) -made
by etherification of iso-butene with methanol- became the predominant
oxygenate used to meet reformulation requirements for adding oxygen to
mitigate emissions from gasoline-powered vehicles.
Environmental issues involving MTBE have made it more desirable to
dimerize isobutene from the catalytic cracking unit rather than etherify it.
Fortunately, iso-butene dimerization may be achieved with minimal
modifications to existing MTBE plants and process conditions, using the
same acidic catalysts. Where olefin levels are not restricted, the extra
blending octane boost of the di-iso-butylene can be retained. Where
olefin levels are restricted, the di-iso-butylene can be hydrotreated to
produce a relatively pure iso-octane stream that can supplement alkylate
for reducing olefins and aromatics in reformulated gasoline.
Oxygenates Maximum, Volume %
Methanol
Ethanol
Iso-propyl Alcohol
Iso-butyl Alcohol
Tert- butyl Alcohol
Ether (5 or more C atoms)
Other oxygenates
3
5
10
10
7
15
10
Table(1.2), Oxygenates allowed on Gasoline.
Ch.1 BASIC PRINCIPLES
6
1.5 REFORMING
Reforming is essentially a treatment process designed to improve a
gasoline octane number and may be accomplished in part by an increase
in the volatility -reduction in molecular size- or chiefly by the conversion
of n-paraffins to iso-paraffins, olefins, and aromatics and the conversion
of naphthenes to aromatics. The process is carried out either thermally or
catalytically. The nature of the final product is of course influenced by
the source (and composition) of the feedstock. In thermal reforming, the
reactions resemble the reactions that occur during gas oil cracking, that is,
molecular size is reduced, and olefins and some aromatics are produced.
1.5.1 Thermal Reforming
Thermal reforming was naturally developed from thermal cracking, as
reforming is also a thermal decomposition reaction. Cracking converts
heavier oils into gasoline; reforming converts (reforms) gasoline into
higher-octane gasoline. The equipment for thermal reforming is
essentially the same as for thermal cracking, but higher temperatures are
used (Nelson, 1958).
In carrying out thermal reforming, a feedstock, such as a 205 °C (400 °F)
end-point naphtha or a straight-run gasoline, is heated to 510 to 595 °C
(950 to 1100 °F) in a furnace much the same as a cracking furnace, with
pressures from 400 to 1000 psi. As the heated naphtha leaves the furnace,
it is cooled or quenched by the addition of cold naphtha. The quenched,
reformed material then enters a fractional distillation tower where any
heavy product is separated. The remainder of the reformed material
leaves the top of the tower to be separated into gases and reformate. The
higher octane number of the product (reformate) is due primarily to the
cracking of longer chain paraffins into higher-octane olefins.
Thermal reforming is in general less effective than catalytic processes and
has been largely supplanted. As it was practiced, a single-pass operation
was employed at temperatures in the range of 540 to 760 °C (1000 to
1140 °F) and pressures in the range 500 to 1000 psi. Octane number
improvement depended on the extent of conversion but was not directly
proportional to the extent of cracking-per-pass.
The amount and quality of reformate is dependent on the temperature. A
general rule is the higher the reforming temperature, the higher the octane
number of the product but the yield of reformate is relatively low. For
CATALYTIC REFORMING
7
example, a gasoline with an octane number of 35 when reformed at 515
°C (960 °F) yields 92.4% of 56 octane reformate; when reformed at 555
°C (1030 °F) the yield is 68.7% of 83 octane reformate. However, high
conversion is not always effective as coke production and gas production
usually increase.
Modifications of the thermal reforming process caused by the inclusion of
hydrocarbon gases with the feedstock are known as gas reversion and
polyforming. Thus, olefinic gases produced by cracking and reforming
can be converted into liquids boiling in the gasoline range by heating
them under high pressure. As the resulting liquids (polymers) have high
octane numbers, they increase the overall quantity and quality of gasoline
produced in a refinery.
The gases most susceptible to conversion to liquid products are olefins
with three and four carbon atoms. These are propylene (CH
3
.CH=CH
2
),
which is associated with propane in the C
3
fraction, butylene
(CH
3
.CH
2
.CH=CH
2
or CH
3
.CH=CH.CH
3
) and iso-butylene
[(CH
3
)
2
C=CH
2
], which are associated with butane (CH
3
.CH
2
.CH
2
.CH
3
),
and iso-butane [(CH
3
)
2
CH.CH
3
] in the C
4
fraction. When the C
3
and C
4
fractions are subjected to the temperature and pressure conditions used in
thermal reforming, they undergo chemical reactions that result in a small
yield of gasoline. When the C
3
and C
4
fractions are passed through a
thermal reformer in admixture with naphtha, the process is called
naphtha-gas reversion or naphtha polyforming.
These processes are essentially the same but differ in the manner in which
the gases and naphtha are passed through the heating furnace. In gas
reversion, the naphtha and gases flow through separate lines in the
furnace and are heated independently of one another. Before leaving the
furnace, both lines join to form a common soaking section where the
reforming, polymerization, and other reactions take place. In naphtha
reforming, the C
3
and C
4
gases are premixed with the naphtha and passed
together through the furnace. Except for the gaseous components in the
feedstock, both processes operate in much the same manner as thermal
reforming and produce similar products.
1.5.2 Catalytic Reforming
Like thermal reforming, catalytic reforming converts low-octane gasoline
into high-octane gasoline (reformate). Although thermal reforming can
produce reformate with a research octane number in the range of 65 to 80
Ch.1 BASIC PRINCIPLES
8
depending on the yield, catalytic reforming produces reformate with
octane numbers of the order of 90 to 95. Catalytic reforming is conducted
in the presence of hydrogen over hydrogenation-dehydrogenation
catalysts, which may be supported on alumina or silica–alumina.
Depending on the catalyst, a definite sequence of reactions takes place,
involving structural changes in the charge stock. The catalytic reforming
process was commercially nonexistent in the United States before 1940.
The process is really a process of the 1950s and showed phenomenal
growth in the 1953–1959 period. As a result, thermal reforming is now
somewhat obsolete.
Catalytic reformer feeds are saturated (i.e., not olefinic) materials; in the
majority of cases the feed may be a straight-run naphtha, but other by-
product low-octane naphtha (e.g., coker naphtha) can be processed after
treatment to remove olefins and other contaminants. Hydrocarbon
naphtha that contains substantial quantities of naphthenes is also a
suitable feed. The process uses a precious metal catalyst (platinum
supported by an alumina base) in conjunction with very high
temperatures to reform the paraffin and naphthene constituents into high-
octane components. Sulfur is a poison to the reforming catalyst, which
requires that virtually all the sulfur must be removed from the heavy
naphtha through hydrotreating before reforming. Several different types
of chemical react ions occur in the reforming reactors:
 Paraffins are isomerized to branched chains and to a lesser extent
to naphthenes, and
 naphthenes are converted to aromatics.
Overall , the reforming reactions are endothermic. The resulting product
stream (reformate) from catalytic reforming has a RON from 96 to 102
depending on the reactor severity and feedstock quality. The
dehydrogenation reactions that convert the saturated naphthenes into
unsaturated aromatics produce hydrogen, which is available for
distribution to other refinery hydro-processes.
The catalytic reforming process consists of a series of several reactors,
which operate at temperatures of approximately 480 °C (900 °F). The
hydrocarbons are reheated by direct-fired furnaces between the
subsequent reforming reactors. As a result of the very high temperatures,
the catalyst becomes deactivated by the formation of coke (i.e.,
essentially pure carbon) on the catalyst, which reduces the surface area
available to contact with the hydrocarbons.
CATALYTIC REFORMING
9
Catalytic reforming is usually carried out by feeding a naphtha (after
pretreating with hydrogen if necessary) and hydrogen mixture to a
furnace where the mixture is heated to the desired temperatures 450 °C to
520 °C (840 °F to 965 °F), and then passed through fixed-bed catalytic
reactors at hydrogen pressures of 100 to 1000 psi. Normally, two (or
more than one) reactors are used in series, and reheaters are located
between adjoining reactors to compensate for the endothermic reactions
taking place. Sometimes as many as four or five are kept on-stream in
series while one or more is being regenerated. The on-stream cycle of any
one reactor may vary from several hours to many days, depending on the
feedstock and reaction conditions.
The product issuing from the last catalytic reactor is cooled and sent to a
high-pressure separator where the hydrogen- rich gas is split into two
streams:
 One stream goes to recycle where it is mixed with the feed, and
 The remaining portion represents excess hydrogen available for
other uses.
The excess hydrogen is vented from the unit and used in hydrotreating, as
a fuel, or for manufacture of chemicals (e.g., ammonia). The liquid
product (reformate) is stabilized (by removal of light ends) and used
directly in gasoline or extracted for aromatic blending stocks for aviation
gasoline. Figure (1.1) shows the relation between reformate yield and its
octane number.
Figure (1.1), Reformate Yield and its Octane Number.
Ch.1 BASIC PRINCIPLES
10
The commercial processes available for use can be broadly classified as
the moving-bed, fluid-bed, and fixed-bed types. The fluid-bed and
moving-bed processes use mixed non-precious metal oxide catalysts in
units equipped with separate regeneration facilities. Fixed-bed processes
use predominantly platinum-containing catalysts in units equipped for
cycle, occasional, or no regeneration.
There are several types of catalytic reforming process configurations that
differ in the manner that they accommodate the regeneration of the
reforming catalyst. Catalyst regeneration involves burning off the coke
with oxygen. The semi-regenerative process is the simplest configuration
but does require that the unit be shut down for catalyst regeneration in
which all reactors (typically four) are regenerated. The cyclic
configuration uses an additional swing reactor that enables one reactor at
a time to be taken off-line for regeneration while the other four remain in
service. The continuous catalyst regeneration (CCR) configuration is the
most complex configuration and enables the catalyst to be continuously
removed for regeneration and replaced after regeneration. The benefits of
more complex configurations are that operating severity may be increased
as a result of higher catalyst activity but this does come at an increased
capital cost for the process.
Although subsequent olefin reactions occur in thermal reforming, the
product contains appreciable amounts of unstable unsaturated
compounds. In the presence of catalysts and hydrogen (available from
dehydrogenation reactions), hydrocracking of paraffins to yield two lower
paraffins occurs. Olefins that do not undergo dehydrocyclization are also
produced. The olefins are hydrogenated with or without isomerization, so
that the end product contains only traces of olefins.
The addition of a hydrogenation–dehydrogenation catalyst to the system
yields a dualfunction catalyst complex. Hydrogen reactions-
hydrogenation, dehydrogenation, dehydrocyclization, and hydrocracking-
take place on the one catalyst, and cracking, isomerization, and olefin
polymerization take place on the acid catalyst sites.
Under the high-hydrogen partial pressure conditions used in catalytic
reforming, sulfur compounds are readily converted into hydrogen sulfide,
which, unless removed, builds up to a high concentration in the recycle
gas. Hydrogen sulfide is a reversible poison for platinum and causes a
decrease in the catalyst dehydrogenation and dehydrocyclization
activities. In the first catalytic reformers the hydrogen sulfide was
removed from the gas cycle stream by absorption in, for example,
diethanolamine. Sulfur is generally removed from the feedstock by use of
CATALYTIC REFORMING
11
a conventional desulfurization over a cobalt–molybdenum catalyst. An
additional benefit of desulfurization of the feed to a level of <5 ppm
sulfur is the elimination of hydrogen sulfide (H
2
S) corrosion problems in
the heaters and reactors.
Organic nitrogen compounds are converted into ammonia under
reforming conditions, and this neutralizes acid sites on the catalyst and
thus represses the activity for isomerization, hydrocracking, and
dehydrocyclization reactions. Straight-run materials do not usually
present serious problems with regard to nitrogen, but feeds such as coker
naphtha may contain around 50 ppm nitrogen and removal of this
quantity may require high-pressure hydrogenation (800 to 1000 psi) over
nickel–cobalt–molybdenum on an alumina catalyst.
The yield of gasoline of a given octane number and at given operating
conditions depends on the hydrocarbon types in the feed. For example,
high-naphthene stocks, which readily give aromatic gasoline, are the
easiest to reform and give the highest gasoline yields. Paraffinic stocks,
however, which depend on the more difficult isomerization,
dehydrocyclization, and hydrocracking reactions, require more severe
conditions and give lower gasoline yields than the naphthenic stocks. The
end point of the feed is usually limited to about 190 °C (375 °F), partially
because of increased coke deposition on the catalyst as the end point
during processing at about 158 °C (278 °F). Limiting the feed end point
avoids redistillation of the product to meet the gasoline end-point
specification of 205 °C (400 °F), maximum.
Dehydrogenation is a main chemical reaction in catalytic reforming, and
hydrogen gas is consequently produced in large quantities. The hydrogen
is recycled through the reactors where the reforming takes place to
provide the atmosphere necessary for the chemical reactions and also
prevents the carbon from being deposited on the catalyst, thus extending
its operating life. An excess of hydrogen above whatever is consumed in
the process is produced, and as a result, catalytic reforming processes are
unique in that they are the only petroleum refinery processes to produce
hydrogen as a by-product.
1.6 FEED TREATMENT BY HYDROGEN
Nondestructive or simple hydrogenation is generally used for the purpose
of improving product quality without appreciable alteration of the boiling
range. Mild processing conditions are employed so that only the more
Ch.1 BASIC PRINCIPLES
12
unstable materials are attacked. Nitrogen, sulfur, and oxygen compounds
undergo reaction with the hydrogen to remove ammonia, hydrogen
sulfide, and water, respectively. Unstable compounds which might lead to
the formation of gums, or insoluble materials, are converted to more
stable compounds.
Hydrotreating, Figure (1.2), is carried out by charging the feed to the
reactor, together with hydrogen in the presence of catalysts such as
tungsten–nickel sulfide, cobalt–molybdenum–alumina, nickel oxide–
silica–alumina, and platinum–alumina. Most processes employ cobalt–
molybdena catalysts which generally contain about 10% of molybdenum
oxide and less than 1% of cobalt oxide supported on alumina. The
temperatures employed are in the range of 260 to 345 °C (500 to 655 °F),
while the hydrogen pressures are about 500 to 1000 psi.
The reaction generally takes place in the vapor phase but, depending on
the application, may be a mixed-phase reaction.
1.6.1 Hydrofining
Hydrofining is a process that first went on-stream in the 1950s and is one
example of the many hydroprocesses available. It can be applied to
lubricating oils, naphtha, and gas oils. The feedstock is heated in a
furnace and passed with hydrogen through a reactor containing a suitable
metal oxide catalyst, such as cobalt and molybdenum oxides on alumina.
Reactor operating conditions range from 205 to 425 °C (400 to 800 °F)
and from 50 to 800 psi, and depend on the kind of feedstock and the
degree of treating required. Higher-boiling feedstocks, high sulfur
content, and maximum sulfur removal require higher temperatures and
pressures.
After passing through the reactor, the treated oil is cooled and separated
from the excess hydrogen which is recycled through the reactor. The
treated oil is pumped to a stripper tower where hydrogen sulfide, formed
by the hydrogenation reaction, is removed by steam, vacuum, or flue gas,
and the finished product leaves the bottom of the stripper tower. The
catalyst is not usually regenerated; it is replaced after about one year’s
use.
CATALYTIC REFORMING
13
Figure (1.2), A distillate hydrotreater for hydrodesulfurization. (From OSHA
Technical Manual, Section IV, Chapter 2, Petroleum Refining Processes.)
Ch.2 The Catalytic Reforming Process
14
CH.2
The Catalytic
Reforming Process
CATALYTIC REFORMING
15
2.1 INTRODUCTION
The catalytic reforming process is designed to transform the low octane
number constituents in the gasoline composition into very high octane
rating aromatics in the range of 6 to 10 carbon atoms. This process aims
to enhance the properties of gasoline to satisfy some basic specifications
such as:
 Maximum Octane Number by increasing aromatic and isomer
contents.
 Minimum capacity to form gums - when storing and shipping -
caused by unstable olefinic compounds.
 Minimum vapor pressure to avoid vapor lock problems.
 Minimum tendency to produce smoke or smog and low carbon
deposition into cylinder caused by high boiling fractions in the
gasoline composition.
A large number of catalytic reforming processes were operational during
the II World War. They used catalysts with alumina as a support and
chromium or molybdenum oxides as active elements and were
implemented in fixed or moving bed reactors. But a great turning point
happened in the beginning of 50s when UOP developed the "Platforming"
process based the use of a platinum catalyst on chlorinated alumina. This
catalyst allowed the operation to be carried out at pressures of
approximately 70 bar. It was a semi-regenerative process, the catalyst was
being regenerated after a few months of operation. Cyclic regeneration
was introduced by EXXON using the same type of catalyst (
Pt/chlorinated Al
2
O
3
or Pt on silica alumina ).
During 50s and 60s, catalysts were improved allowing lower operating
pressures of about 30 bar. The hydrogenation reaction favors lower
operating pressures to enhance the production of aromatics from
naphthenes. That was before the use of bimetallic catalysts - in the late
60s - which allowed lower operating pressures.
In the early 70s, the third major modification occurred when the
continuous regeneration was introduced in the catalytic reforming units.
This allowed pressures of approximately 10 bar. In the late 80s, even
lower pressures were achieved: 3 bar.
These continuous modifications of catalysts caused the operating
conditions be more sever, higher RON and space velocity and an effort to
get better yield. These modification didn't stop in the past and will
Ch.2 The Catalytic Reforming Process
16
continue in the future with more and more sever operating conditions and
producing gasoline with higher specifications.
2.2 FEED TO CATALYTIC REFORMING
The typical feed to the catalytic reforming process is the heavy straight-
run gasolines (HSR) or naphthas (90 °C to 160 °C). The reason for the
use of heavy naphthas as feeds for Catalytic Reforming is that the ease of
cyclization and isomerization reactions in the process increases with the
increase of carbon atoms. Light naphtha (C
5
+
- 90 °C) tends to crack
forming butane and light gases causing a lose in yield, hence it is not
economical. Heavier feeds than the heavy naphtha causes formation of
carbon deposits on the catalyst and partially deactivate it.
Table (2.1) gives the composition of two typical feeds. The RON is low:
50 for the paraffinic feed and 66 for the naphthenic feed. The average
molecular weigh is about 115, centered around C
8
. Sulfur is present in the
feed in the range of 500 and 350 ppm, which are representative of straight
run gasolines (SR) coming from atmospheric distillation of crude. But
values lower than 100 ppm are found in a few particular crudes (Hassi
Messauod, for example). These SR feeds contain limited amounts (a few
ppm) of nitrogen in the form of amines, or oxygenated compounds in the
form of phenol or carboxylic acid. In some cases, traces (<1 ppm) of
metals or metalloids can be found in the feed, depending on the origin of
the crudes. For instance, mercury and, more seldom, arsenic are found in
some crudes.
If the "Octane Barrel" requirements can't be met by reforming heavy
naphtha (90 - 160 °C), then it may be necessary to increase the amount of
feed processed in reforming, by using cuts distilling in the same range of
SR naphtha which is produced from conversion units and have low
octane number. For instance, visbreaking or coking gasolines can be sent
to reforming which are characterized by – in comparison with SR feeds –
a high olefin and acid sulfur content and larger amounts of nitrogen
compounds. Hydrocracking gasoline is another feed, it is clean since it is
free of sulfur and nitrogen compounds because the use of hydrogen in the
hydrocracking process works as a hydrotreating process, but such a feed
is mainly made up of cyclopentane-structure naphthenes and isoparaffins.
FCC gasoline is another possible feed . Its is characterized by significant
olefins and aromatics concentrations as well as by the presence of
molecules containing heteroatoms such as S or N.
CATALYTIC REFORMING
17
Table (2.1), The composition of two typical feeds.
2.3 PRODUCT FROM CATALYTIC REFORMING
As stated before, the main objective of any reforming process is to
increase the octane number by increasing the aromatic content in the
gasoline. As a result of the reactions taking place during the process,
reformates consist – mainly – of branched paraffins and especially
aromatics, most of which have fewer than 10 carbon atoms. Figure (2.1)
shows the total changes taking place in the reformer to produce the
desired aromatics and isoparaffins. Olefins are saturated to form paraffins
by hydrogenation. Paraffins from the feed and from olefins saturation are
essentially isomerized to iso-paraffins and, to some extent, cyclized to the
corresponding naphthenes. Naphthenes are then dehydrogenated to
aromatics. Aromatics of the feed are essentially left without change. In
addition to the reformate, the reactions produce considerable amounts of
gases such as Hydrogen, Methane, Ethane, Propane and (i + n) Butanes.
Paraffinic
(Arabian Light)
Naphthenic
(Nigeria)
RON 50 66
Av. Mw. 114 119
S
(weight ppm)
500 350
Paraffins 66.8 29.3
Naphthenes 21.8 61.85
Aromatics 11.4 8.85
Ch.2 The Catalytic Reforming Process
18
Figure (2.1), Total changes to produce iso-Paraffins and Aromatics.
2.3.1 The Typical Yield
As mentioned before, catalytic reforming produces C
5
+
gasoline,
hydrogen, but also a little amount of methane, ethane propane and
butanes. In the last few decades the importance of the production of
hydrogen, beside C
5
+
, has risen gradually with pressures going down to
10 bar and less as a result of improving catalysts.
Table (2.2) gives an average product distribution from a paraffinic feed
on a bimetallic at 15 bar and RON = 98. The desired products account for
85% weight and the ones with lower added value represent less than 5%
weight (methane and ethane).
Products % wt/feed
H
2
CH
4
C
2
H
6
C
3
H
8
(i + n) C
4
H
10
C
5
+
2.5
1.7
3.1
4.2
6.0
82.5
Table (2.2), Typical yields on a Middle
Eastern feed.
RON = 98 P = 15 bar.
CATALYTIC REFORMING
19
2.3.2 Reformate Composition
Olefins and naphthenes concentrations are lower than 1% wt except for
low pressure reformates which approach 1% wt. Table (2.3) shows a
typical analysis for a low pressure reformate. It should be noted that to
achieve RON = 98, the aromatic content should be close to 70% wt. The
octane rating in a reformate is generally provided by C
7
to C
10
aromatics
and by light iso-paraffins, especially C
5
. This is because the C
6
, C
7
and C
8
isoparaffins are not very branched and so they have a low RON.
The reformate is basically made up of C
6
to C
10
aromatics, but
increasingly it is limited to C
7
, C
8
and C
9
. The aromatics concentration is
directly related to the desired research octane number. It is important also
to note that reformates don't contain any sulfur (S ≤ 0.1 ppm).
Number
of carbon
atoms
nP iP P O N A Total
4
5
6
7
8
9
10
11
Total
0.57
1.51
1.69
2.5
1.16
0.26
0.07
0
7.76
2.37
1.97
8.42
4.91
1.04
0.28
0.02
21.01
0.57
3.88
5.66
10.92
6.07
1.3
0.35
0.02
28.77
0.1
0.16
0.35
0.44
0.08
0
0
1.13
0
0.19
0.4
0.34
0
0
0
0.93
2.34
14.16
26.28
21.08
4.76
0.55
69.17
3.98
8.35
25.83
33.13
22.46
5.11
0.57
100
nP: normal paraffins. iP: branched paraffins. P: total paraffins.
O: olefins. N: naphthenes. A: aromatics
Table (2.3), Analysis for a low pressure reformate ( % wt ).
RON = 98 sp.gr = 0.85 S ≤ 0.1 ppm.
The RON is related to the aromatics concentration as indicated in figure
(2.2). High pressure reformates contain few olefins. However, in modern
units running at low hydrogen partial pressure, there are more and more
olefins, as indicated in figure (2.3), since the RON is the fixed parameter
for the run. These olefins lower the MON of gasolines and often make
hydrogen purification more complicated.
Ch.2 The Catalytic Reforming Process
20
2.3.3 Reformate Specifications
Table (2.4) lists the main administrative specifications in effect for
Eurosuper in the first of January 2000. Developments are expected with
respect to the maximum allowable sulfur (≤ 50 ppm), the mandatory
presence of oxygenated compounds (oxygen content ≥ 2% wt), and a
more stringent limit on total aromatics (≤30% wt). Also expected is a
reduction in the end point in order to lower the heavier aromatics
concentration along with a limit on high volatility C
4
-C
6
olefin
concentrations, whose effect on ozone production has been demonstrated.
Figure (2.2), Relationship between the RON and % aromatics in the reformate.
CATALYTIC REFORMING
21
Figure (2.3), Olefin content in the reformate.
Properties Values
RVP (kpa) max
Distillation (% vol min)
at 100 °C
at 150 °C
Benzene (% vol max)
Aromatics (% vol max)
Olefins (% vol max)
Oxygen content (% wt max)
Sulfur max (ppm)
Lead (g/l max)
60
46
75
1
42
18
2.8
150
0.005
Table (2.4), Main Specifications for Eurosuper (January 2000).
Table (2.5) shows the ASTM distillation analysis for the same low
pressure reformate discussed above. The end point is limited, usually to
around 205 °C, to comply with the corresponding gasoline specification,
but mainly to prevent large-scale formation of naphthalene derivatives
which color the reformate and cause rapid catalyst deactivation.
Ch.2 The Catalytic Reforming Process
22
Table (2.5), Distillation characteristics of a low pressure reformate.
RON = 98 sp.gr = 0.85 S ≤ 0.1 ppm.
2.4 CATALYTIC REFORMING TECHNIQUES
The first commercial units of catalytic reforming were built practically
simultaneously in the United States, in November 1940, under the name
of Hydroforming, and in Germany, under the name of D.H.D. They used
a catalyst of molybdenum or chromium oxide on alumina, discovered by
Moldavschi and Kamusher in 1936. At the time, the process was used
especially for producing toluene, which was necessary during World War
II for the production of trinitrotoluene, by nitration. The catalysts of
chromium and molybdenum oxide could not compete with platinum
catalysts and were gradually abandoned, despite improvements achieved
over the years, including the processes in moving bed or fluidized bed.
The first catalytic reforming unit using platinum catalyst on Al2O3
support was built by Dutch Refining in 1949.
The continuously improved performances were the result of modified
process conditions with the corresponding modifications in the unit
design and the use of bi- and poly-metallic catalysts. As an example, the
evolution of the UOP process ‘‘Platforming.’’. The high octane rating of
the reformed gasoline, the efficiency of the process, and the broad
availability of feedstock (naphtha) contributed to make Platforming in a
% distilled °C
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
56
83
92
103
113
121
128
135
142
150
160
168
194
% distilled
% residue
% losses
98.4
1.5
0.1
CATALYTIC REFORMING
23
relatively short period of time, the premier process for high octane
gasoline. In addition, through continuous improvements, the process was
capable of satisfying the increasing market requirements in the conditions
of the gradual prohibition of the leaded gasoline.
In January 1990, the worldwide Platforming capacity was 373.9 million
tons/year (excluding the former Eastern Block), placing it in second place
in the production of gasoline, after catalytic cracking with 539.5 million
tons/year. The evolution of reforming capacities from 1990–2010 is
shown in Table (2.6).
At the same time, the position of catalytic reforming increased strongly
for the production of aromatic hydrocarbons, feedstocks for the
petrochemical industry. It provides almost all the world’s need for
xylenes.
Table (2.6), Evolution of Reforming Capacity from 1990–2010
(thousands bpsd).
The different technologies basically involve three configurations:
1. Fixed-bed type.
2. Moving-bed type.
3. Fluid-bed type.
The fixed bed could be operated whether cyclic or semi-regenerative,
according to the time required to regeneration. Moving bed is only
operated continuously. These different types of configurations are going
to be discussed in details in the following sections.
Region 1990 1995 1998 2000 2010
North America 4,487 4,278 4,333 4,380 4,700
Western Europe 2,017 2,268 2,386 2,420 2,500
Pacific Rim and South Asia 1,090 1,700 2,050 2,360 3,450
Eastern Europe and C.I.S. na
a
1,654 1,746 1,850 2,400
Latin America na
a
329 429 480 600
Middle East 311 640 790 850 1,100
Africa 530 404 429 470 690
Total 8,766 11,273 12,163 12,810 15,440
a
Not Available.
Ch.2 The Catalytic Reforming Process
24
2.4.1 Fixed-Bed Technology
This is the oldest technology. The fixed bed configuration implies that the
catalyst is fixed in its location in the reactor, while the feed is passed over
it until the time of regeneration. The fixed bed configuration has two
different types of runs:
 Non-regenerative, in which the spent catalyst is replaced without
regeneration in the end of its life (months).
 Semi-regenerative, which involves the total regeneration of all the
catalyst after finishing the running period (usually years), with the
unit being shutdown during regeneration.
 Regenerative (Cyclic), which involves the regeneration of a part of
the catalyst after its deactivation (occurs in days), during switching
the operation to a substitute (swing) reactor, with no shutdown of
the unit.
2.4.1.1 Type of reactors
In the beginning, the pressures used were greater than 50 bar and reactor
pressure drop had little influence in comparison with total pressure drop.
This is why axial reactors - which have simple internals and therefore less
costly - were chosen to implement the process at these times.
Figure (2.4) shows the two types of reactors. Radial reactors made their
appearance some time in the seventies at the same time of the appearance
of the bimetallic catalysts that allow operation at pressures lower than 25
bar. Here, pressure drop in the reactors became significant in relation to
the total pressure drop. In addition, the cost of recycle hydrogen
compression became a non-negligible item.
The evolution toward continuous reforming and the implementation of
continuous catalyst circulation imposed the radial type of low-pressure
drop reactor once and for all. The trend toward a total pressure of 3 bar
left no other choice.
Reactors are built of low-alloy carbon steel that can withstand hydrogen
corrosion and oxidizing atmosphere during regeneration and
oxychlorination operations.
CATALYTIC REFORMING
25
Figure (2.4), Reactor types.
2.4.1.2 Reactor Configuration
As mentioned earlier, catalytic reforming involves mostly endothermic
and equilibrated reactions whose rates differ by a factor of 50. A set of
isothermal reactors with a heat input could have been the solution, but it
is expensive and lacking in flexibility. The choice of adiabatic reactors in
conjunction with furnaces was eventually made. Differences in rate
between cyclohexane dehydrogenation, cyclopentane hydro-
isomerization-dehydrogenation and paraffin dehydrocyclization as a ratio
is approximately 50/5/1. As a result, the final is a series of 3 or 4 (
furnace + reactor ) groups depending on the type of feed: 3 for paraffinic
feeds and 4 for naphthenic feeds.
Figure (2.5) shows a simple reactors layout. Each ( furnace + reactor )
group takes reaction rates into account. F
1
is large and R
1
is small, while
F
3
is small but R
3
is large. The figure also shows the variation in
temperature in the reactors: significant drop in R
1
, smaller drop in R
2
and
finally less variation in R
3
, where the endothermicity of
dehydrocyclization is partially offset by the exothermicity of cracking,
since the two reaction rates are comparable. The aromatics concentration
rises gradually. Catalyst distribution among the three reactors is usually
around 15% (R
1
), 15 - 30% (R
2
) and 55 - 60% (R
3
).
Ch.2 The Catalytic Reforming Process
26
Figure (2.5): A. Furnace (F
1
, F
2
, F
3
) and reactor (R
1
, R
2
, R
3
) layout.
B. Variation in temperature in reactors R
1
, R
2
, R
3
.
C. Variation in effluent composition (paraffins-naphthenes-aromatics)
in the reactors.
CATALYTIC REFORMING
27
2.4.1.3 Non-Regenerative Process
The non-regenerating system was used in the first type of catalytic
reforming unit, the ‘‘Platforming’’ of UOP. Operation at high pressure
(above 35 bars) ensured a catalyst life of over 10 months when using as
feed a naphtha with final boiling point between 192–205 °C. For this
reason, the units are not provided with the means for regenerating the
catalysts. The coked catalyst is replaced and sent off-site for regeneration.
The advantages of operating at a higher severity, i.e., at lower pressure
led to switching the non-regenerative units to semi-regenerative ones.
2.4.1.4 Semi-Regenerative (SR) Fixed Bed Process
This type of process is given its name because catalyst regeneration
causes the unit to be shut down at the end of the run. The semi-
regenerative system provides a total duration of catalyst utilization of
about 7–10 years and even longer. The necessary equipments are added
for the regeneration of catalyst without its removal from the system. On
contrary of, non-regenerative process which send the spent catalyst off-
site to be regenerated outside the system. Figure (2.6) shows a semi-
regenerative process flow scheme. The reactor configuration is the same
as described earlier in the previous section.
Ancillary units are designed to allow optimum use of catalysts and to
offset some of their drawbacks:
 The catalyst is sensitive to impurities: nitrogen-, oxygen- and
sulfur-containing compounds and metals. Consequently, a feed
purification section must be provided. The feed is purified by
hydrotreating, which blocks the metals and produces ammonia,
hydrogen sulfide and water, eliminated in the purification section.
The feed can be further treated on molecular sieves to knock out
the few ppm of residual water and also on a sulfide compound
trapping agent.
 The catalyst becomes rapidly deactivated in the absence of
hydrogen. Deactivation is considerably reduced by hydrogen, so
high hydrogen partial pressure is created (H
2
/HC > 8 for
monometallic catalysts) by compressing and recycling part of the
hydrogen produced during the reaction. It may contain some
impurities : water, hydrochloric acid and sometimes H
2
S, and
needs to be dried, dehydrochlorinated and desulfurized on specific
Ch.2 The Catalytic Reforming Process
28
adsorbers. Such installations are mainly used during start up but
not only.
 Finally, the catalyst produces light C
1
to C
4
hydrocarbons in
addition to hydrogen, and they are separated from the reformate in
a stabilization section. Depending on the operating pressure,
separation systems of varying degrees of complexity will be
implemented to get relatively pure hydrogen and high gasoline
recovery: a simple separating drum, re-contacting purification
systems, ultra-cooling, etc.
2.4.1.5 Regenerative (Cyclic) Process
An initial solution, to avoid shutting down units, was carried out by using
an extra reactor. With a complex valve system, three reactor can be
running while the fourth is being regenerated. Here, the four reactors are
of the same size and are located in position R
1
, R
2
, R
3
alternatively. This
line up requires installation of a regeneration system and doesn't always
allow the regenerated catalyst to be restarted in optimum conditions.
The operation of the unit can be cyclic, a mode of operation in which one
of the reactors is constantly under regeneration, or in a swinging mode
where the spare reactor (swing reactor), is coupled, occasionally when
regeneration becomes necessary.
The regeneration of the catalyst without stopping the operation of the unit
allows for a higher severity than that in the semi-regenerative system. In
general, this means a lower pressure in the reaction system, which leads
to a higher octane rating at equal yield, or to a higher yield of reformate
for a given octane rating. That also allowed the use of higher reactor inlet
temperatures that may reach 550 °C. Such operation can lead to octane
ratings higher by approximately 5 units than the semi-regenerative
system.
The regeneration of the catalyst is carried out at short time intervals, on
average 5-15 days. The reactor of the last step is regenerated more often.
In many designs, the additional reactor occupies a central position on the
platform of the industrial plant in order to shorten the length of the
connecting lines.
The first plant of this type was patented in 1953 and built in 1954 under
the name of ‘‘Ultraforming’’ by Standard Oil of Indiana (Amoco). In
CATALYTIC REFORMING
29
1956, the process ‘‘Powerforming’’ was patented and built by EXXON.
Figure (2.7) shows a schematic flow of EXXON Powerformer.
In January 1984, the regenerative system represented 22% of the total
capacity of catalytic reforming units operated in the United States.
Compared with the semi-regenerative units, their investment is about 10–
15% higher.
Worldwide at the end of 1982, there were 39 ‘‘Ultraforming’’ units in
use, with a total processing capacity of 84,000 m
3
/day, while the
‘‘Powerforming’’ units had a total processing capacity of 220,000
m
3
/day.
2.4.1.6 Commercial Processes
2.4.1.6.1 Hydroforming
The hydroforming process made use of molybdena–alumina (MoO
2

Al
2
O
3
) catalyst pellets arranged in fixed beds; hence the process is known
as fixed-bed hydroforming. The hydroformer had four reaction vessels or
catalyst cases, two of which were regenerated; the other two were on the
process cycle. Naphtha feed was preheated to 400 °C to 540 °C (900 °F
to 1000 °F) and passed in series through the two catalyst cases under a
pressure of 150 to 300 psi. Gas containing 70% hydrogen produced by
the process was passed through the catalyst cases with the naphtha. The
material leaving the final catalyst case entered a four-tower system where
fractional distillation separated hydrogen-rich gas, a product (reformate)
suitable for motor gasoline and an aromatic polymer boiling above 205
°C (400 °F).
After 4 to 16 h on process cycle, the catalyst was regenerated. This was
done by burning carbon deposits from the catalyst at a temperature of 565
°C (1050 °F) by blowing air diluted with flue gas through the catalyst.
The air also re-oxidized the reduced catalyst (9% molybdenum oxide on
activated alumina pellets) and removed sulfur from the catalyst.
Ch.2 The Catalytic Reforming Process
30
F
i
g
u
r
e

(
2
.
6
)
,

S
e
m
i
-
r
e
g
e
n
e
r
a
t
i
v
e

p
r
o
c
e
s
s

f
l
o
w

s
c
h
e
m
e
.
CATALYTIC REFORMING
31
F
i
g
u
r
e

(
2
.
7
)
,

P
o
w
e
r
f
o
r
m
e
r

f
l
o
w

s
c
h
e
m
e
(
E
x
x
o
n
)
.
Ch.2 The Catalytic Reforming Process
32
2.4.1.6.2 Houdriforming
The introduction of an additional reactor followed by a stripping column,
before the classical reaction system, for the protection of the catalyst
against compounds of S, N, and O, was patented by Houdry in 1951. The
first unit of this type was built in 1953. The guard reactor used the same
catalyst as the main reaction system.
The subsequent practice of hydrotreatment of the feed to catalytic
reforming eliminated the need for such a solution. The purification of the
feedstock within the unit before the reactors, is current practice. The
distinction is that the purification is made by adsorption. Such a system
was developed by Chevron in the ‘‘Reniforming’’ process. The heavy
naphtha passes through an adsorber before being mixed with recycle
hydrogen. As suggested by the name of the process, it uses a Pt-Re
catalyst that allows operating at low pressures.
2.4.1.6.3 Platforming
The first step in the platforming process, Figure (2.8), is the preparation
of the naphtha feed. For motor gasoline manufacture, the naphtha feed is
distilled to separate a fraction boiling in the 120 °C to 205 °C (250 °F to
400 °F) range. As sulfur adversely affects the platinum catalyst, the
naphtha fraction may be treated to remove sulfur compounds. Otherwise,
the hydrogen-rich gas produced by the process , which is cycled through
the catalyst cases, must be scrubbed free of its hydrogen sulfide content.
The prepared naphtha feed is heated to 455 °C to 540 °C (850 °F to 1000
°F) and passed into a series of three catalyst cases under a pressure of 200
to 1000 psi. Further heat is added to the naphtha between each of the
catalyst cases in the series. The material from the final catalyst case is
fractionated into a hydrogen-rich gas stream and a reformate stream. The
catalyst is composed of 1/8 in. pellets of alumina containing chlorine and
about 0.5% platinum.
CATALYTIC REFORMING
33
Figure (2.8), Platforming Process.
Each pound of catalyst reforms up to 100 bbl of naphtha before losing its
activity. It is possible to regenerate the catalyst, but it is usual to replace
the spent catalyst with a new catalyst.
Other fixed-bed processes include Catforming, in which the catalyst is
platinum (Pt), alumina (Al
2
O
3
), and silica–alumina (SiO
2
–Al
2
O
3
)
composition, which permits relatively high space velocities and results in
very high hydrogen purity. Regeneration to prolong catalyst life is
practiced on a block-out basis with a dilute air in-stream mixture. In
addition, Houdriforming is a process in which the catalyst may be
regenerated, if necessary, on a blockout basis. A guard bed catalytic
hydrogenation pretreating stage using the same Houdry catalyst as the
Houdriformer reactors is available for high-sulfur feedstocks. Lead and
copper salts are also removed under the mild conditions of the guard bed
operation.
2.4.1.6.4 Powerforming
The cyclic Powerforming process, figure (2.7), is based on frequent
regeneration (carbon burn-off) and permits continuous operation.
Reforming takes place in several (usually four or five) reactors and
regeneration is carried out in the last (swing) reactor. Thus, the plant need
not be shutdown to regenerate the catalyst. The cyclic process assures a
continuous supply of hydrogen gas for hydrotreatment operations and
Ch.2 The Catalytic Reforming Process
34
tends to produce a greater yield of higher octane reformate . Choice
between the semi-regenerative process and the cyclic process depends on
the size of plant required, type of feedstocks available, and the octane
number needed in the product.
2.4.1.6.5 Rexoforming
Rexoforming is a combination process using platforming and aromatic
extraction processes in which low-octane raffinate is recycled to the
platformer. Operating temperatures may be as much as 278 °C (508 °F)
lower than conventional platforming, and higher space velocities are
used. A balance is struck between hydrocyclization and hydrocracking,
excessive coke and gas formation thus being avoided. The glycol solvent
in the aromatic extraction section is designed to extract low-boiling high-
octane iso-paraffins as well as aromatics.
2.4.1.6.6 Magnaforming
The ‘‘Magnaforming’’ system, built by Engelhard Corp., is characterized
by a small hydrogen/feed molar ratio in the first two reaction steps. This
is followed by the injection of additional hydrogen-rich recycle gases, so
that the ratio reaches normal values in the latter reaction steps.
The advantage of the system is that it favors the aromatization and the
dehydrocyclization in the first two reaction stages as a result of the
reduced (H
2
/hydrocarbon) ratio that displaces the thermodynamic
equilibrium in the desired direction. Since in the latter and especially the
last reaction steps the danger of coke formation is higher, the
(H
2
/hydrocarbon) ratio is increased to prevent this occurrence.
2.4.2 Moving-Bed Technology
2.4.2.1 Reactor Configuration
Although the moving bed was used on MoO
3
/Al
2
O
3
type catalyst before
1940, its use on platinum-alumina catalysts came into being only in the
early seventies. UOP put a continuous regeneration system on the market,
figure (2.9), where three or four reactors are located one on top of the
other. The effluent coming out of each reactor goes through a furnace
before entering the next one. The catalyst moves downward by gravity
CATALYTIC REFORMING
35
from R1, to R2 then R3, loaded with coke, by a lift to the top of the
regenerator. It goes through the regenerator by gravity then sent back to
the top of R1. The rest of the unit flow scheme is very close to the fixed
bed process.
The technology developed by IFP uses the conventional SR reformer
layout of "side by side" reactors. The catalyst at the bottom of each
reactor is raised by lifts to the top of the following reactor. From the last
reactor it goes to the regenerator, figure (2.10), and then back to the top
of the first reactor.
UOP regeneration is continuous, while IFP's can be either continuous or
batch.
2.4.2.2 Advantages of the Moving Bed
The introduction of moving bed technology has had the following effects:
 Reformates are produced with a very high octane number even
from difficult feeds and without any run duration problems.
 Units are operational all year round, regularly producing the
hydrogen that modern refineries constantly need.
 Catalysts are less stable over time but more selective, making it
possible to improve yields.
 Recycle rates are lower, thereby improving yields and reducing
operating costs.
 Operating pressures are significantly lower and this is highly
favorable for the reformates and the hydrogen yields.
Generally, as shown in figure (2.11), pressure has gone from P = 35 bar
and H
2
/HC = 7 to P = 3 bar and H
2
/HC = 2 with yield gains of nearly 10
points for C
5
+
and over 1% for hydrogen.
Ch.2 The Catalytic Reforming Process
36
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CATALYTIC REFORMING
37
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Ch.2 The Catalytic Reforming Process
38
Figure (2.11), Various types of reforming units.
2.4.2.3 Commercial Processes
2.4.2.3.1 IFP "Octanizing" Process
The French Institute of Petroleum developed a process with integral
circulation of the catalyst named "Octanizing", as shown in Figure (2.10).
IFP also developed two solutions for the problem of revamping the
existing old semi-regenerative processes. The first solution is called
"Dualforming" and the second is called "Dualforming Plus". Both
solutions involve the addition of extra moving-bed equipments to narrow
the gap between the fixed- and the moving-bed techniques. Procatalyse
offers the bimetallic catalyst CR201 in the form of spheres with high
resistance to attrition. This is useful for systems with circulating catalyst
such as Dualforming, Dualforming Plus, and Octanizing. For the
production of aromatic hydrocarbons, Procatalyse offers the catalysts
AR401 and AR405.
The catalyst discharged at the bottom of a reactor is conveyed by a stream
of gas, through lift lines and is introduced at the top of the next reactor
and so on, until the catalyst exits the last reactor where it is lifted to the
top of the regenerator. The agent of transport is hydrogen between
reactors and nitrogen between the reactor and the regenerator. The
catalyst regeneration system consists of four interdependent zones:
primary combustion, final combustion, oxychlorination, and calcination.
CATALYTIC REFORMING
39
2.4.2.3.2 UOP "CCR" Platforming Process
The Platforming
®
process is a UOP
®
-developed and -engineered catalytic
reforming process in widespread use today throughout the petroleum and
petrochemical industries. The first UOP Platforming unit went on-stream
in 1949. The Platforming process has since become a standard feature in
refineries worldwide. For this reason, it will be discussed in some details.
Historical Background In the years following the invention of
Platforming, the need for high-octane gasoline blend components and the
demand for aromatics for petrochemicals steadily increased. This
increasing market demand required refiners to operate their Platforming
units at ever higher severity. Eventually, improvements in the catalyst and
process could not keep up, and the need to regenerate catalyst at shorter
and shorter intervals became a serious limitation of the SR Platforming
units. UOP developed the CCR Platforming process, figure (2.9), to
overcome this limitation. In the CCR Platforming unit, partially coked
catalyst in the reactors is continuously replaced with catalyst that has
been freshly regenerated in an external regenerator (CCR section) to
maintain a low average coke for the reactor catalyst. Thus, continuous
high-selectivity and high-activity characteristics associated with new
catalyst can be achieved at significantly higher severities than with the
SR Platforming process. For example, a SR Platforming unit operates at a
severity that steadily builds coke up on the catalyst surface over the
length of a cycle (6 to 18 months), at which point the unit is shut down
and the catalyst regenerated. Throughout the cycle, yields decline. In
contrast, with a modern CCR Platforming unit, the catalyst is regenerated
approximately every 3 days, and yield remains constant at fresh catalyst
levels.
Reactor Configuration In a conventional SR Platforming unit, the
reactors are configured side-by-side. The CCR Platforming unit uses a
UOP-patented reactor stack. The reactors are stacked one on top of
another to achieve a compact unit that minimizes plot area requirements.
The catalyst flows gently by gravity downward from reactor to reactor,
and this flow simplifies catalyst transfer and minimizes attrition. This
configuration eliminates the need to lift the catalyst between reactors,
used in the IFP "Octanizing" unit, which leads to a great simplification of
the process. In the CCR process, catalyst is lifted only twice during each
cycle: from the bottom of the reactor stack to the top of the regenerator
and then from the bottom of the regenerator back to the top of the reactor
stack. The catalyst transfer requires no operator intervention. Catalyst
transfer rates have been designed from as low as 91 kg/h (200 lb/h) to as
Ch.2 The Catalytic Reforming Process
40
high as 2721 kg/h (6000 lb/h), depending on the capacity and the
operating severity of the Platforming unit.
CCR System The ability to continuously regenerate a controlled quantity
of catalyst is the most significant innovation of the CCR Platforming unit.
The catalyst flows by gravity from the last reactor into an integral (to the
reactor) catalyst collector vessel. The catalyst is then lifted by either
nitrogen or hydrogen lifting gas to a catalyst hopper above the
regeneration tower. Catalyst flows to the regeneration tower, where the
catalyst is reconditioned. Regenerated catalyst is then returned to the top
of the reactor stack by a transfer system similar to that used in the reactor-
regenerator transfer. Thus, the reactors are continuously supplied with
freshly regenerated catalyst, and product yields are maintained at fresh
catalyst levels.
The regeneration and reactor sections of the unit are easily isolated to
permit a shutdown of the regeneration system for normal inspection or
maintenance without interrupting the Platforming operation.
Improvements are continuously being made in the CCR regeneration
section design. In addition to its atmospheric and pressurized
regenerators, UOP introduced the CycleMax
®
regenerator in 1995 which
combines new innovations with the best aspects of previous CCR designs
at lower cost.
UOP Commercial Experience UOP has designed more than 730
Platforming (both SR and CCR) units around the world with a total
feedstock capacity of more than 9.1 million barrels per standard-day
(BPSD). The feedstocks range from benzene-toluene (BT) cuts to full-
range, lean Middle East naphthas and rich U.S. and African naphthas and
hydrocracked stocks with capacities ranging from 150 to 60,000 BPSD.
Research octane numbers run from 93 to 108 over a wide range of
catalysts.
The UOP CCR Platforming process is the most successful reforming
process offered by any licenser. As of mid-2002, UOP unparalleled
commercial experience included:
 171 UOP CCR Platforming units operating around the world.
 52 units operating at state-of-the-art reactor pressure of 75 lb/in
2
gage.
 82 units operating at or below 100 lb/in2 gage reactor pressure.
 4,000,000 BPSD CCR Platforming unit operating capacity.
 99.5% of all CCR Platforming units ever started up still operating.
 31 more UOP CCR Platforming units in design and construction.
CATALYTIC REFORMING
41
2.4.2.3.3 UOP "RZ" Platforming
RZ Platforming is the latest development in UOP long tradition of
reforming process improvements. The process is built around a new type
of catalyst called RZ-100. RZ-100 is a zeolitic catalyst, activated with
platinum, that gives the highest obtainable yields of benzene (B) and
toluene (T) from naphtha feedstocks. The RZ process is ideally suited for
use in aromatics production facilities especially when large amounts of
benzene are required. The ability of the RZ Platforming process to
convert light paraffinic feeds and its flexibility in processing straight-run
naphtha fractions provide many options for improving aromatics
production and supplying highly desired hydrogen. Figure (2.12) shows
the RZ Platforming Process.
2.4.3 Fluid-Bed Technology
In catalytic reforming processes using a fluidized solids catalyst bed,
continuous regeneration with a separate or integrated reactor is practiced
to maintain catalyst activity by coke and sulfur removal. Cracked or
virgin naphtha is charged with hydrogen-rich recycle gas to the reactor. A
molybdena (Mo
2
O
3
, 10.0%) on alumina catalyst, not materially affected
by normal amounts of arsenic, iron, nitrogen, or sulfur, is used. Operating
conditions in the reactor are about 200 to 300 psi and 480°C to 950°C
(900°F to 950°F).
Fluidized-bed operation with its attendant excellent temperature control
prevents over- and under-reforming operations, resulting in more
selectivity in the conditions needed for optimum yield of the desired
product.
Ch.2 The Catalytic Reforming Process
42
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CATALYTIC REFORMING
43
CH.3
Process Chemical
Reactions &
Thermodynamics
Ch.3 Process Chemical Reactions And Thermodynamics
44
3.1 INTRODUCTION
Platforming reactions can generally be grouped into four categories:
dehydrogenation, isomerization, dehydrocyclization, and cracking. The
reactions are promoted by two kinds of active sites on the catalyst, acidic
and metallic. The extent to which each of the reactions occurs for a given
Platforming operation depends on the feedstock quality, operating
conditions, and catalyst type.
Because the Platforming feed is made up of many paraffin and naphthene
isomers, multiple reforming reactions take place simultaneously in the
Platforming reactor. The rates of reaction vary considerably with the
carbon number of the reactant. Therefore, these multiple reactions occur
in series and in parallel to one another. The generalized reaction network
is illustrated in Figure (3.1), and examples of the individual reactions are
shown in Figure (3.2).
Figure (3.1), Generalized Platforming reaction network.
3.2 PROCESS REACTIONS
3.2.1 Dehydrogenation of Naphthenes
The principal Platforming reaction in producing an aromatic from a
naphthene is the dehydrogenation of an alkylcyclohexane. This reaction
takes place rapidly and proceeds essentially to completion. The reaction
is highly endothermic, is favored by high reaction temperature and low
pressure, and is promoted by the metal function of the catalyst. Because
this reaction proceeds rapidly and produces hydrogen as well as
aromatics, naphthenes are the most desirable component in the
Platforming feedstock.
CATALYTIC REFORMING
45
3.2.2 Isomerization of Paraffins and
Naphthenes
The isomerization of an alkylcyclopentane to an alkylcyclohexane must
take place before an alkylcyclopentane can be converted to an aromatic.
The reaction involves ring rearrangement, and thus ring opening to form a
paraffin is possible. The paraffin isomerization reaction occurs rapidly at
commercial operating temperatures. Thermodynamic equilibrium,
however, slightly favors the isomers that are more highly branched.
Because branched-chain isomers have a higher octane than straight-chain
paraffins, this reaction improves product octane. Isomerization reactions
are promoted by the acid function of the catalyst.
3.2.3 Dehydrocyclization of Paraffins
The most-difficult Platforming reaction to promote is the
dehydrocyclization of paraffins. This reaction consists of molecular
rearrangement of a paraffin to a naphthene. Paraffin cyclization becomes
easier with increasing molecular weight of the paraffin because the
probability of ring formation increases. Partially offsetting this effect is
the greater likelihood of the heavy paraffins to hydrocrack.
Dehydrocyclization is favored by low pressure and high temperature and
requires both the metal and acid functions of the catalyst.
3.2.4 Hydrocracking and Dealkylation
In addition to naphthene isomerization and paraffin cyclization reactions,
the acid function catalyzes paraffin hydrocracking. Paraffin
hydrocracking is favored by high temperature and high pressure. As
paraffins crack and disappear from the gasoline boiling range, the
remaining aromatics become concentrated in the product, thereby
increasing product octane. However, hydrogen is consumed, and the net
liquid product is reduced, making this reaction undesirable.
Dealkylation of aromatics includes both making the alkyl group (a side
chain on the aromatic ring) smaller and removing the alkyl group
completely. Examples are converting ethylbenzene to toluene and
converting toluene to benzene, respectively. If the alkyl side chain is
large enough, the reaction is similar to paraffin cracking. Dealkylation is
favored by high temperature and high pressure.
Ch.3 Process Chemical Reactions And Thermodynamics
46
Figure (3.2), Generalized Platforming Individual Reactions.
CATALYTIC REFORMING
47
3.3 RELATIVE REACTION RATE
The primary reactions for the C
6
and C
7
paraffins proceed at vastly
different rates. Because the hydrocracking rate for hexane is at least 3
times greater than the dehydrocyclization rate for hexane, only a small
fraction of normal hexane is converted to aromatics. The rate of heptane
dehydrocyclization is approximately 4 times that of hexane. Therefore, a
substantially greater conversion of normal heptane to aromatics occurs
than for hexane.
Reactions of naphthenes in the feedstock show significant differences
between the alkylcyclopentanes and the alkylcyclohexanes. The
alkylcyclopentanes react slowly and follow two competing paths. The
desired reaction is isomerization to an alkylcyclohexane followed by
dehydrogenation to aromatics. The competing reaction is decyclization to
form paraffins. In contrast, the alkylcyclohexanes dehydrogenate rapidly
and nearly completely to aromatics.
The relative ease of isomerization to an alkylcyclohexane increases with
increasing carbon number. For example, the ratio of alkylcyclopentane
isomerization rate to total alkylcyclopentane reaction rate is 0.67 for
methylcyclopentane at low pressure. This ratio increases to 0.81 for
dimethylcyclopentane, one carbon atom higher.
The conversion of hydrocarbon types as a function of position in the
catalyst bed for a moderate-severity Platforming operation is shown in
Figures (3.3 to 3.6). The feedstock is a rich BTX naphtha with a paraffin,
naphthenes, and aromatics (PNA) content of 42, 34, and 24 wt %,
respectively. As the naphtha feed passes through the catalyst bed, total
aromatics concentration increases and the concentration of naphthenes
and paraffins decreases as they undergo conversion Figure (3.3). The high
rate of conversion of cyclohexanes is shown by the rapidly decreasing
concentration of naphthenes in the first 30 percent of the catalyst volume.
The remaining naphthene conversion occurs at a slower rate and is
indicative of cyclopentane conversion and dehydrocyclization of
paraffins through a naphthene intermediate. By the reactor outlet, the
naphthene concentration approaches a low steady-state value, which
represents the naphthene intermediary present in the paraffin
dehydrocyclization reactions. In contrast, paraffin conversion is nearly
linear across the reactor bed.
Figure (3.4) illustrates the conversion of the three reactive species in the
Platforming feedstock. The relative rates of conversion are markedly
Ch.3 Process Chemical Reactions And Thermodynamics
48
different. In the first 20 percent of the catalyst, 90 percent of the
cyclohexanes are converted, but conversion is only 15 percent for
cyclopentanes and 10 percent for paraffins. Cyclopentanes are much less
reactive than cyclohexanes.
Figure (3.5) shows the relative reaction rate of cyclopentanes by carbon
number. Heavier components, which have a greater probability of
isomerizing from a five- to six-carbon ring, convert more readily than do
the lighter components. The most-difficult reaction, the conversion of
paraffins, is characterized by carbon number in Figure (3.6). As with the
cyclopentanes, the heavier paraffins convert more readily than do the
lighter paraffins. The relative ease of conversion associated with
increasing carbon number for alkylcyclopentanes and paraffins explains
why higher-boiling-range feedstocks are easier to process.
In summary, paraffins have the lowest reactivity and selectivity to
aromatics and are the most difficult components to process in a
Platforming unit. Although alkylcyclopentanes are more reactive and
selective than paraffins, they still produce a significant amount of
nonaromatic products. Alkylcyclohexanes are converted rapidly and
quantitatively to aromatics and make the best reforming feedstock. As a
general rule, heavier components convert more easily and selectively to
aromatics than do the lighter components.
Figure (3.3), Hydrocarbon Type Profiles.
CATALYTIC REFORMING
49
Figure (3.4), Reactant-Type Conversion Profiles.
Figure (3.5), Cyclopentane conversion by carbon number.
Ch.3 Process Chemical Reactions And Thermodynamics
50
Figure (3.6), Paraffin Conversion by Carbon Number.
3.4 HEATS OF REACTION
Typical heats of reaction for the three broad classes of Platforming
reactions are presented in table (3.1). The dehydrocyclization of paraffins
and dehydrogenation of naphthenes are endothermic. In commercial
Platforming units, the majority of these reactions take place across the
first two reactors, as indicated by the large negative-temperature
differentials observed. In the final reactor, where a combination of
paraffin dehydrocyclization and hydrocracking takes place, the net heat
effect in the reactor may be slightly endothermic or exothermic,
depending on processing conditions, feed characteristics, and catalyst.
Table (3.1), Heats Of Reactions.
CATALYTIC REFORMING
51
CH.4
Catalytic Reforming
Catalyst
Ch.4 Catalytic Reforming Catalyst
52
4.1 INTRODUCTION
Platinum-based reforming catalysts are used in the late of 1940. By time,
in 1960, their performance was improved by the addition of some metals
such as Ge, Sn, Re, and Ir. These additions have given the catalyst a
better selectivity, a better stability of performance over time, and the
possibility of operating at lower pressure. Most of the reforming catalysts
are based on well-dispersed platinum on an alumina promoted by
halogen, usually chlorine. Since 1970, many attempts were made to find a
better performing system of catalyst. Nowadays the reforming process is
generally carried out over bi-functional catalysts which consist of one or
more metals, most commonly platinum or platinum combined with
rhenium or tin or iridium, dispersed on an acidic support.
4.1.1 Classification of Catalyst
4.1.1.1 Empirical Classification
It distinguishes, on the one hand, the active element causing homolytic or
radical activation. On the other hand there are the active elements
responsible for heterolytic or ionic activation of hydrocarbons (insulating
oxides). An example of the empirical classification is given in Table
(4.1).
CATALYTIC REFORMING
53
Table (4.1), The Empirical Classification of Catalyst.
4.1.1.2 Explicative Correlations
They relate catalytic properties of active elements alone or associated
with the intrinsic properties of the active solid or with the interaction
properties that the solid exhibits with the reaction medium, especially
with the properties characterizing, absorption and adsorption.
Active phase catalyst properties can be radically modified by adding
promoters, sometimes only as traces.
Ch.4 Catalytic Reforming Catalyst
54
4.1.2 Main Types of active phases of Catalyst
There are four types of active phases of catalysts:
1. Bulk catalysts : Are exclusively made up of active phase. For
Example: Claus catalysts, and heterogeneous oligomerzation
catalysts.
2. Supported catalysts : The active phases of refining catalysts are
usually consists of an active phase dispersed on an oxide support
under control on a previously shaped oxide support. For Example:
catalytic reforming catalyst made up of approximately 0.5%
platinum and a promoter dispersed on a chlorinated γ alumina
support. In contrast to bulk catalysts the use of a pre-shaped oxide
allows control of its genesis and especially the optimization of its
textural, structure, mechanical and morphological properties.
3. Catalysts resulting from unit operation : Combining shaping and
the addition of an active phase or precursor salts. For Example:
Catalytic cracking catalysts.
4. homogeneous catalysts : Are produced from organo-metallic
complexes interacting with an appropriate solvent medium. They
are added in trace amounts in the reaction medium. They are used
especially in light olefin oligomerization for motor fuel production,
in gasoline and kerosene sweetening.
4.1.3 General Catalyst Characteristics and
Properties
4.1.3.1 Basic Characheristics
Three basic features characterize the catalyst's action:
4.1.3.1.1 Catalyst Activity
Expresses reactant transformation rate under given operating conditions
in several different ways.good activity means a high reaction rate with
two possible advantages:either a small amount of catalyst can be used or
operating conditions can be less severe, especially the operating
temperature which can be relatively low.
CATALYTIC REFORMING
55
4.1.3.1.2 Catalyst Selectivity
Characterizes the aptitude to activate reactant transformation towards the
required product among all those that could be formed. High selectivity
allows a good yield of the required product to be achieved and reduces
side reactions to a minimum.
4.1.3.1.3 Catalyst Stability
Defined as the period during which its activity and selectivity remain
unchanged.
4.1.3.2 Intrinsic Characteristics
4.1.3.2.1 Structural Properties
The quality of sites dispersed on the active surface, which governs
catalysis as such, is determined by the characteristics of the accessible
active phase (structure, local chemical composition, defects). These
characteristics in turn determine the intrinsic characteristics of the
accessible sites (nature, strength, density, stability, etc.).
4.1.3.2.2 Textural Properties
These properties govern the possibility of reactant access (by diffusion) to
the above-mentioned sites as well as the possibility of evacuating the
reaction products outside by diffusion. Catalyst texture is determined by
the total specific surface area, the active specific surface area (expressed
in per cent of accessibility for dispersed metals), the accessible pore
volume, and the interconnectivity of the pore network.
4.1.3.3 Non-Catalytic Characteristics
4.1.3.3.1 Mechanical Properties
during its lifetime the catalyst is exposed to a number of different
mechanical constraints (production, transportation, storage, loading into
the reactor, unit start up and shut down which cause settling, utilization in
the unite, unloading, off site regeneration, reloading, etc.) with the
resulting breakage, abrasion and attrition. Actual use in the unit is
sometimes a critical period, especially when the catalyst circulates.
Ch.4 Catalytic Reforming Catalyst
56
Resistance to mechanical degradation is therefore an important property
and should be monitored.
4.1.3.3.2 Thermal Properties
When reactions are highly endothermic or exothermic, good thermal
conductivity allows temperature gradients to be limited in the catalyst
grain and bed, thereby promoting the heat transfer. If the catalyst is to
function as a heat carrier (in catalytic cracking for example) it should
have maximum heat capacity: the heat energy stored during coke
combustion will be returned during the reaction, thereby offsetting its
endothermicity.
4.1.3.3.3 Morphology of Catalyst (shape and granulometry)
Depends on where it is used. Ex:-a spherical shape is recommended for
entrained or bulleting fluid beds and rings are used when minimum
pressure drop is required.
CATALYTIC REFORMING
57
4.2 TYPES OF CATALYTIC REFORMING
CATALYST
All current catalysts are derived from platinum on chlorinated alumina as
introduced by UOP in 1949.
4.2.1 Platinum on Chlorinated Alumina
A few hundred tons of this type of catalyst are still being used in the
world. Table (4.2) gives its main characteristics.
Table (4.2), Main Characteristics of Pt/Al
2
O
3
.
The base is γ
c
alumina; chlorinated at approximately 1% wt. the specific
area ranges from 150 to 250 m
2
/g, and the pore volume from 0.5 to 0.8
cm
3
/g. The average pore diameter is approximately 10nm. The alumina
used are very pure and the alkaline metals, alkaline earths, iron etc.,
always account for less than 500 ppm on new catalysts and usually less
than 100 ppm. The amount of platinum is on a downward trend, usually
ranging between 0.2 and 0.6% wt. the catalyst is implemented in the form
of beads ( fixed and moving beds) or extradites ( fixed bed),
approximately 1.2 to 2.2 mm in diameter.
Ch.4 Catalytic Reforming Catalyst
58
In addition to the properties of the support and the amount of platinum, it
is crucial to make the most of the small amount of platinum (cost of
platinum = $15/g) on the catalyst. As such, each platinum atom should be
accessible to the reactants and therefore should be in unit amounts of the
smallest size possible. A gram of platinum well dispersed on the surface
of an alumina will represent an area of approximately 260 m
2
and will
have maximum hydrogenating or dehydrogenating activity. If on the
contrary non-optimum operations are carried out during catalyst
implementation, values lower than 100 m
2
/g of platinum will be obtained
and the catalyst will be approximately three times less active.
Dispersion D is define by the ratio between the real area and the
theoretically possible area per gram of platinum. The theoretical area can
be achieved on industrial catalysts.
4.2.2 Bimetallic
They consist of platinum associated with another metal (iridium,
rhenium, tin or germanium). The use of Pt/Re is now most common in
semi-regenerative processes and Pt/Sn in moving beds. Catalyst
properties can be adapted to the unit's operating conditions. An
interaction between two metals, whose properties and chemistry are
widely different, must be achieved on the scale of the nanometer and this
is the manufacturers' secret.
The effects of different metals on performance have not been publicly
quantified, since there is no non-proprietary literature available.
However, it can be stated that the different elements do have a positive
effect, although the effects differ. The following properties are involved:
stability of dispersion over time, modification of coking resistance,
change in selectivity and especially for high concentrations of iridium,
and a significant effect on activity.
Figure (4.1) illustrates the influence of elements such as tin, indium,
rhenium and iridium on the evolution in the platinum surface over time as
compared with platinum alone. In all cases, the effect is highly positive.
This is why these elements have been selected for numerous industrial
catalysts.
CATALYTIC REFORMING
59
Figure (4.1), Effect of Different Metals on Platinum Sintering Under Hydrogen
Pressure.
Figure (4.2) shows the variation in octane number in a constant
temperature test versus time. In these operating conditions-feed end point
very high and test duration short-deactivation is related only to coke
formation and/or coke toxicity with respect to activity. The bimetallic
catalyst, here platinum-rhenium, proves incomparably more stable than
the monometallic one. The other "second metals", Sn and Ir, give the
same type of effects.
Ch.4 Catalytic Reforming Catalyst
60
Figure (4.2), Compared Stability of mono- and bi-metallic Catalysts.
4.3 EFFECT OF PLATINUM CONTENT OF
CATALYST
Platinum content of the catalyst is in the range (0.3 – 0.8 % wt).
- At higher levels there is some tendency to effect dimethylation and
naphthene ring opening, which is undesirable, while at lower levels the
catalyst tends to be less resistance to poisons.
- Platinum is extremely expensive. As the platinum content of catalyst is
reduced, it's resistance to deactivation is also reduced.
- The high platinum catalysts (0.6 – 0.8 % wt pt) are used for sever
operations such as the production of 100 octane number gasoline from
feeds with only moderate naphthene contents.
-The latest development is the use of bimetallic catalyst which
incorporated other metals (Rhenium and Tin) in addition to platinum this
catalyst can operate at lower hydrogen partial pressure than can the
normal platinum catalyst without deactivation.
CATALYTIC REFORMING
61
4.4 CATALYST PREPARATION
There are two methods for catalyst preparation:
4.4.1 Optimizing the formulation
Step 1
The choice of active phases is based on experience (empirical or
scientific correlation).
Step 2
Aims to identify which initial reactants include or prefigure the desired
active phase.
Step 3
Design an operating mode.
Finally to implement it.
Step 4
Determining basic catalyst properties in addition to the test reaction in
order to validate the result.
Step 5
Once an initial result has been obtained and the active phase has been
characterized, the required catalyst qualities are ranked: catalyst,
physicochemical and mechanical properties. The most critical are singled
out and the key preparation unit operations are listed. To the extent
possible, the textural and structure properties that can be correlated to
performance are identified.
At the same time, on the basis of published data and initial kinetic
experiments, a simplified approach to the reaction mechanism is used to
identify the limiting steps and the possible inhibiting effects. In particular,
it is used to define the level of diffusional limitations.
At this stage, the activity and selectivity of an initial catalytic formula
have been established and performance stability has proved satisfactory.
Then the evolution of the active phase (and/or the support) should be
assessed in the reaction medium and if possible its stationary state should
be characterized.
The catalyst formula under study can now be considered valid and a
number of correlations can be established linking its catalytic properties,
the intrinsic characteristics of the active phase (and/or the support) , the
Ch.4 Catalytic Reforming Catalyst
62
preparation conditions, then the pretreatment conditions in the reactor and
the stabilization conditions in the reaction medium.
As soon as laboratory formulation has been optimized and the catalysis
results have been validated in a continuous pilot on a real feed, it will be
possible to scale up the operating mode to produce a pilot test batch of
catalyst (10 to 50 liters) and then to begin optimizing the operating
conditions of the future production process. This will result in a
representative pre-industrial sample which will be tested in a large pilot
unit.
4.4.2 Unit Operations
The aim is to produce a catalyst at the lowest possible cost, consisting of
the required active agents, with the desired surface area and porosity,
external morphology and necessary mechanical properties for the process
technology under consideration.The choice being made between different
possible manufacturing methods. The resulting manufacturing technique
will be based on a sequence of unit operations. The number and
sequencing order of these operations must be optimized to minimize the
manufacturing cost and obtain the most high-performance and
reproducible product possible. Figure (4.3) describes the sequence of
main unit operation.
CATALYTIC REFORMING
63
Figure (4.3), The Sequence of Unit Operations.
Ch.4 Catalytic Reforming Catalyst
64
The following will be examined by way of examples:
 Shaping supports and catalysts.
 Preparing catalyst.
 Preparing supports, their properties.
 Catalysts impregnated on supports.
4.4.2.1 Shaping supports and catalysts
The choice of the catalyst shaping process is generally the result of a
compromise after asset of constraints has been studied, particularly with
respect to:
 The characteristics of the catalytic process (Catalyst slurry, fixed,
circulating or fluid bed).
 The intrinsic characteristics of the solid that is to be shaped
(crystallinity, chemical reactivity, plasticity).
 Economic imperative (cost of the shaping process).
4.4.2.2 Preparing catalyst
Catalyst can be prepared by precipitating an:
a) Alumina hydro gel by reaction of ammonium hydroxide with Al
chloride and washing the gel until the chloride content is less then 0.1 wt
b) The gel is filtered
c) The correct quantity of halogen ( as HCL or HF ) solution is added
d) The Platinum is then added in the form of Chloroplatinic acid solution
treated with H
2
S
e) After mixing, the gel is dried, pelleted and calcined at about 500 C
°
.
Zeolite containing Tellurium is very selective for the dehydrocyclization
of n-hexane to benzene but is rapidly deactivated. Especially K-1,
K-Ba-1 are highly selective for the dehydrocyclization of n-hexane and n-
heptane, but are sensitive to poisoning by sulfur compounds.
Activity and selectivity performances similar to these of platinum on
zeolite were obtained by replacing the latter zeolite with a support based
on mixed aluminum and Mg oxide obtained by the decomposition of
hydro-talcite.
CATALYTIC REFORMING
65
4.4.2.3 Preparing supports: Properities
Refining catalyst supports consist of alumina, silica, silica-alumina or
titanium oxide. They can also contain some zeolite (mordenite, Y zeolite,
ZSM5, etc.)
They are characterized by:
1. High chemical purity.
2. Morphology, grain size distribution and texture suited to the
process chemistry:
- Surface acid-base properties.
- Ion exchange properties.
- Mechanical properties suited to the process
technology.
 Economic feasibility that allows significant production.
Aluminas represent a large group including alumina hydrates, transition
alumina, and a- Al
2
O
3
4.4.2.3.1 The methods for preparing the hydrates
a) Acidification of sodium aluminates
b) Neutralization of an aluminum salt
c) Hydrolysis of an aluminum alcholate
The two main alumina supports used in catalytic reforming are two
transition alumina N & Y Al
2
O
3
:-
1- N-Al
2
O
3
:- is obtained by calcinations above 250-300
o
C of alumina
tri-hydrate bayerite in air or in vacuum of gibbsite.
2- Y-Al
2
O
3
:- is obtained by calcinations of bohmite in air
4.4.2.3.2 Influence of alumina acidity
The increased acidity caused by the fixation of halogen on the surface of
an alumina. The acidity promoted in different ways according to the
halogen used (F or Cl). The type of acidity seems to depend on fixed
chloride content and the chloride precursor used.
Ch.4 Catalytic Reforming Catalyst
66
The catalyst must have an acid activity, to activate for isomerization of
both paraffins and naphthenes, but balance between these two activities,
is most important in a reforming catalyst.
For example :
1- In the case of gasoline production from a naphthenic feed, the
hydrocracking should be minimized to avoid loss of yield by lowering the
acid activity.
2- In the case of gasoline production from a paraffinic feed, the acid
activity can be obtained by means of halogens (F or Cl) or silica
incorporated in the Alumina base.
4.4.2.4 Catalysts impregnated on a support
This can be done by two ways:
4.4.2.4.1 Impregnation Without Interaction
The support is simply wetted by the precursor solution (by spraying or
immersion). The solution penetrates the pore network, gradually filling it
(in a few minute to a few hours). The three characteristics of the method
are:
 Its exothermicity (heat of adsorption).
 The high pressure developed in the pores, since part of the air
initially present is trapped by the liquid and compressed. The
Young-Laplace law:
∆p= (2γ /r
p
) cos θ
(γ : surface tension, θ : junction angle of the meniscus, r
p
:pore
radius)
Shows that pressure can reach several hundred bars in the
mesopores with r
p
<10nm. Under such pressure the support particles
can burst.
 The duration of impregnation. The solution penetrates very rapidly
by means of capillary forces (a few minutes), but its diffusion is
slowed down in the meso- and micro pore network by dissolution
and diffusion of the trapped air. During the operation of solution
equidistribution, then subsequent maturation and drying, the active
phase precursor becomes deposited.
CATALYTIC REFORMING
67
4.4.2.4.2 Impregnation with interaction
The support is immersed in an excess of solution containing the precursor
salt. The salt interacts with the surface as shown in figure (4.4).
 Interaction can consist in formation of a chemical bond between
the precursor and the support: the interaction is then a grafting. In
this way it is possible to fix silicon or tin from tetrabutoxy tin in a
hyper dispersed form. Later on, thermal activation releases the
organic fragments and forms the surface oxide molecule.
 Precursor-support interaction can also be ionic in nature, of the
acid –base type for example. This is the case for anionic and
cationic exchanges. A competitor ion(Cl
-
for PtCl
6
2-
, NH
4
+
for
Pt(NH
3
)
4
2+
)is generally added to the reaction medium in order to
control exchange kinetics and get homogeneous distribution of
active elements in the grain in a hyper dispersed form. The
support-anchored hyper dispersed phases are obtained after drying
and thermal activation.
Figure (4.4), Impregnation with Interaction.
Ch.4 Catalytic Reforming Catalyst
68
4.5 REACTION MECHANISMS
The platinum on chlorinated alumina catalyst has two functions, table
(4.3):
 A hydrogenating-dehydrogenating function provided by the
platinum, and
 An acid function provided by the alumina.
In catalytic reforming, an operation where gaseous hydrocarbons are in
contact with the catalyst solid, the reaction occurs on the surface of the
solid as long as temperatures remain lower than 550 °C. Above this,
thermally activated homogeneous phase reactions can take place. On the
catalyst surface there are a large number of adsorbed species that are
dehydrogenated to a greater or lesser extent, either on the metal or on the
acid part of the support. The adsorbed species change by isomerization,
cyclization or cracking and are then desorbed. Note that there is naturally
also adsorbed hydrogen.
Table (4.3), Reactions Mechanisms.
CATALYTIC REFORMING
69
4.5.1 Hydrogen Action
Hydrogen is not involved as a reactant in most reactions, except for
hydrogenolysis and hydrocracking. It is involved in the reactant and
product adsorption- desorption equilibrium and as a product of
equilibrium reactions. It limits the conversion of certain hydrocarbons.
4.5.1.1 Product Yield and Quality
The impact of hydrogen on reformat quality is related mainly to the
presence of more or fewer residual naphthenes. However, the principle
effect is the presence of olefins, which can go up to more than 1% when
the process is run at pressure lower than 5 bar.
4.5.1.2 Effects on Reaction Kinetics
The kinetics of heterogeneous reactions is generally very complex and
this is particularly true for the dehydrocyclization reaction. As illustrated
in figure (4.5), this with the variation in dehydrocyclization rate of n-
heptane at 470°C versus the hydrogen pressure P
H2
for different
hydrocarbon partial pressures. Note that, depending on P
H2
, there is a
maximum whose ordinate and abscissa depend on the hydrocarbon
pressure.
Hydrogen is involved in generating unsaturated species on the catalyst
surface (it limits formation of overly unsaturated species that could
develop solely into coke and would block part of the catalyst), but also by
the fact that it is adsorbed on the catalyst, thereby blocking certain sites
that are no longer available to activate reactions. As an example, figure
(4.6) shows the variation in methyl-cyclopentane conversion, either to
benzene which has a high RON, or to C
6
paraffin which have a lower
RON, versus hydrogen pressure for three different catalysts: platinum,
platinum-tin and platinum-rhenium. At a hydrogen pressure of 25 bar,
benzene is formed twice as fast as hexanes, while at 7 bar, it is formed
five to six times faster with platinum and platinum-rhenium and 12 times
faster with platinum-tin.
Ch.4 Catalytic Reforming Catalyst
70
Figure (4.5), Dehydrocyclization Rate vs. Hydrogen Pressure.
Figure (4.6), Influence of hydrogen pressure on the selectivity of
Methylcyclopentane conversion.
CATALYTIC REFORMING
71
4.5.1.3 Effect on Coking
Hydrogen influence polyunsaturated species concentrations on catalysts.
It therefore limits the average concentration in intermediates likely to
develop into coke. For instance, the time required to lay down an amount
of coke on a catalyst is determined, 1.5% wt in figure (4.7). The time is
seen to increase very quickly as the molar ratio H
2
/heptane rises at
constant total pressure.
Figure (4.7), Effect of Hydrogen Pressure on Coke Formation Rate.
4.5.2 Sulfur Action
Sulfur influences the performance of mono and bimetallic reforming
catalyst. In such cases:-
- (Pt-Re/Al
2
O
3
), it was found that sulfur on Rhenium restricts the
formation of graphitic coke, thus improving the stability of the catalyst.
- (Pt-Ir /Al
2
O
3
)
,
the high activity resulting from the addition of Iridium
allows some degree of sulfur in the feed
- For the reforming of industrial naphtha it was found the sulfur has an
effect on aromatic yield when its concentration in the feed stock exceeds
0.03 wt %.It was observed in these experiments , an increase in sulfur
conc. has two principles effects:
Ch.4 Catalytic Reforming Catalyst
72
1. Initial inhibition of aromatics formation.
2. Declined the accelerated catalyst activity.
C
5
and lighter Sulfur Catalyst. age
9 0.026 9.7-10.3
9.4 0.026 7.6-8.6
9.7 0.052 8.7-9.6
- These result show that the sulfur acts to enhance the acidity and inhibit
the dehydrogenation activity of catalyst.
4.5.2.1 The different options
- The presence of sulfur reduces the pt life span of catalyst.
- If the catalyst is presulfided, the activity can be prolonged.
- Sulfur introduced with feed has a stabilizing effect on the overall
activity.
- The sulfiding of Pt/Al
2
O
3
catalyst increase the thermal stability but
decrease the activity for dehydrogenation of cyclohexane.
- In studying the reforming of naphtha and pure hydrocarbons, indicated
that the beneficial effect on catalyst stability, involving high severity
processing conditions is related to the formation of Pt-S complex of lower
reactivity than the original Platinum species to reactions such as coking.
And this is due to an adsorption phenomenon in which only a fraction of
the available platinum sites are deactivated by Pb adsorption and the
identity of those deactivated sites changes constantly because of the
dynamic nature of sulfur adsorption.
CATALYTIC REFORMING
73
4.6 CATALYST DEACTIVATION
In the oil refinery, the deactivation of the catalyst by carbonaceous
deposits is an important technological problem.
Deactivation in the reforming process is attributed to coke formation and
deposition. In fact, for reforming reactions of naphtha's, the
thermodynamics are such that it would be desirable to work at high
temperature and low pressure. However, such operating conditions favor
coke formation, and many reforming units operate under high pressure in
order to increase the life time of the catalyst.
It is obvious that reducing the rate of coking formation would represent a
desirable improvement, particularly at a time when production of lead-
free gasoline is requiring more severe operating conditions (higher
temperature and lower pressures).
4.6.1 Characterization of Coke
Coke deposit on bifunctional catalyst is characterized by:
4.6.1.1 Quantitative analysis and localization of coke
This can do by the combustion under oxygen of coked catalysts. It was
found that the coke is not deposits in the form of a monolayer but, on the
contrary, three-dimensional deposition appear from the onset of coking.
The coke localized on metallic particle and support, this show the
heterogeneity of the coke distribution on the catalyst.
4.6.1.2 Composition and structure of coke
The composition of coke calculated by analysis of coke combustion
products to determine the H/C ratio.
Measuring the amounts of oxygen consumed and carbon dioxide
produced during temperature-programmed oxidation figure (4.8).
Ch.4 Catalytic Reforming Catalyst
74
Figure (4.8), Temperature-Programmed combustion of a coked Pt/Al
2
O
3
catalyst
(A) CO2 production; (B) O2 consumption.
4.6.2 Effects of reaction conditions on coking
Deactivation
4.6.2.1 Hydrogen and hydrocarbon pressure, space
velocity
From thermodynamic view, it would be best to operate reforming units at
the lowest possible hydrogen pressure; however, catalysts are unstable
under such operating condition.
Figure (4.9) shows that although deactivation is relatively slow at 50 bar,
it becomes very fast under 10 bar of hydrogen pressure.
Figure (4.9), Typical influence of pressure on stability.
CATALYTIC REFORMING
75
4.6.2.2 Temperature of the reaction
Temperature is the operating variable used for activity maintenance in an
industrial unit and therefore it is important to know its influence on coke
fouling.
On platinum single-crystal surface its shows that the morphology of the
carbonaceous deposit appears to vary continuously from two-dimensional
at low reaction temperature (<277°c) to three-dimensional for higher
temperature than about 327°C. Thus is the range of reforming
temperature s, coke deposits will be always three-dimension.
The amount of coke increase with increasing temperature and this
evolution can be explained by the effect of high temperatures on the
number of unsaturated products which are coke precursors.
The evaluations capable explain by the effect of high temperatures on the
number of unsaturated products which are coke precursors.
Increasing temperature also accelerates the graphitization process of
coke, its shows that the fraction of reversible coke (partially
hydrogenated) decrease as the temperature and amount of coke increase.
The coke grows mainly on the support with increasing temperature and
that is more dehydrogenated.
Increasing temperature not change the location of coke (on the metal or
on the support) because the catalytic activity of the metal for constant
coke conversion is comparable on the different samples, what ever the
coking temperature. Table (4.4).
Table (4.4), Effect of the coking temperature on the characteristics of coke.
a
coking with cyclopentane at atmospheric pressure; H
2
/H.C ration 2.33.
b
Relative activity in benzene hydrogenation.
Ch.4 Catalytic Reforming Catalyst
76
4.6.2.3 Nature of hydrocarbons in feed
Reforming feed stocks very widely in their boiling range and
hydrocarbon type distribution (paraffin's, aromatics and naphthenes)
depend on their origin, generally, heavier cuts produce more coke.
It was state that for cuts around 204°C end boiling point there is (1.6-2.3
%)in cycle length per °c increase in feed end, whereas at end boiling
point are 216°c the decease in cycle length (2.1-2.8%) per °C, but the
cut's with the lowest boiling range have a high content of cyclopentanic
compounds are great coke producers.
Hydrocarbons such cyclopentane, n-dodecane turned out to be very good
coke precursors. Adding low amounts of di-cyclic aromatics to n-paraffin
(n-hexane, n-heptane) increase catalyst aging significantly.
Figure (4.10) is studied the coke fouling on Pt/Al
2
O
3
catalyst for different
hydrocarbon have 6 carbon atoms. Methyl cyclo pentane >3-methyl
pentane > n-hexane >2-methyl pentane >benzene > cyclo hexane.
Figure (4.10), Coke deposition on Pt/Al
2
O
3
for various H.C at 500 °C.
Effect of n-paraffin, on deactivation found that coke deposition and
catalyst deactivation is minimum for n-heptane, but aromatics with
paraffin chain tendency to produce coke increase.
For naphthenes if the ring has five carbon atoms, coke formation and
catalyst deactivation higher than six carbon atoms rings.
CATALYTIC REFORMING
77
The coke deposition increase in order cyclopentane < cyclopentene
<cyclo pentadiene, which is the coke agent responsible for the deposition
of coke.
In case of bi functional catalyst the coke deposition occurs mainly on the
acidic sites of support.
4.6.2.4 Effect of sulfur on the coking reaction
Sulfur compounds are recognized as poisons for reforming catalysts and
they can cause a complete loss of activity. In order to avoid deactivation,
sulfur concentrations need to be less than 1 ppm in feed. But on the other
hand sulfur is not totally unwanted because a low concentration of sulfur
in feed or during start-up of units can reduce excessive hydrogenolysis at
beginning of run and improve the catalyst stability.
The presence of sulfur implies a higher reaction temperature for the same
performance, figure (4.11), and therefore a higher coke fouling rate.
Figure (4.11), Rate of deactivation versus sulfur content of the feed. Monometallic
Pt/Al
2
O
3
at approximately 500 °C.
Ch.4 Catalytic Reforming Catalyst
78
4.6.2.5 Effect of carbon deposits on reforming
reactions
We can say coke deposits are poison that can alter the selectivity of bi-
functional catalyst, as they show different toxicities according to the
reaction taken into consideration. Table (4.5) shows that dealkylation of
toluene most sensitive to coke.
Reagent Reaction toxicity
n-heptane Dehydrogenation
Cracking
Isomerization
Coke formation
430
300
125
360
Methylyclohexane Dehydrogenation
Coke formation
110
720
Toluene Dealkylation
coke formation
700
750
3,3Dimethylbutene Isomerization 30
Table (4.5), Initial toxicity of coke (in g. of deactivated catalyst per g. of deposited
coke) at 430°C.
4.6.2.6 Effect of deactivation on the performance of
reforming catalyst
The stability of activity and selectivity of catalyst over a period of time is
dictated by the nature of deactivation, which may by sintering of the
catalyst activity or poisoning/coking caused deposition of the feed stream
impurities or the formation of some surface residue (coke) by other side
reactions.
4.6.3 Mechanism of Coke Formation
Coking of bi-functional catalyst results from accumulation of coke on the
metal and on support, and therefore two mechanisms of coke formation
have to be proposed.
CATALYTIC REFORMING
79
4.6.3.1 On Metal Sites
There are two typical models for coke production:
4.6.3.1.1 The first model
Involves a series of fragmentation reactions and successive
dehydrogenation reaction which lead to the formation of carbon atoms,
this atoms are partially hydrogenated intermediate may combine to form
more graphitic and more toxic coke deposits.
4.6.3.1.2 The second mechanism
Suggests that the routs of coke deposition are based on polymerization
reactions with the formation of different types of carbonaceous deposits
on the metal surface. For large platinum crystallites increase the rate of
coke deposition because of the ability to give higher stabilization for
adsorbed cyclopentadiene precursor produced during the reaction.
4.6.3.2 On acid sites
It's assumed that coke arise from the polymerization of dehydrogenated
intermediates generated by the metallic function. In case of coking
reaction with cyclo pentane, this cyclo pentane can lead to naphthalene or
heavier poly aromatics compounds through the following sequence of the
reaction:
Ch.4 Catalytic Reforming Catalyst
80
4.6.4 Poisoning of Naphtha Reforming Catalyst
Catalyst poisoning is on of the most severe problems associated with the
operation of commercial catalysts. The most common type of catalyst
poisoning is caused by any impurity that is either present in the gas
stream or formed by some process during reactions.
The poison formed by some process during reactions. The poison
becomes adsorbed on the active sites of the catalyst causing either a
temporary or permanent decrease in the all over activity.
Poisoning of naphtha reforming catalysts occur typically as result of
inadequate use of naphtha pretreatment conditions. In commercial
practice, the life of naphtha reforming catalyst may be reduced to a few
months or weeks into the presence of only small concentration of poison
contaminants in the feed.
In most cases, because of the essentially irreversible adsorption of poison
compounds on the metal surface, regenerations usually impossible or
impractical. The importance of poison molecules in the inhibition of the
reforming-type reaction is shown in table (4.6) This shows the initial
CATALYTIC REFORMING
81
toxicities of different compounds obtained for hydrogenation of benzene
on a pt/Al
2
O
3
catalyst.
It seems that the adsorption of a poison deactivates the surface on which
it adsorbed, and the toxicity depends on the number of geometrically
blocked metal atoms.
The quantity of poison absorbed on the metal sites cannot be readily
measured. It is only possible to know the quantities of impurities injected
or deposited on the whole catalyst.
Sulfur present as impurities in the naphtha feed stock in concentrations of
organic sulfide of up to 1500 ppm.
Poisoning due to nitrogen compounds are known to inhibit principally the
acid function of the catalyst. Metal impurities most commonly named as
poisons of reforming catalysts are arsenic, sodium, copper, mercury, and
lead.
It was found that they have a strong affinity for platinum that results in an
irreversible poison effect as result of the formation of stable chemical
compounds with platinum.
4.6.4.1 Poisoning by Sulfur Compounds
Sulfur is known to adsorb strongly at very low gas phase concentration
and can remain as a very stable adsorbed species under different reaction
condition.
In case of catalytic reforming, sulfur compound, in high concentrations in
the hydrocarbon feed, have been found to have an adverse effect on the
catalytic properties of the catalyst.
Catalyst poisoning typically results from strong chemisorption of sulfur
compounds on the surface of the metal.
4.6.4.1.1 The sulfur limits in each catalyst
 Monometallic pt/Al
2
O
3
; sulfur concentration in the feed must be
kept below 20 ppm.
 Bimetallic catalyst (Pt-Re/ Al
2
O
3
); the level should be maintained
well below 1 ppm.
 Catalysts containing higher Re/Pt ratio; are more sensitive to sulfur
compound, maximum sulfur of 0.5 ppm is allowed.
Ch.4 Catalytic Reforming Catalyst
82
Table (4.6), Initial Toxicities of various compounds on Pt/Al
2
O
3
catalyst.
CATALYTIC REFORMING
83
In case of the bimetallic t-Re/ Al
2
O
3
catalysts, it was found that sulfur on
rhenium restricts the formation of graphitic coke; it's improving the
stability of the catalyst. However, for Pt-Ir/ Al
2
O
3
,
The high activity resulting from the addition of iridium allows some
degree of sulfur in the feed. Figure (4.12) shows the effect of sulfur on
reforming of naphtha feed.
Figure (4.12), Effect of sulfur on Reforming of naphtha feed at constant catalyst
life.
4.6.4.1.2 Increasing sulfur concentration has two principal
effects
1. Initial inhabitation of aromatic formation and accelerated catalyst
activity decline. The inhibition of the catalyst activity appeared to
be a reversible reaction.
2. It was found that for n-heptane reforming with 0.8% sulfur,
dehydrocyclization is reduced and hydrocracking is increased.
These results show that sulfur acts to enhance the acidity and
inhibit the dehydrogenation activity of the catalyst.
Ch.4 Catalytic Reforming Catalyst
84
4.6.4.1.3 The effect of varying concentration of sulfur on the
activity and selectivity of platinum reforming catalyst
They found that sulfiding of Pt/Al
2
O
3
catalyst increases the thermal
stability but decreases the activity for dehydrogenation of cyclo-hexane.
The concept of selective and nonselective poisoning on reforming
reactions working with Pt/Al
2
O
3
,they found that certain poisons such as
H
2
s and SO
2
are nonselective; they have the same effect in the different
reaction studies: hydrogenation of benzene (nondemanding reaction) and
hydrogenolysis of cyclopentane, a (demanding reaction.).
On other hand, Atomic sulfur is a selective poison that reduces the rate of
hydrogenolysis of cyclopentane more than that of hydrogenation of
benzene.
The figure (4.11) shows clearly the importance of the effect of sulfur on
catalyst deactivation rate expressed as inlet reactor temperature necessary
to achieve a constant reformate quality as a function of operating time.
4.6.4.2 Poisoning by Nitrogen Compounds
Nitrogen compounds are generally present in the form organic
compounds that decompose into ammonia at reforming conditions.
They inhibit principally the acid function of the catalyst, but to some
extent they can alter the metallic properties of the platinum.
It is clear that nitrogen compounds have a little effect on the
dehydrogenation reaction. On the other hand, hydrocracking,
Isomerization, and dehydrocyclization are adversely affected, indicating
that acid sites are more involved in these reactions. Figure (4.13) shows
the effect of nitrogen content on catalyst aging
CATALYTIC REFORMING
85
Figure (4.13), The effect of nitrogen content on catalyst aging.
4.6.4.3 Poisoning by Metals
Deactivation of naphtha reforming catalysts by metal contaminates has
received little attention and only a few fundamental investigation has
been reported it is known that the metallic poisons are rarely eliminated
by regeneration, and as a consequence all necessary precaution need to be
taken to prevent them from coming into contact with the catalyst.
It is known that platinum metal can be activated by metallic ions such a
mercury, arsenic, lead, bismuth, copper and iron.
One of the most affected reactions is dehydrogenation. Studies carried out
using lead showed this effect, figure (4.14).
Ch.4 Catalytic Reforming Catalyst
86
Figure (4.14), Poisoning of dehydrogenation by lead.
Similarly, small amounts of iron and copper can accelerate the
deactivation in the dehydrocyclization reaction figure (4.15).
Figure (4.15), Poisoning by copper and iron.
From the results it is clear that metal contamination generally causes a
decrease in the dehydrogenation and dehydrocyclization functions.
4.6.4.3.1 Effect of arsenic on Pt/AL
2
O
3
They found 0.01-0.02 wt % on the catalyst have little effect on reforming
reaction. An increase in arsenic concentration on catalyst to 0.5 wt%
decreases dehydrogenation activity.
CATALYTIC REFORMING
87
4.7 CATALYST REGENERATION
They found 0.01-0.02 wt % on the catalyst have little effect on reforming
reaction. An increase in arsenic concentration on catalyst to 0.5 wt%
decreases dehydrogenation activity.
4.7.1 Effect of the Type of Process on Cycle
Length
a. Semi-regenerative: the operation may last several thousand
to more than 10,000hours before it's interrupted for
regeneration.
b. Fully regeneration :(swing- reactor type) or continuous
(moving bed reactor type) cycle may last only a few hundred
hours or even less.
4.7.2 Catalyst Regeneration Steps
1. Elimination of coke by controlled burning
2. Catalyst rejuvenation, which comprises:
a. Restoration of the acid function and metallic dispersion by
chlorination.
b. Reduction with hydrogen.
c. Passivation by sulfiding.
4.7.3 Factors affecting coked catalyst reactivity
1. Coke structure which is dependent on the nature of catalyst and
reaction conditions.
2. The chemistry and the nature of carbon deposition and the
3. Characterization of coked catalyst.
4.7.4 Regeneration of Coked Catalyst
4.7.4.1 Regeneration with Hydrogen
Hydrogen is found to have a significant impact on hydrocarbon reaction
over the naphtha reforming process. It's already known that high
hydrogen pressures lower the concentration of coke precursors, thereby
Ch.4 Catalytic Reforming Catalyst
88
keeping the coke rates low. This because the strong dehydrogenation
reactions involved in coking are restricted by the presence of hydrogen.
On the metal surface, coke levels controlled by hydrogen cleaning. The
cleaning action of hydrogen occurs by catalytic hydrogenation, whereas
the slow removal of coke occurs by catalytic hydrogasification.
The mechanism showed in figure (4.15) is for the hydrogen cleaning of
platinum surfaces. This mechanism is based on the distribution of two
types of coke on metal sites, one being easily removed by hydrogen
(Reversible coke) and the other less readily removed (irreversible coke).
Figure (4.15), Model of carbon removal by hydrogen.
- For bi-functional catalysts, a small amount of the coke is deposited
on the metal where the majority is accumulated on the alumina.
- Hence a large part of the coke which is destroyed by hydrogen
treatment is deposited on the support.
- These phenomena can be explained by either the mobility of
carbonaceous deposits on the catalyst surface or the hydrogen
mobility.
- The presence of an optimum surface chloride concentration in the
regeneration of Pt / Al
2
O
3
catalysts by H
2
was found to be an
important parameter.
CATALYTIC REFORMING
89
A catalyst with about 0.5 wt% Cl shows a complete regeneration during
static and dynamic H2 spillover from Pt alumina which restores
the catalyst surface freeing it from H.C residues.
4.7.4.1.1 The effect of the nature of bi-functional catalysts on
their regeneration by H
2
:
The carbon remaining decrease and the activity of the catalyst for
benzene hydrogenation increases with the temperature of hydrogen
treatment.
4.7.4.1.2 The effect of time of H
2
treatment on the amount of
coke remaining on the catalyst:
It was found that increasing the time of treatment result in
decreasing coke content. But the carbonaceous deposits become
more and more dehydrogenated showing that more hydrogenated
compounds are eliminated first.
The metallic activity is totally regenerated but a large amount of
coke still remains on the catalyst at 430°C at 20 hrs.
4.7.4.2 Regeneration with oxygen
Regeneration in presence of oxygen can be complicated by the fact that
metal sintering can be promoted at high temperature.
The burning of coke start with the coke deposited on the platinum
because of the catalytic action of platinum and because the deposit is
richer in hydrogen.
The burning then spreads to the carbon on the support by the action of
oxygen spillover, with burning at lower temperatures when more
platinum is present.
The last part of the coke to be burned is the most distant from the metal
and the coke poorest in hydrogen. Comparing the pt/Al2O3 catalysts with
different metal-to-acid ratios, it is accepted that pt catalyzes the burning
of the coke.
The higher the metal-to-acid ratio, the lower the burning temperature.
Also Pt deceases the oxidation temperature of graphite.
Ch.4 Catalytic Reforming Catalyst
90
Greater amounts of Pt are present; the coke is less polymerized because
of the Pt-catalyzed hydrogenation of coke precursors occurring during the
reaction. The less polymerized deposit would oxidize at a lower
temperature.
The acceleration of coke burning in the presence of pt can be explained
by:
1- Oxygen is adsorbed on Pt in an activated form.
2- Travels by spillover along the support (Al
2
O
3
) to the coked
alumina particles.
3- The activated oxygen spills along the pores of the coked alumina,
eliminating the coke by burning at lower temperature than that of
the gaseous oxygen.
The effect concentration of Rhenium in pt Re/Al
2
O
3
catalyst on the
regenerative behavior:
1- For the catalyst which have less than 50% Re :
The regeneration occurs at the same temperature as for pt/ Al2O3
(500C)
2- For Re is above 50% :
The coke would not burn off until much high temperature was reached.
The presence of Re decrease of spillover cause it's not capable of
promoting spillover.
Figure (4.16) shows that when Pt is present, the oxidation starts at lower
temperatures and the temperature peak is also at lower temperature.
Although the amount of carbon is the same.
Figure (4.16), TPO of alumina samples mixed with platinum –alumina after coking
with naphtha during 6 hr.
CATALYTIC REFORMING
91
4.7.5 Regeneration of sulfur- contaminated
catalysts
When naphtha reforming catalysts are contaminated with sulfur, a special
procedure has to be employed during the regeneration to diminish the
sulfation of the support . When the sulfur content of the catalyst exceeds
1000 ppm, a special regeneration procedure to remove the sulfur is
followed before any attempt to burn the coke.
Oxidation and reduction studies of the formation and elimination of
sulfated on Pt/Al
2
O
3
catalysts indicate the oxidation eliminated the
sulfur, deposited on the metal , however the oxidized sulfur compounds
were strongly held on the support.
4.7.5.1 Effect of sulfur on catalyst performance
In industrial units, sulfur cause the formation of iron sulfide from the
reactor materials .When carbon removal takes place, the iron sulfide is
oxidized into metal oxide (fe
2
O
3
) and sulfur trioxide (SO
3
) .The (SO
3
)
formed reacts with the alumina to form the thermally very stable alumina
sulfate, diminishing the surface hydroxyl concentration.
Sulfur can be removed either after oxy-chlorination or before catalyst
regeneration by this procedure:
1- It consists of reduction of the sulfur species under hydrogen at
about (500°C) .
2- The formed hydrogen sulphide is eliminated from the gas by
washing with an aqueous sodium carbonate solution.
3- It is recommended that the procedure be continues until the
hydrogen sulphide concentration is lower than 2 ppm, for at least l
hour.
4- When performed after oxy-chlorination: This is in order to increase
the Al sulfate reduction and limit the loss of chloride from the
catalyst, a chlorinated compound is injected during the operation.
In the presence of sulfate ions, operating temperatures have to be
increased of rapidly to maintain the octane number constant until
the sulfate removal step is employed. Stated that during reduction
at 500 ˚C, the sulfate is reduced to H
2
S, escaping with the exist
gases of the reformer .Where the reduction at 300 ˚C cannot
convert sulfates to H
2
S. The Pt-Re/Al
2
O
3
regeneration was found to
Ch.4 Catalytic Reforming Catalyst
92
be more complicated if sulfate and sulfite species were present on
the alumina surface during calcinations, theses sulfite are converted
to H2S during reduction.
4.8 PROCEDURE OF REGENERATION
4.8.1 Pre-shutdown
1-Prepare auxiliary regeneration equipment.
2-Ensure that all necessary chemicals and materials are available.
4.8.2 Shutdown
1. Reduce reactor inlet temperatures to 454˚C (850˚F) then stop
charge to the unit.
2. Lower reactor inlet temperatures to 400˚C (750 ˚F ).
3. Remove residual liquid hydrocarbons.
4. Nitrogen blankets the unit.
4.8.3 Carbon Burn
1. Conditions of carbon :
a. 400˚C (750˚F ) reactor inlet temperatures and 454˚C (850˚F )
maximum reactor outlet temperatures .
b. Maximum pressure consistent with air supply and
equipment.
c. Maximum recycle circulation consistent with equipment.
d. 0.6 to 0.8 mole % oxygen at the compressor discharge
2. Maintain chloride addition at 20: 1 mole ratio of water: chloride at
the inlet of reactor 1. Also hold 30: 1 mole ratio of water: chloride
at the inlet of the last reactor when the last reactor is being burned
in parallel.
3. Maintain corrosion control (caustic or carbonate circulation
through the air cooler – separator).
4. Hold carbon burn conditions until the reactor outlet temperatures
have remained at their base levels for four hours.
CATALYTIC REFORMING
93
4.8.4 Oxidation
1. Conditions of oxidation:
a. 510˚C (950 ˚F) reactor inlet temperatures.
b. 5 mole % oxygen in circulating gas.
2. Hold a 20: 1 mole ratio of water: chloride for eight hours.
3. Stop chloride injection.
4. Flash and drain separator: Drain all low points thoroughly before
stopping heater firing.
4.8.5 Cool down
1. Stop heater firing continues maximum gas circulation.
2. Maintain 5 mole % oxygen in the circulating gas throughout the
cool down.
3. Continue gas circulation until all reactor outlet temperatures are
below 204 ˚C (400 ˚F).
4.8.6 Nitrogen purge
1. Purge in reverse from the first reactor inlet unit the oxygen level is
less than 0.3 mole % and the carbon dioxide level is less than 0.1
mole % at the compressor discharge.
2. Purge forward from the first reactor inlet until the oxygen level is
less than 0.3 mole % and the carbon dioxide level is less than 0.1
mole % at the compressor suction.
3. Measure the sulfur dioxide level in the purge gas. Hold purges until
the sulfur dioxide level has peaked, and declined to a low level
(less than 50 ppm).
4.8.7 Reduction
1. Purge 10 catalyst volumes of hydrogen through the plant, purging
all lines.
2. Pressure the unit to a minimum of 7 kg / cm
2
absolute (100 psia)
with grade hydrogen.
3. Begin maximum gas circulation. Increase inlet temperatures at 55
0
C / hour to 427
0
C ( 100
0
F / hours to 800
0
F ) for all catalysts
except R – 30 series which will be 480
0
C (900
0
F) .
4. Hold required reactor outlet temperatures for one hour.
Ch.4 Catalytic Reforming Catalyst
94
5. During the heat – up, water should be frequently drained from the
separator and system low points and the circulating gas hydrogen
sulfide content should be monitored.
6. After we holding required reactor outlet temperatures for one hour ,
reduce heater firing and begin cooling to 371
0
C ( 700
0
F ) reactor
inlet temperatures in preparation for cut in.
4.8.8 Sulfate Removal
1. If a sulfate removal step is to be used, complete the regeneration
through step G – 4 of the Reduction. The oxidation hold period,
step D – 2, can be shortened to four hours. The reduction may also
be done with catalyst reformer hydrogen of 75% minimum purity.
2. At the 510
0
C (950
0
F) conditions of step G-4 of reduction, start
chloride injection at 20:1 mol ratio water: chloride, maintain a
circulating water pH of 7.5 to 8.0.
3. Maintain 510
0
C (950
0
F ) and 7.0 kg/cm
2
absolute (100 psia )
hydrogen partial pressure and all reactor effluent hydrogen sulfide
concentrations are below 5 ppm .
4. When 5 ppm hydrogen sulfide concentration is reached at all
reactor outlets, stop chloride injection, flush and drain the
separator, and reduce heater firing.
5. Continue gas circulation until all reactor outlet temperatures are
below 400
0
C ( 750
0
F ) .
6. Depressurize and nitrogen purge the unit .
7. Re-establish the conditions of the carbon burn , step C . when the
proof burn is complete , continue with the procedure through the
oxidation , cool down , purge reduction , and startup steps as
outlined
4.8.9 Start-up
1. Pressure to 8.8 kg/cm
2
(125 psia) minimum hydrogen partial
pressure.
2. Start naphtha charge at 371
0
C (700
0
F ) reactor inlet temperatures .
3. Follow programmed chloride addition.
4. Hold the reactor temperatures at reduced levels until the water and
sulfur specification are met.
CATALYTIC REFORMING
95
CH.5
Catalytic Reforming
Parameters
Ch.5 Catalytic Reforming Parameters
96
5.1 INTRODUCTION
Catalytic reformers are designed for flexibility in operation, whether for
motor fuel production or to produce aromatics such as benzene, toluene,
and xylenes (BTX). To meet these drastically varying demands, the
reforming catalyst must respond to change in unit operating condition.
The variables, which affect the performance of the catalyst and change
the yield and quality of reformat are; feedstock properties, reaction
temperature, space velocity, reaction pressure and hydrogen to
hydrocarbon mole ratio.
5.2 TEMPERATURE
The operator has very little freedom to act on an industrial unit in normal
operation. In fact temperature is the only operating variable he can use to
adapt changes in feed quality or to produce reformats of different quality.
Reformers are generally designed with three or more reactors in usually
series each of them contain different quantity of catalyst so there are
changes of temperature as feed flow through the catalyst from one reactor
to another.
Reaction temperatures are chosen to balance the advantage of increased
reformats quality (research octane number) and disadvantage of increased
deactivation rate as temperature increased.
T (SOR) or start of run temperature is the reactor inlet temperature, which
yields the required octane number at full capacity at the beginning of the
run, and its related to the RON under certain condition is shown in figure
(5.1).
CATALYTIC REFORMING
97
Figure (5.1), Variation in octane number versus T
SOR
.
Also temperature variation curve with time depends on the severity of an
operating and naturally on the catalyst quality. Platinum catalyst alone or
bimetallic Pt-Re catalyst will allow the required octane number to be
achieved at the same starting temperature but the variation will be much
faster with monometallic catalyst. As shown in figure (5.2).
Figure (5.2), Variation in temperature during a run.
Ch.5 Catalytic Reforming Parameters
98
Yield doesn’t vary in the same way. Monometallic catalyst shows a drop
in yield as soon as the temperature rises. While bimetallic C5+ selectivity
remains the same, until the end of the run as shown in figure (5.3).
Figure (5.3), Variation in C
5+
during the run.
Another important parameters is (∆T) across each reactor which give
indication about the reaction occur as well as the H
2
/H.C ratio used. In
the first reactor there are negative (∆T) due to the dehydrogenation
reaction that take place in this reactor. But positive (∆T) observed in last
reactor due to the hydrocracking that takes place in this reactor as
dehydrogenation is endothermic reaction but hydrocracking is exothermic
reaction.
5.3 REACTION PRESSURE
The reformer units in 1950 typically operated in the pressure higher than
that operated nowadays .Reformers have three or more reactors usually in
series and the pressure is different in each reactor. It is preferable to use
the average reactor pressure, if it is available, for estimating yields and
cycle length.
CATALYTIC REFORMING
99
The pressure under which reforming take place affect on yields and cycle
length. Decreasing pressure increase the production of aromatics and
hydrogen by dehydrogenation of naphthenes and dehydrocyclization of
paraffins and reducing hydro cracking as shown in figure (5.4).
Figure (5.4), Influence of P and the feed on C
5+
yield.
The disadvantages of increasing pressure are:
 increased catalyst coking;
 reduce the product yield and;
 shorter cycle length.
Notes
At 100 RON there is an increase in percent yield of reformat from 79.7 to
83.5 by a reduction in pressure from 300 to 100 psig.
5.4 HYDROGEN TO HYDROCARBON RATIO
In catalytic reformers hydrogen is recycled in order to maintain a certain
ratio of H
2
/H.C and high partial pressure.
The advantage of increasing H
2
/H.C ratio is the hydrogen react with coke
precursors, removing them from the catalyst before they form significant
amount of polycyclic aromatics and deactivation the catalyst also reduce
Ch.5 Catalytic Reforming Parameters
100
catalyst deactivation rate. The disadvantage of increasing H
2
/H.C ratio it
affects aromatization and increases hydro cracking.
A lower hydrogen partial pressure favors dehydrogenation of naphthenes
and dehydrocyclization of paraffins. However, it affect on the catalyst life
due to increasing density to form coke.
Monometallic catalyst in seventies worked at high ratio (7-8) to achieve
stability comparable to the modern catalyst with H
2
/H.C=4 as shown in
figure (5.5).
Figure (5.5), Catalyst stability versus H
2
/H.C.
Notes
By reducing H2/H.C from 8 to 4 and 4 to 2 the carbon on catalyst is
increased by a factor of 1.75 and 3.6 respectively. By reducing H2/H.C
ratio from 5 to 4 shorten cycle length about 20%.
CATALYTIC REFORMING
101
5.5 SPACE VELOCITY
It is a measure of the contact time between the reactants and the catalyst
and expressed as liquid hourly space velocity or weight hourly space
velocity.
LHSV = volume per hour of reactor charge / vol. of catalyst.
WHSV = weight per hour of reactor charge/weight of catalyst.
The choice represents a compromise between allowable hydro cracking
and desired dehydrocyclization. Aromatization and isomerzation aren’t
affected by changes in space velocity because these reaction approach
equilibrium even at high space velocity.
Modern reformers usually operate between from 1.0 to 2.0 h
-1
(LHSV).
As below 1.0 h
-1
undesired side reaction, increased hydro cracking and
reducing reformat yield.
Figure (5.6) show that beginning with space velocity=2 to 3 requires
raising the reactor inlet temperature by 8 degree centigrade to maintain
reformat octane number, in contrast a drop of 1.5 allow the inlet
temperature to be lowered by 6 degree centigrade. These values may vary
little depending on the operating condition and catalyst used.
Figure (5.6), Influence of Space Velocity on Octane Number.
Ch.5 Catalytic Reforming Parameters
102
5.6 FEEDSTOCK PROPERTIES
In reforming operation, the feed properties are parameters which can
significantly influence the performance of the catalyst such as:
 Straight run naphtha generally constitutes the major feedstock for
reformers. Feedstock containing an appreciable concentration of
unsaturated hydrocarbons such as thermal cracked, cat-cracked,
coker and pyrolysis naphtha must usually be hydro-treated before
reforming in order to prevent undue hydrogen consumption in the
reformer and excessive catalyst deactivation. In addition to being
high in sulfur and nitrogen, these stocks contain substantial amount
of mono-olefins. These olefinic species are undesirable in reformer
feed for several reasons. First, in a reformer reactor, olefins
hydrogenate, consuming hydrogen that might be needed for hydro-
treating other stocks. Second, hydrogenation of olefins markedly
lowers their octane numbers, resulting in lower octane reformat.
The third is increasing the tendency to polymerize and form coke
on the reforming catalyst.
 Sulfur in the feed poisons the metal and organic nitrogen
compounds, which can form ammonia, poisons the acid function,
of the catalyst, so concentration must be maintained at less than
about 1 PPM by hydro-treating before reforming.
 Water and chlorine compounds as they alter the acidity of the
support, and their concentration must be carefully controlled to
maintain the proper catalyst acidity.
 Metal such as As, Pb and Cu must be kept at low concentration,
because they deposit on the Pt component and deactivate it.
Table (5.1) summarizes the effects of cut points on the different variables.
The temperature T (SOR) increases if the initial boiling points are low.
The run duration is shortened by low initial boiling points due to the
higher operating temperature, and by high end point due to the presence
of coke precursors.
Initial boiling points are too low, indicating the presence of a lot of C
6
,
cause a large amount of benzene to be produced. Since light paraffins are
hard to convert, the desired octane will be achieved only by production
more C
7+
aromatics. High endpoints reduce benzene production, but can
CATALYTIC REFORMING
103
cause substitute naphthalene to be produced, which it run cause rapid
catalyst coking.
Figure (5.7) show that the difference between the amount of naphthenes
on the yields, higher naphthenes give higher amount of yields.
Table (5.1), Influence of IBP and EP at constant space velocity and RON.
Figure (5.7), Influence of P and the feed on C
5+
yield.
Ch.5 Catalytic Reforming Parameters
104
Operating pressure for present day processes is summarized in table (5.2)
to have a possible yield with a possible quality with different type of
catalyst (monometallic and bimetallic catalysts).
Table (5.2), Operating conditions for present-day processes.
CATALYTIC REFORMING
105
CH.6
Hazard Assessment
Ch.6 Hazard Assessment
106
Hazard
[1] Chemical and catalyst handling:
A. Labels and Other Forms of Warning:
All portable containers of hazardous chemicals must have a large,
readable label or tag which states:
• Name and address of manufacturer
• Name of chemical
• Numerical hazard warning or other appropriate warning supplied by
manufacturer
Labels can be color coded according to following:
• Orange Carcinogen Hazard (ie benzene)
• Red Chemical Burn Hazard (ie acids, bases)
• Yellow Toxic Vapor Hazard (ie H
2
S)
• White All Others
B. Material safety data sheet (MSDS):
Chemical manufacturers, importers and distributors are required to
provide MSDSs to purchasers of hazardous chemicals.
Although format of MSDS can vary, they must include following
information:
• Chemical and common name
• Ingredient information
• Physical and chemical characteristics
• Physical hazards - potential for reactivity, fire and/or explosion
• Health hazards
• Symptoms of exposure
• Primary route of likely entry into body on exposure
• OSHA permissible exposure levels
• Precautions for use
• Waste disposal
• Protective measures and equipment, including during spills and
maintenance
• Emergency and first-aid procedures
• Date of MSDS preparation and last revision
• Emergency contact of manufacturer or distributor
CATALYTIC REFORMING
107
[2] Hydrogen sulfide poisoning:
Hydrogen sulfide is both an irritant and an extremely poisonous gas.
Many natural and refinery gases contain more than 0.10 mol-percent H
2
S.
Current OSHA permissible exposure limits are 20 mol-ppm ceiling
concentration and 50 mol-ppm peak concentration for maximum ten
minute exposure.
Any unit processing gases containing H
2
S can be operated safely,
provided ordinary precautions are taken and poisonous nature of H
2
S is
recognized and understood.
A-Acute hydrogen sulfide poisoning:
Breathing air or gas containing more than 500 mol-ppm H
2
S can cause
acute poisoning and may be fatal.
B-Symptoms of acute hydrogen sulfide poisoning:
Symptoms of acute H2S poisoning are muscular spasms, irregular
breathing, lowered pulse, odor to breath and nausea. Loss of
consciousness and suspension of respiration quickly follow.
After victim recovers, there is still risk of edema (excess accumulation of
fluid) of lungs which may cause severe illness or death in 8 to 48 hours.
C- First aid treatment of acute hydrogen sulfide poisoning:
Move victim at once to fresh air. If breathing has not stopped, keep
victim in fresh air and keep quiet.
If possible, put him to bed. Secure a physician and keep patient quiet and
under close observation for about 48 hours for possible edema of lungs.
If victim has become unconscious and breathing has stopped, artificial
respiration must be started at once. Speed in beginning artificial
respiration is essential. Do not give up. Men have been revived after more
than four hours of artificial respiration.
If other persons are present, send one for a physician. Others should rub
patient's arms and legs and apply hot water bottles, blankets or other
sources of warmth to keep him warm.
After patient is revived, he should be kept quiet and warm, and remain
under observation for 48 hours for appearance of edema of lungs.
Ch.6 Hazard Assessment
108
D-Sub acute hydrogen sulfide poisoning:
Breathing air or gas containing H
2
S anywhere between 10 to 500 mol-
ppm for an hour or more may cause sub acute or chronic hydrogen sulfide
poisoning.
E- Symptoms of sub acute poisoning:
Symptoms of sub acute H
2
S poisoning are headache, inflammation of
eyes and throat, dizziness, indigestion, excessive saliva, and weakness.
Edema of lungs may occur.
F- Treatment of sub acute poisoning
Keep patient in dark to reduce eyestrain; have a physician treat inflamed
eyes and throat. Watch for possible edema.
Where sub acute poisoning is suspected, atmosphere should be checked
repeatedly for presence of H
2
S.
G-Prevention of hydrogen sulfide poisoning:
Best method for prevention of H
2
S poisoning is to stay out of areas
known or suspected to contain it.
Fresh air masks or gas masks suitable for use with hydrogen sulfide must
be used in all work where exposure is likely to occur. Masks are checked
frequently to make sure they are not exhausted.
Persons who must work on or in equipment containing appreciable
concentrations of H2S, must wear fresh air masks and work in pairs so
that one may effect a rescue or call for help should other be overcome.
As mentioned above, atmosphere in which people work should be
checked from time to time for appreciable concentrations of H
2
S.
CATALYTIC REFORMING
109
[3] Precautions for entering contaminated or inert
atmosphere:
Nitrogen is non-toxic. However in vessels or areas where there is a high
nitrogen concentration, there is also a deficiency of oxygen for breathing.
Breathing an atmosphere deficient in oxygen will rapidly result in
dizziness, unconsciousness, or death depending on length of exposure.
Do not enter or even place your head into a vessel which has a high
concentration of nitrogen.
Do not stand close to a valve where nitrogen is being vented from
equipment at a high rate which may temporarily cause a deficiency in
oxygen close to valve.
Refinery personnel who must enter a contaminated or inert atmosphere
follow all prescribed standard safety precautions and regulations which
apply for refinery.
It is important to emphasize that if a person has entered a vessel and
become unconscious, no individual should go in to help him without first
donning a fresh air mask.
A. Safe Vessel Entry
Precautions apply equally to entry into all forms of vessels, including
enclosed areas which may not normally be considered vessels. Examples
include:
Reactors Separators
Fractionators Drums
Receivers Pumps
Fired Heaters Storage Tanks
Neutralizing Basins Water Treatment Basins
API Separators
(1) General precautions:
Vessel must be positively isolated.
Safe access to vessel must be assured.
Man way and internals must be provided.
Personnel entering vessel must be provided with safety harnesses.
Two persons must be available outside vessel to assist personnel
inside.
Ch.6 Hazard Assessment
110
Safety of atmosphere inside vessel must be confirmed by checks
for toxic gases (eg H2S), oxygen content, and explosive gases.
A supply of fresh air must be available for people who will rescue
personnel entering vessel in event they encounter difficulty.
A vessel entry permit must be obtained and registered with
responsible persons.
(2) Positive isolation:
Every line connecting to a nozzle on vessel to be entered must be blinded.
Area around vessel man ways is surveyed for possible sources of
dangerous gases which may enter vessel while person is inside. Any
hazards found during survey are isolated or removed.
(3)Vessel access:
Proper access is provided both to exterior and interior of vessel to be
entered. Exterior access should be a solid, permanent ladder and platform
or scaffolding strong enough to support people and equipment who are
involved in work to be performed.
Access to interior must be strong and solid. Scaffolding is preferred when
vessel is large enough to permit its use.
(4) Safety harness:
Any person entering a vessel should wear a safety harness with attached
safety line.
Minimum of one harness for each person entering vessel and at least one
spare harness for persons watching at man way should be provided.
(5)Man way watch:
Before a person enters a vessel, there should be minimum two people
available outside vessel; one of whom is specifically assigned
responsibility to observe activity of people inside vessel.
These people should not leave their post until those inside vessel have
safely exited.
A communication system must be provided for man way watch so that
they can quickly call for help in event personnel inside vessel encounter
difficulty. Radio, telephone, or public address system is necessary for that
purpose.
CATALYTIC REFORMING
111
(6) Fresh air:
Vessel must be purged completely free of any noxious or poisonous gases
and inventoried with fresh air before permitting anyone to enter. Safety
department must test atmosphere within vessel for toxic gases, oxygen
and explosive gases before entry. This must be repeated every 4 hours
while there are people inside vessel. Each point of entry and any dead
areas inside vessel, such as receiver boots or areas behind internal baffles
where there is little air circulation, should be checked.
Fresh air can be circulated through vessel using an air mover, fan, or, in
cases where moisture is a concern, vessel can be purged using dry
certified instrument air from a hose or hard piped connection.
When instrument air is used, a check of supply header is made to ensure
it is properly lined up and there are no connections where nitrogen can
enter system (nitrogen improperly used as backup for instrument air by
some refiners). Fresh air purge should be continued as long as people are
inside vessel.
Minimum one fresh air mask for each person entering vessel and at least
one spare mask for manhole watcher should be provided at vessel entry.
Each mask must have backup air supply completely independent of main
supply. It must also be independent of electrical power. Auxiliary supply
must have an alarm that alerts user he is on backup supply, and should be
sufficiently large to give user five minute autonomy to escape from
danger.
(7) Vessel entry permits:
Before entering vessel, a vessel entry permit must be obtained. Vessel
entry permit ensures that all responsible parties know that work is being
conducted inside vessel and establishes safe preparation procedure to
follow in order to prevent mistakes which can result in an accident.
Permit is typically issued by safety engineer or shift supervisor.
(8) Checkout prior to startup:
Risk of exposure to hydrocarbons, toxic or poisonous gases, and catalyst
dust is low during new unit checkout. Primary danger is nitrogen. Vessel
entry procedure must be rigorously followed during checkout of new unit.
Oxygen content of atmosphere inside vessel is checked before every entry
and vessel is blinded.
Independent blinds at each vessel nozzle are preferred.
Ch.6 Hazard Assessment
112
(9)Turnaround inspections:
In turnaround inspections, possibility that vessels contain dangerous
gases is much higher. Equipment which has been in service must be
thoroughly purged before entry. Vessel should have been steamed out
(unless steam presents hazard to internals), then fresh air circulated
through it until all traces of hydrocarbons are gone. If liquid hydrocarbon
remains or if odors persist afterwards, repeat purging procedure until
vessel is clean.
In a turnaround inspection, every vessel nozzle must be blinded with no
exceptions. Blinds must all be in place before vessel is purged.
Another factor to be cautious of is heat stress especially if entering a
vessel immediately after unit has been shut down.
B. Aromatic Hydrocarbons:
i. Benzene:
Benzene is extremely toxic.
Special instruction: If clothing (including gloves, shoes) becomes
contaminated with benzene, it should be removed immediately. Wash any
skin areas exposed to benzene with soap and water.
Take complete bath if body area is wetted with benzene. Do not wear
clothing that has been wet with benzene until garment is decontaminated
by washing or dry cleaning.
Wearing clothing that has been wet with benzene almost guarantees that
person will inhale benzene vapors over a long period of time, resulting in
potential health hazards.
Avoid draining benzene to concrete or into sewers where it can vaporize
and create health hazard. Do not use hot water or steam which aggravates
vaporization of benzene.
If you must enter an area of high benzene vapor concentration resulting
from a spill, wear appropriate respiratory protection such as self-
contained breathing apparatus, or air mask with external supply.
CATALYTIC REFORMING
113
ii. Toluene, xylenes and heavier aromatics:
These compounds are moderately toxic and are believed not to have
destructive effects on blood forming organs as does benzene. If clothing
(including gloves, shoes, etc) becomes wet with such aromatics, remove
clothing, bathe, and put on fresh clothing. Avoid breathing aromatic
vapors.
iii. Minimizing exposure to aromatics:
Operating and laboratory personnel involved in obtaining samples wear
chemical-type safety goggles or shield, protective apron or laboratory
coat, solvent-resistant gloves, and approved respiratory protective
equipment where ambient concentrations exceed allowable limits.
This protective equipment is not, however, substitute for safe working
conditions, proper ventilation, good personal practices, and proper
maintenance of operating and safety equipment.
In all cases, skin contact (Especially eyes) and inhalation must be
minimized.
Sampling liquid hydrocarbons requires some care to limit personal
exposure and release to atmosphere.
To minimize vaporization, hot hydrocarbon streams must be routed
through a cooler before drawing a sample. In all sampling situations,
personnel are instructed to remain at arm's length from sample container
and to situate themselves upwind of container if possible. These simple
precautions greatly minimize exposure to hydrocarbon vapors.
iv. Medical attention:
U.S. NIOSH/OSHA guidelines for toluene, xylene and ethylbenzene set
forth recommendations for medical monitoring of personnel working in
environments where exposure to these materials can occur.
All new or current employees should be alerted to early signs and
symptoms resulting from exposure to aromatics, and any workers
experiencing such symptoms must seek professional medical attention.
Ch.6 Hazard Assessment
114
C. Safety Information for UOP Platforming Catalysts:
It is during periods of opening and cleaning equipment or in sampling
that bodily exposure to UOP Platforming catalyst can occur and caution
must be exercised.
Material Safety Data Sheets should be obtained from UOP at the time of
catalyst supply and should be available to the operating personnel.
Major constituent of UOP Platforming catalyst is alumina, which is not
currently listed by OSHA as a hazardous substance. These catalysts do
contain other constituents, in lesser amounts, which might present
hazards to human health and/or the environment if handled or disposed of
improperly. It is the purpose of this safety section to provide information
and recommendations which will allow safe handling and proper disposal
of these catalysts.
Only following fresh catalysts (R-11, R-12, R-14, R-16, R-18, R-19, R-
50, R-51, R-55, R-60, R-62) contain hydrogen sulfide.
Spent Platforming catalysts may also contain additional hazardous
chemicals, such as: arsenic, carbon, hydrocarbons, iron pyrites, iron
sulfide, lead, and vanadium. The toxic properties and exposure limit of
the most hazardous of these chemicals follow:
i. Hydrogen sulfide:
Hydrogen sulfide is both an irritant and an asphyxiant. Current OSHA
permissible exposure limits are 20 ppm ceiling concentration and 50 ppm
peak concentration for a maximum 10 minute exposure.
ii. Arsenic:
Arsenic is a recognized carcinogen and can cause acute and chronic
toxicity. Symptoms of acute toxicity are somewhat dependent upon route
of contact and can include (for ingestion or inhalation): irritation of the
stomach and intestines, with nausea, vomiting and diarrhea; liver damage;
kidney damage; blood disturbances; and allergic reactions. The OSHA 8-
hour time weighted average exposure limit to inorganic arsenic
compounds is 10 micrograms per cubic meter of air.
Greatest potential for human exposure to catalyst materials comes from
catalyst dust during reactor loading and from dust, fumes, and vapors
during catalyst unloading operations.
For the unprotected worker, hazardous dust, fumes, and vapors may be
inhaled, ingested, or contaminate the eyes and skin.
CATALYTIC REFORMING
115
• Handling Catalyst spills and Deposited Catalyst Dust:
Always wear NIOSH-approved self-contained breathing apparatus or
combination of toxic dust respirator-rubber frame eye goggles, protective
clothing, and gloves. Avoid cleaning methods which raise dust. Dispose
of all catalyst wastes properly in containers, which should then be labeled
as to the contents and hazards.
Do not dispose of catalyst wastes in a public water system or in the
normal solid waste. Return material to supplier for metal recovery.
• Handling UOP Catalysts Safely:
UOP believes that OSHA exposure limits to catalyst chemicals will not
be exceeded if proper handling procedures and worker protective
clothing/safety devices are used.
UOP recommends that the following minimum safety procedures be
established and adhered to:
Handle catalysts only in a well ventilated area. In areas where
natural ventilation is insufficient, use local mechanical exhaust
ventilation
Wear a NIOSH-approved toxic dust respirator with full face-piece,
protective clothing, and gloves for normal catalyst handling
operations
Reactor loading and unloading operations present extraordinary
health risks, especially to personnel working in the reactor. During
loading operations, large quantities of catalyst dust may be
generated. During unloading, the hazards may include inert
(nitrogen) atmosphere, toxic feedstock, product, or purge materials
present with the catalyst, or toxic forms of catalyst chemicals.
Personnel working in reactors should wear a supplied air respirator
with a hood or helmet, operated in a pressure-demand or other
positive-pressure mode, or in a continuous flow mode (NIOSH
Respirator Code SAFE: PD, PP, CF). This respirator should have a
primary, secondary, and emergency supply of air. In addition,
personnel in the reactor should be equipped with safety harnesses
and safety lines for rescue and a means for visual, voice or signal
line communication with standby personnel, who should be
strategically located with suitable rescue equipment. The OSHA
regulations concerning use of respirators (29 CFR, Subpart 1,
Section1910.134) should be read and thoroughly understood before
undertaking to place personnel in reactors during catalyst loading
and unloading operations.
Ch.6 Hazard Assessment
116
Protective clothing and all safety devices should be thoroughly
decontaminated after each use. Worn-out, broken or defective
safety equipment and clothing should be removed from service and
repaired or replaced. Good personal hygiene after handling a
catalyst or being exposed to catalyst dust is an essential part of a
responsible catalyst safety program. Do not eat, drink, or smoke in
areas where the catalyst is being handled or where exposure to
catalyst dust is likely
National Fire Protection Association
Identification of Color Coding:
Color Blue: Type of possible injury
Materials which on very short exposure may cause death or major
residual injury even though prompt medical treatment was given
Materials which on short exposure may cause serious temporary or
residual injury even though prompt medical treatment was given
Materials which on intense or continued exposure may cause
temporary incapacitation or possible residual injury unless prompt
medical treatment is given.
Materials which on exposure cause irritation but only minor
residual injury even if no treatment is given.
Materials which on exposure under fire conditions offer no hazard
beyond those of ordinary combustible materials.
Color Red: Susceptibility of material burning
Materials which will rapidly or completely vaporize at atmospheric
pressure and normal ambient temperature, or which are readily
dispersed in air and which will burn readily.
Liquid and solids that can be ignited under almost all ambient
temperature conditions.
Materials that must be moderately heated or exposed to relatively
high ambient temperatures before ignition can occur.
Materials that must be preheated before ignition can occur.
Materials that will not burn.
CATALYTIC REFORMING
117
Color Yellow: Susceptibility of release of energy
Materials which in themselves are readily capable of detonation or
of explosive decomposition or reaction at normal temperature and
pressure
Materials which in themselves are capable of detonation or
explosive reaction but require a strong initiating source or which
must be heated under confinement before initiation or which react
explosively with water
Materials which in themselves, are normally unstable and readily
undergo violent chemical change but do not detonate. Also
materials which may react violently with water or which may form
potentially explosive mixtures with water
Materials which in themselves are normally stable, but which may
become unstable at elevated temperatures and pressures or which
may react with water with some release of energy but not violently
Materials which in themselves are normally stable, even under fire
exposure conditions and which are not reactive with water
Hazardous materials:
List of attached material safety data sheets:
Naphtha
Reformate
LPG, sweetened
Hydrocarbons, (C1-C4)
Hydrogen
Hydrogen Sulfide
Benzene
Toluene
Xylene
Phosphate
DMDS
Caustic Soda
UOP Platforming Catalyst
Ch.7 Plant Design
118
CH.7
Plant Design
CATALYTIC REFORMING
119
PLANT LOCATION
The final choice of the plant site usually involves a presentation of the
economic factors for several equally attractive sites. The exact type of
economic study of plant location will vary with each company making a
study.
Factors Affecting Plant Location
1. Raw materials supply
The location of the raw materials of an industr y contributes more
toward the choice of plant site than any other factor. This is especiall y
noticeable in those industries in which the raw material is inexpensive and
bulky and is made more compact and obtains a high bulk value.
2. Markets and transportation
The existence of transportation facilities has given rise to many of the
greatest trade centers of the world.
A location should be chosen, if possible which has several competition
will help to maintain low rates and given better service.
3. Markets for Finished products
The large oil refiners are located along the seacoast or near large cities
where a market exists for the finished products.
Crude oil is easily pumped by pipelines or shipped from the oil well sin
the interior.
Cheap rates are thus secured for a crude low-priced commodity.
Consumed in large quantities while the finished products are made in the
center of the market in order to lower the distribution cost.
4. Power and fuel supply
The fuel best plan is to locate near large coal field if coal is the primary
fuel or to tie up by long contracts sufficient gas and /or oil to ensure the
continuity of operation over a long term.
Sources of power:
Power for chemical industry is primarily from coal water and oil. The
turbines or engines used to generate electricity can be operated non
condensing and supply exhaust steam for processing purposes.
5. Water Supply
Water for industrial purposes can be obtained from two general sources;
the plants own source or principle supply if the demands for water are
large. It is more economical for the industry to supply its own water such a
supply may be obtained from drilled will rivers, lakes, damned streams
Ch.7 Plant Design
120
before a company enters up on any project, it must ensure it self of as
insufficient supply of water for all industrial. Sanitary and fire demands
both present and future.
Water natural quality is as diverse as the sites and regions from which it is.
Water temperature and chemical characteristics such as organic and
inorganic contaminants, the relative price are of greatest economic
importance in determining the value of water to the chemical industry. The
relative importance of each of these depends upon the service for which the
water is wanted.
6. Climate
Chemical plants as general rules are rather difficult to insulate or to
provide with artificial heat or conditional air.
Essentially a process must be designed for production of a commodity or
commodities under the most economic conditions, if out side plant
climate does not fit into the picture of production, then process and
process equipment.
7. Labor
Before locating an industry in any particular location a careful study of
the supply of available labor must be made.
Factors to be considered in labor studies are supply. Kind, diversity,
intelligence, wage scale, regulations, ef ficiency and costs.
8. Community and site characteristics
In the selection of a definite plant site in a designated area there are many
minor factors to which some attention should be given. The chemical
industry is usually of minor importance. Of great importance is a nature of
the subsoil the need of piling or other expensive foundations can materially
affect construction costs. Also the site information is essential in the
selection of apian location.
PLANT LAYOUT
For marketing, many factors must be considered such as:
1. New sites development or addition previously development.
2. Future expansion.
3. Economic distribution of services-water process steam, power and gas.
4. Weather condition are they amenable to out door construction.
5. Safety consideration possible hazards of fire explosion and fumes.
6. Building code requirements.
7. Waste disposal problems.
8. Sensible use of floor and elevation space.
CATALYTIC REFORMING
121
The layout will bed one by the use of (unite areas) concept method which are
particularly well adopted to large plant layout. Unite areas are often
delineated by means of distant process phase and operational producers by
reasons of contamination and by safety consideration requirement. Thus the
delineation of the shape and extent of a unite area and of interrelation ships of
each area in a master plot plan is one of the first take of layout planning.
Ch.8 Design
122
CH.8
Design
CATALYTIC REFORMING
123
Material balance
Crude flow rate = 1.2 * 10
6
ton/yr
Sweet naphtha flow rate = 18 % of crude flow rate
∴ Naphtha flow rate =
hr lb / 60125
24 330
2046 . 2 10 18 . 0 10 2 . 1
3 6
=
×
× × × ×
Molar flow rate of naphtha = 60125 / 107.6 = 558.78 lb
mol
/hr
By using catalytic reforming yield correlations at (K =11.7,
R.O.N.C.=98):-
1) From fig. (6-3): [C
5
+
vol% =82%]
2) From fig. (6-4): [C
4
vol% = 6.4%]
3) From fig. (6-5): [(C
1
+ C
2
) wt% = 2.25%,C
3
wt% = 3%]
4) From fig. (6-6): [H
2
wt% = 2.8%]
From Kern by t
mean
= 40 * 1.8 + 32 = 104 f
°
∴ ρ
Naphtha
= 0.71 * 62.4 = 44.3 lb/ft
3
∴ Volume flow rate of Naphtha = 60125 / 44.3 = 1357.22 ft
3
/hr
∴ Volume flow rate of C
5+
= 0.82 * 1357.22 = 1112.92 ft
3
/hr
At t
mean
= 104 f
°
,and 45
°
API:
∴ ρ
C5+
= 0.787 * 62.4 = 49.11 lb/ft
3
∴ Mass flow rate of C
5+
= 49.11 * 1112.92 = 54655.5 lb/hr
∴ Mass flow rate of (C
1
+ C
2
) = 0.0225 * 60125 = 1352.81 lb/hr
∴ Mass flow rate of C
3
= 0.03 * 60125 = 1803.75 lb/hr
∴ Mass flow rate of H
2
= 0.028 * 60125 = 1683.5 lb/hr
Ch.8 Design
124
∴ Mass flow rate of C
4
=
60125 – (54655.5+1352.81+1803.75+1683.5) =629.44 lb/hr
Assume recycle ratio of H
2
= 8000 Scf /bbl
= 0.00151 lb H
2
/lb Naphtha
∴ Mass flow rate of recycled H
2
= 60125 * 0.00151 = 90.79
lb/hr
∴ Mass flow rate of total H
2
= 1683.5 + 90.79 = 1774.29
lb/hr
Material balance on flash drum:-
1352.81 lb/hr C1-C2
629.44 lb/hr C
4
54655.5 lb/hr C
5+
1774.29 lb/hr H
2
1803.75 lb/hr C
3
90.79 lb/hr recycle H
2
75.16 lb/hr C
1-
C
2
1683.5 lb/hr net H
2
1277.65 lb/hr C
1
-C
2
54655.5 lb/hr C
5+
1803.75 lb/hr C
3
629.44 lb/hr C
4
CATALYTIC REFORMING
125
Material balance on stabilizer:-
1803.75 lb/hr C
3
629.44 lb/hr C
4
54655.5 lb/hr C
5+
629.44 lb/hr C
4
1803.75 lb/hr C
3
54655.5 lb/hr C
5+
Ch.8 Design
126
CATALYTIC REFORMING
127
Shell and tube exchangers:
Heat Exchanger:
Heat exchangers are devices build for efficient heat transfer
from one fluid to another .they are used widely in refinery
industry to cooled products or preheat feed.
Role of heat exchanger in chemical processing:
Heat or cool a stream flowing from item of equipment to
another. The stream may be:
-A liquid.
-A gas.
-A multiphase mixture.
To vaporize a liquid stream.
To condense a vapor stream.
Types of heat exchangers:
1-parallel flow heat exchanger:
In this type of heat exchanger the two fluids flow in the same
direction .If we assume that specific heat capacity is constant ,so
A.Counter flow heat exchanger:
In counter-flow heat exchanger fluids flow in opposite direction.
Ch.8 Design
128
So rate of heat transfer between two fluids will be
dQ/dT= U*A*dT
lm
where:
U : overall heat transfer coefficient.
A : area of tubes
dT
lm
= (dt
1
-dt
2
)/Ln (dt
1
/dt
2
).
B.Cross flow heat exchanger:
In it the direction of fluids are perpendicular to each other .the
required surface area for this heat exchanger is calculated from
tables it's between surface area for counter flow and parallel
flow.
Preparation of design heat exchanger:
1. A phase change involved in the system: A quick look
at the boiling points compared with the entrance and exit
temperatures.
2. The flow rates and operating pressures:
This information is critical in establishing the mass and energy
balance around the exchanger. Operating pressures are
particularly important for gases as their physical properties vary
greatly with pressure.
3. The physical properties of the streams involved:
you should get the physical properties for each zone separately
to ensure accuracy, but in some cases it is acceptable to use an
average value. Physical properties that you will want to collect
for each phase of each stream will include: heat capacity,
viscosity, thermal conductivity, density, and latent heat (for
phase changes). These are in addition to the boiling points of
the streams at their respective pressures.
CATALYTIC REFORMING
129
4. The allowable pressure drops and velocities in the
exchanger:
Pressure drops are very important in exchanger design
(especially for gases). As the pressure drops, so does viscosity
and the fluids ability to transfer heat. Therefore, the pressure
drop and velocities must be limited.
The velocity is directly proportional to the heat transfer
coefficient which is motivation to keep it high, while erosion
and material limits are motivation to keep the velocity low.
Typical liquid velocities are (3-10 ft/s). Typical gas velocities
are (50-100 ft/s). Typical pressure drops are (5-8 psi) on the
tube side and (3-5 psi) on the shell side.
5. The Heat duty of the system:
This can be calculated by a simple energy balance from one
of the streams.
6. The Area of the exchanger:
These can be found in most textbooks dedicated to the subject.
Once you've estimated the overall heat transfer coefficient, use
the equation Q=U A dT
lm
to get your preliminary area estimate.
7. Prepare layout for my exchanger:
selecting a shell diameter, tube sheet layout, baffle and tube
spacing, then check your velocity and pressure drop
requirements to see if they're being met. Some guidelines may
be as follows: 3/4 in. and 1.0 in. diameter tubes are the most
popular and smaller sizes should only be used for exchangers
needing less than 30 m
2
of area. If your pressure drop
requirements are low, avoid using four or more tube passes as
this will drastically increase your pressure drop.
Ch.8 Design
130
Other Considerations:
 Materials of Construction
 Ease of Maintenance
 Cost of Exchanger
 Overall Heat Integration
The tubular element:
The full filament of many industrial services requires the use of
large number of double pipe hairpins (double pipe heat
exchangers).
Double pipe exchanger:
Heaters are used primarily to heat process fluid; steam is usually
employed for this purpose, although in oil refineries hot
recalculated oil serves the same purpose.
- Water is the main cooling medium.
- The principal parts are two sets of concentric pipes, two
connecting, tees and a return head and a return bend.
-The inner pipe is supported within the outer pipe by packing
glands.
-The return bends which is usually exposed and does not
provide effective - heat transfer surface - Hairpins are useful as
inexpensive heat - transfer surface.
Double pipe exchanger fittings:
Outer pipe , IPS Inner pipe , IP
2 1
1
/
2
2
1
/
2
1
1/4
3 2
4 3
- Double pipe exchangers are usually assembled in 12 , 15 or
20ft effective length .
CATALYTIC REFORMING
131
- The use of a large number of double pipe hairpins consumes I
considerable ground area and also entail a large number of
points at which leakage may occur.
- They can best be obtained by means of shell and tube
equipment.
- Shell and tube equipment involves expanding a tube into a
tube sheet and forming a seal which does not leak under
reasonable conditions.
- In some industrial uses it is desirable to install tubes in a tube
sheet so that they can be removed easily.
-The tubes actually packed in the tube sheet by means of
ferrules using a soft metal packing ring.
Heat exchanger tubes:
The outside diameter of heat exchanger or condenser tubes is the
actual outside diameter in inches with in a very strict tolerance.
- Heat exchanger tubes are available in a verity of metals
which include steel, copper, admiralty, brass, 70 – 30 copper
- nickel, aluminum bronze, aluminum, and the stainless
steels.
- They are obtainable in a number of different wall thickness
defined by Birmingham wire gage, which is usually referred
to as BWG or gage of the tube. The most common diameters
arc % and 1 inch O.D.
Tube pitch:
Tube holes can not be drilled very close together, the shortest
distance between two adjacent tube holes is the' clearance or
ligament, and these are now fairly standard. I1 Tubes are laid
out on cither square or triangular pattern
Ch.8 Design
132
Shells:
Shells are fabricated from steel pipe with nominal IPS diameters
up to 12 in above 12 in the actual outside diameter and the
nominal pipe diameter are the same.
The standard wall thickness for shells with inside diameters
from 12 to 24 inch inclusive is 3/8 inch , which is satisfactory
for shell-side operating pressure up to 300 psi.
Baffles:
It is apparent that higher heat - transfer coefficients result when
a liquid is maintained in a state of turbulence to include
turbulence outside the tube it's customary to employ baffles
which cause the liquid to how through the shell at right angles o
the axes of the lubes. The center - to - center distance between
baffles is called balled pitch or baffle spacing.
CATALYTIC REFORMING
133
Heat exchanger design:
Choosing heat exchanger which used to exchange heat between
the hot vapor from third reactor and naphtha feed need to
preheated before enter the furnace.
Data given:
Hot fluid: Vapor from 3
rd
reactor
m
vapor
= 60290 lb/hr
T
1
=550 ˚f
T
2
=250 ˚f
Cold fluid: Naphtha feed
m
naphtha
= 60125 lb/hr
t
1
=100˚f
Design Steps:
Step (1): Heat duty of heat exchanger.
For hot vapors:
1. T
mean
= (550+250)/2 = 400 ˚f & API= 61.8˚
2. from kern book find physical properties of hot fluid:
a- From fig.(5) C
P
= 0.545 Btu/lb.˚ f
b- From Fig.(1) K= 0.082 Btu/hr.ft.˚f
c- From fig.(14) μ = 0.14*2.42=0.3388 lb/hr.ft
d- From fig.(6) Sp.gr= 0.57
3. Assume 85% of hot vapor amount used to heat naphtha and
15% used to heat recycle H
2
in separated heat exchanger
So M
1
= 0.85*60290 = 51246.5 lb/hr
Ch.8 Design
134
4. Heat duty Q Btu/hr:
Q = M
1
C
P
(T
1
- T
2
)
= 51246.5*0.545*(550-250)
= 8378802.75 Btu/hr
Step (2): Outlet temperature of naphtha feed
t
2
=? ˚f
for cold fluid :
m
cold
= 60125 lb/hr
t
1
=100˚f t
2
= ? ˚f
Q
constant
= m
cold
Cp
c
(t
2
-100)
8378802.75=60125 Cp
c
(t
2
-100)
139.356= Cp
c
(t
2
-100)
Assume t
2
˚f T
mean
˚f Cp
c
Btu\lb.˚ f Y=139.356
300 200 0.586 116.6
350 225 0.602 150.5
330 215 0.593 136.39
335 217.5 0.595 139.4 ≈ y
So t
2correct
=335˚f and t
mean
= 217.5 ˚f , API=61.8˚
From Kern Book:
 Cpc=0.595 Btu\lb.˚ f
CATALYTIC REFORMING
135
 Kc= 0.087 Btu\hr.ft.˚f
 μ c=0.31*2.42=0.7502 lb\ft.hr
 Sp.gr= 0.653
Step (3): L.M.T.D:
Use counter-flow heat exchanger which fluids flow in opposite
direction.
So rate of heat transfer between two fluids will be
Hot: T1=550˚f T2=250˚f
Cold: t1=100 ˚f t2=335˚f
∆T1=215˚f ∆T2=150 ˚f
LMTD =(215-150)/ln (215/150)
=180.55˚f
Correction factor for ∆Tlm:
Ch.8 Design
136
A- Capacity rate ratio:
P = (335-100)/(550-100)
= 0.52
B- The cold-side effectiveness:
R = (550-250)/(355-100)
= 1.1765
From fig. (10-34)A [1shell pass and 2 or more tube passes]
We found f=0.9
LMTD
corrected
= 0.9*180.55=162.5 ˚f
Step (4): Assuming overall heat transfer
coefficient U Btu/ft
2
.˚f.hr
From table (10-17)
U Range= (40-75) Btu/ft
2
.˚f.hr
Assume U=57 Btu/ft
2
.˚f.hr
Step (5): Area calculation
A= Q /U*∆T
lm
CATALYTIC REFORMING
137
A
cal
= 8378802.75 / (57*162.5) = 904.6 ft
2
Step (6): Heat exchanger layout
Using floating head heat exchanger for expansion
and [ 1"O.D , 1.25" P , ∆BWG14, L=16 ft ]
1. Number of tubes required N
tubes
:
N
tubes
=A/ (L-0.5)*a
i
a
i
: area of tubes per ft of length ft
2
/ft
N
tubes
= 904.594/ (16-0.5)*0.2618 = 222.92 ≈ 223 tubes
2. Actual no of tubes N
t
:
From table (10-10)E
Choosing 4 passes, N
tubes
= 242 tube, ID
S
=24 in
,N
tubes/pass
=242/4 = 60.5 ≈ 61 tubes
Step (7): Velocity inside tubes
Choosing naphtha feed (cold fluid) inside tubes
V= W(lb/hr) /3600*Sp.gr*62.4*N
tubes/pass
*0.00379
Ch.8 Design
138
= 60125/3600*0.653*62.4*61*0.00379
= 1.79 ft/sec < 3 ft/sec
(1) Increase no of passes to 6 passes
From table N
tubes
=232 tubes ,N
tubes/pass
=232/6=38.6=39 tubes
V=2.81 ft/sec < 3 ft/sec
(2) Increase no of passes to 8 passes
From table at N
tubes
=228 tubes, N
tubes/pass
= 228/8=28.5=29 tubes
V= 3.79 ft/sec ≈ 3.8 ft/sec
Check: V in range (3-6) ft/sec ok
Choose : N
tubes
=228 tubes N
tubes/pass
= 29 tubes,
No of passes =8 ID
s
=24 in
Step (8): Tubes side film coefficient (h
io
):
1- a
t
= N
tubes/pass
* cross section area of tubes(ft
2
)
= 29*0.00379
= 0.1099≈ 0.11 ft
2
2- G
t
= 60125/0.1099
= 547038.486 lb/ft2.hr
3- Re =G
t
*D
i

c
=547038.486*0.0965/0.7502
=50692.23
4- L/D
i
=16/0.069=230
5- from fig(10-46) by Re, L/D
i
J
H
=160
6- h
i
= J
H
*(K/D
i
)*(µ*C
p
/K)
1/3
CATALYTIC REFORMING
139
= 160*(0.087/0.0695)*(0.7502*0.595/0.087)
1/3
= 345.4 Btu/ft
2
.˚f.hr
7- h
io
= 345.4*(0.834/1)
=288.076 Btu/ft
2
.˚f.hr
Step (9): Shell side film coefficient (ho):
1- assume baffle spacing B= 24 in its range(24"-2")
2- a
s
= ID*C*B/144*P , C=0.25 in, P=1.25 in
= 24*0.25*24/144*1.25
= 0.8 ft
2
3- Gs =51246.5/0.8
= 64058.125 lb/ft2.hr
4- Re = G
s
*D
e

h
= 64058.125*0.06/0.3388
= 11337.72
5- From fig. (10-54) by Re, baffle cut Δ ,25%
J
H
= 57
6- h
o
= J
H
*(K/D
e
)*(µ
h
*C
p
/K)
1/3
= 57*(0.082/0.06)*(0.3388*0.545/0.082)
1/3
= 102.1 Btu/ft
2
.˚f.hr
Step (10): Fouling resistance R
o
,R
i
R
i
=reformer charge = 0.0015 from table (10-12)
Ch.8 Design
140
R
o
=reformer effluent = 0.0015
Step (11): Calculation of overall heat transfer
coefficient U Btu\ft
2
.˚f.hr
(1/u) = (1/hio)+(1/ho)+Ri+Ro
=(1/288.076)+(1/102.1)+0.0015+0.0015
U = 61.48 Btu/ft
2
.˚f.hr > U assume =57 Btu/ft
2
.˚f.hr so ok
Step (12): Area required and Area available
A-Area required:
A
req
=Q/U*∆T
lm
=8378802.75/ (61.48*162.5)
= 838.7 ft
2
B- Area available:
A
av
=N
t
*(L-0.5)*0.2618
= 228*15.5*0.618
= 925.2 ft
2
C- Check: Excess Area % = [(Aav- Areq)/ Areq]*100
= [(925.2-838.7)/838.7]*100
= 10.3% ok in range (10-25%)
Step (13): Pressure drop
A-Pressure drop in Shell side:
1- φ
s
is neglect
CATALYTIC REFORMING
141
2- Ns+1=L/B =16*12/24=8
3- from fig. (10-140) at Δ ,25% and Re=11337.72
f=0.00251
4- D
S
=ID=24 in ,De=0.06 ft
0.00251*(64058.125)
2
*24*8
5-Δ P
s
=
5.22*10
10
*0.06*12*0.57
= 0.09231≈ 0.1 psi < 5 psi ok
B- Pressure drop in tubes side:
Δ P
tubes
=Δ P
t
+Δ P
r
f *Gt
2
*L*N
passes
[1] Δ P
t
=
5.22*10
10
*D
i
*S
a- N
passes
=8 pass ,L=16 ft
D
i
=0.0695 ft, S=0.653
b- from fig (10-138) at Re=50692.23
f=0.00017
0.00017*(547038.486)
2
*16*8
Δ P
t
=
5.22*10
10
*0.0695*0.653
= 2.7486 ≈ 2.75 psi
Ch.8 Design
142
[2] End Return Losses(Δ P
r
):
a- from fig.(10-139) by V=3.8 ft/sec , Sp.gr=0.653
Δ p
r
(fig) = 0.6 psi
b- Δ P
r
= Δ p
r
(fig)* no of passes
= 0.6*8
= 4.8 psi
Δ P
tubes =
Δ P
t
+Δ P
r
= 2.75+4.8 = 7.55 psi < 10 psi check is o.k.
CATALYTIC REFORMING
143
Ch.8 Design
144
FURNACE DESIGN
A fired heater is necessary for heating the feed to the desired
temperature (Process temperature). This heating is made by
burning the fuel and use the heat liberated from this operation to
heat the feed to the wanted temperature.
In the study of furnace we will choose some items help in
knowledge of its performance, and these are as follow:
1- Furnace start up
2- Heat transfer and combustion
3- Furnace equipment
First: furnace start up
This is made by 5 steps
1- Inspection: the pilots inspect the furnace before it starts so as
to ensure its stable performance
2-purging the furnace
3- Lighting pilots: protection of pilots by wearing the safety
clothes while working
4- Lighting furnace: slowly open the gas valve then start lighting
procedure
5- Normal operations
Second: heat transfer and combustion
- Heat transfer:
Heat is produced by the combustion of fuel in the burners, this
heat is circulated around the tube of the furnace (in which the
liquid exists) in heater.
Heat transfer has two methods in furnace Radiation &
Convection
In radiation section: heat is transferred to the tubes (Radiant
tubes) by radiation
In convection section: flue gases carry heat to the tubes
(convection tubes), and this increase furnace efficiency by
allowing more heat to be used before it leaves through the stack
CATALYTIC REFORMING
145
-Combustion:
To make the combustion there must be three factors present in
the same time fuel + air + ignition source
fuel: it could be natural gas or fuel oil ( mazot ) or both , but in
industry we prefer natural gas as it has some advantage like
- More cleaner
- Gives a more amount of heat
- Less expensive
- Don't cause problems with environmental laws
* Air: in furnace we use air with specified ration to fuel and it is
as follow
20 % excess air in case of natural gas
25 % in case of mazot
air is used to give the Oxygen necessary for complete
combustion because incomplete combustion doesn't make the
best benefit of fuel heat it also produces Co which cause
conflicts with environmental laws , incomplete combustion also
leaves some fuel in furnace which accumulated causing bad
furnace performance .
Air also is used to keep the flame temperature in its range
because if it increased it causes No
x
production which causes
cancer.
As air help in complete combustion it helps in utilizing the
maximum amount of heat in the fuel.
Third: furnace equipment
1- Radiant tubes: in which the fluid pass in the radiation section
.
2- Fire box: it produces the flames to heat the fluid
Ch.8 Design
146
Note that: the flame doesn't touch the tube this is called flame
impingement it destroys the tubes, and doesn't permit any air to
enter the combustion zone
3- A covering material covers the floor and walls of the furnace
this material:
- reduces heat losses
- reflects heat back into the tubes
4- Chock bank: bank of tubes between convection section and
radiation section. These tubes rows are usually being subjected
to the highest heat-transfer rates in the fired heater, so they are
termed as (shield), or (shock) tubes
5- Convection section
6- Draft: for the pass of flame gases organizing
7- Damper: control the flow of hot gases out of the furnace
8- Burner: it mixes fuel with air in a
manner to keep stable combustion and it
differs according to the fuel type.
Classification of furnce:-
The principal classification of fired heaters relates to the
orientation of the heating coil in the radiant section, whether
the tubes are vertical or horizontal.
Types of vertical fired heaters:-
1-Vertical-cylindrical, all radiant:
Here the tube coil is placed vertically along the walls of the
combustion chamber. Firing is also vertical, from the floor of
the heater.
Properties:-
1-heaters of this type represent a low-cost.
2-low efficiency design.
3- it requires a minimum of plot area .
4-typical duties are 0.5 to 20 million Btu/hr.
CATALYTIC REFORMING
147
2-Vertical-cylindrical, helical coil:
The coil is arranged helically along the walls of the combustion
chamber, and firing is vertical from the floor.
Properties:
1-This design also represents low cost.
2- Low efficiency.
3-requires a minimum of plot area.
4-one limitation on these units is that generally only one flow
path is followed by the process fluid.
5-heating duties run from 0.5 to 20 million Btu/hr.
3-Vertical-cylindrical, with cross flow convection:
These heaters, also fired vertically from the floor, feature
both radiant and convection sections. The radiant-section
tube coil is disposed in a vertical arrangement along the
walls of the combustion chamber.The convection section
tube coil is arranged as a horizontal bank of tubes
positioned above the combustion chamber. This
configuration provides an economical, high-efficiency
design that requires a minimum of plot area. Typical duties
are 10 to 200 million Btu/hr.
So we will include vertical furnace design in our study.
4- Vertical-cylindrical, with integral convection:
Although this design is rarely chosen for new installations, the
vast number of existing units of this type warrants its mention in
any review of fired heaters.
This design is likewise vertically fired from the floor, with its
tube coil installed in a vertical arrangement along the walls. The
distinguishing feature of this type is the use of added surface
area on the upper reaches of each tube to promote convection
heating. This surface area extends into the annular space formed
between the convection coil and a central baffle sleeve. Medium
Ch.8 Design
148
efficiency can be achieved with a minimum of plot area. Typical
duties are 10 to 100 million Btu/hr.
5- Arbor or wicket:
The radiant heating surface is provided by U-tubes connecting
the inlet and outlet terminal manifolds. This type is especially
suited for heating large flows of gas under conditions of low
pressure drop. Typical applications are found in petroleum
refining, where this design is often employed in the catalytic-
reformer charge heater, and in various reheat services. Firing
modes are usually vertical from the floor, or horizontal between
the riser portions of the U-tubes.
In addition, a cross flow convection section is normally installed
to provide supplementary heating capacity for chores such as
stream generation. Typical duties for each arbor coil of this
design are about 50 to 100 million Btu\hr.
6- Vertical-tube, double fired:
Vertical radiant tubes are arranged in a single row in each
combustion cell (there are often two cells) and are fired from
both sides of the row. Such an arrangement yields a highly
uniform distribution of heat-transfer rates (heat flux) about the
tube circumference.
Another variation of these heaters uses multilevel side-wall
fired, which gives maximum control of the heat-flux profile
along the length of the tubes. Multilevel side-wall fired unites
are often employed in fired-reactor services and in critical
reactor-feed heating services.
Single-cell models are available for smaller duties. As a group,
these represent the most-expensive fired heater configuration.
The typical duty range for each cell runs from about 20 to 125
million Btu/hr.
CATALYTIC REFORMING
149
Types of horizontal fired heaters:-
1- Horizontal tube cabin:
The radiant-section tube coils of these heaters are arranged
horizontally so as to line the sidewalls of the combustion
chamber and the sloping roof or "hip." .the convection-section
tube coil is positioned as a horizontal bank of tubes above the
combustion chamber. Normally the tubes are fired vertically
from the floor, but they can also be horizontally fired by
sidewall-mounted burners located below the tube coil.
This economical, high-efficiency design currently represents the
majority of new, horizontal-tube, fired-heater installations.
Duties run 10 to 100 million Btu/hr.
2- Two-cell horizontal tube box:
Here the radiant section tube coil is deployed in a horizontal
arrangement along the sidewalls and roof of the two combustion
chambers. The convection section tube coil is arranged as a
horizontal bank of tubes positioned between the combustion
chambers. Vertically fired from the floor, this is again an
economical, high-efficiency design. Typical duties range from
100 to 250 million Btu/hr. for increased capacity, the basic
concept can be expanded to include three or four radiant
chambers.
3- horizontal tube-cabin with dividing bridge wall:
The radiant-section tube coil is arranged horizontally along the
sidewalls of the combustion chamber, and along the hip. The
convection-section tube coil takes the form of a horizontal bank
of tubes positioned above the combustion chamber. A dividing
bridge wall between the cells allows for individual firing control
over each cell in the combustion chamber. Available options
permit horizontal firing with sidewall-mounted burners or
Ch.8 Design
150
vertical firing from the floor along both sides of the bridge wall.
A typical duty range for this design is 20 to 100 million Btu/hr.
4- End-fired horizontal tube box:
The radiant-section tube coil is disposed in a horizontal
arrangement along the sidewalls and roof of the combustion
chamber. The convection-section tube coil is arranged as a
horizontal bank of tubes positioned above the combustion
chamber. These furnaces are horizontally fired by burners
mounted in the end walls. A typical duty range for this design is
5 to 50 million Btu/hr.
5- End-fired horizontal tube box with side-mounted
convection section:
Here the radiant section tube coil is disposed in a horizontal
arrangement along the sidewalls and roof of the combustion
chamber. The convection-section coil is arranged as a horizontal
bank of tubes positioned along side the chamber. The unit is
horizontally fired from burners mounted on the end wall.
These furnaces are found in many older installations, and
occasionally in new facilities that burn particularly poor grades
of fuel oil containing a high ash concentration. This relatively
expensive design provides duties ranging from 50 to 200 million
Btu/hr.
6- horizontal-tube, double-fired:
Horizontal radiant tubes arranged in a single row and are fired
from both sides to achieve a uniform distribution of heat-
transfer rates around the tube circumference. Such heaters are
normally fired vertically from the floor. They are often selected
for critical reactor-feed heating services. For increased capacity,
the concept can be expanded to provide for a dual combustion
chamber. A typical duty range for each cell of this design is
about 20 to 50 million Btu/hr.
CATALYTIC REFORMING
151
In industry we prefer the vertical furnace as it has some
advantage than the horizontal.
Which are:
- Little space used
- Easy maintenance
- Less expensive
- Better draft
Data given:-
Fluid:-
Heavy sweet naphtha, 61.8

API, Flow rate (G
naphtha
) = 60125
lb/hr,
Boiling range (171-400 F

)
Recycle H
2
, Flow rate (G
H2
) = 90.79 lb/hr
Recycle (C
1
–C
2
), Flow rate (G
(C1-C2)
) =75.16
lb/hr
[Total flow rate= 60290.95
lb/hr]
Inlet temperature (t
1
) = 871 F

Outlet temperature (t
2
) =1010 F
°
Fuel gas, LHV=19700 Btu/lb
Ch.8 Design
152
Design basis:-
Vertical –cylindrical heater with horizontal –tube convection
section.
Excess air, 15%
Average radiant rate, 10000 Btu/hr ft
2
Design steps:-
Step 1:- Efficiency
1- FGT= 871 + 150 =1021 F

[>400 F°] O.K.
2- From fig. (3) Berman:
By excess air =15 %, and FGT = 1021 F°
Ha, FGT = 14733.33 Btu/lb
3- % heat extracted = (14733.33 / 19700) * 100 =74.788%
4- Calculated efficiency = 74.788 - 2
CATALYTIC REFORMING
153
ξ =72.788%
5- At (t
m
= (871 + 1010) / 2 = 940.5 F°) of fluid and 61.8 API
from Kern obtain its physical properties:-
Cp
naphtha
= 0.765 Btu/lb F°,Cp
H2
= 3.5 ,Cp
(C1-C2)
= 0.85
6- Q duty = [60125 * 0.765 + 90.79 * 3.5 + 75.16 * 0.85] *
[1010 - 871]
= 6446441.364 Btu/hr
7- Heat fired = 6446441.364 / 0.72788 = 8856461.73 Btu/hr
8- Fuel consumed = 8856461.73 / 19700 = 449.567 lb/hr
9- from fig. (2) Berman:
By excess air =15%, L.H.V=1000 Btu/ft
3
Flue gas / fuel ratio =19.0625 lb-flue/lb-fuel
10-flue- gas flow = 449.567 * 19.0625= 8569.863 lb/hr
Step 2:- Radiant /convection duty split
1-select tube coil having 3 passes of 4 in IPS Sched. 40
[4.5 in O.D. * 0.237 in avg. wall]
2- Fluid mass velocity=
(60125 + 90.79 + 75.16) / (3600 * 3 * 0.0884) = 63.15 lb/s ft
2
O.k. in the range [45-70 lb/s/ft
2
]
Radiation
T
2
T
1
F.G.T
Ch.8 Design
154
3-fluid temperature at radiant inlet (t
c
)=
12
5
1010
871
=
÷
÷
c
c
t
t
t
c
= 911.88 F°
Assume fluid temperature at radiant inlet = 915 F°
4-radiant section average fluid temperature:
° =
+
= F t
B
5 . 962
2
915 1010
5- Radiant section average tube metal temperature:
t
m
= 962.5 + 75 = 1037.5 F°
6- Bridge wall temperature (Bwt)
From fig. (6a) Berman by
t
m
= 1037.5 F°and aveg. Radiant rate (q
r
) =10000 Btu/ft
2
hr
Bwt =1658.76 F
1010F° 915F° 900F° 871F°
t
flame
1021F°
1658.76F° 1448.76F°
7- from fig. (3) Berman:
By excess air=15% and Bwt=1658.76 F°
H
a
,Bwt = 10790 Btu/lb
Q
R
=(10790 / 14733.33) * 6446441.364 = 4721071.361 Btu/hr
Q
c
= 6446441.364 - 4721071.361 = 1725370 Btu/hr
Step 3:- Furnace layout
1- A
R
= (4721071.361 / 10000) = 472.11 ft
2
2- Assume 24 radiant tubes on 8 in center
3- Tube circle diameter (TCD) =(24* 8) / (12*π ) = 5.093 ft
shield radiation convection
Fluid
Flue gas
CATALYTIC REFORMING
155
4- ETL
shield bank
= 5.093 – 1 = 4.093 ft ≃ 4.1 ft
5- With 6 tubes per row on 8 in center
6- Shield bank free area = 6* 4.1* ((8 - 4.5) / 12) = 7.175 ft
2
7- g
flue gas
= 8569.863 / (3600 * 7.175) = 0.332 lb/s/ft
2
8-surface area of one shield row = 6 * 4.1 * π * (4.5 / 12) =
28.981 ft
2
9- Vertical tube radiant surface area= 472.11-28.981
= 443.129 ft
2
10-vertical tube radiant length= (443.129 * 12) / (24* π * 4.5)
vertical tube radiant length = 15.672 ft
11-check for L/D ratio = 15.672 / 5.093 = 3.08
O.k. in the range [2-4]
4.093 ft
5.093 ft
Ch.8 Design
156
1658.76
Step 4:- Shield bank
1- average fluid temperature in shield bank=(915 + 900) / 2
=907.5 F°
2-
° =
÷
= A F
Ln
T
lm
53 . 640
)
26 . 541
26 . 751
(
26 . 541 26 . 751
3-T
ga
= ((1658.76 + 1448.76) / 2) + 460 = 2013.76 R°
1448.76
907.5
∆T
min
=541.26
∆T
max
=751.26
4-
hr F ft
Btu
h
c
°
= =
2 4 . 0
28 . 0 6 . 0
0925 . 5
) 5 . 4 (
) 76 . 2013 ( * ) 332 . 0 ( * 14 . 2
5-h
rg
= 0.0025* (2013.76 - 460) - 0.5 = 3.3844 Btu/ft
2
F°hr
6- h
0
=1.1 * (5.0925 + 3.3844) = 9.3246 Btu/ft
2
F°hr
Flue gas
fluid
907.5
CATALYTIC REFORMING
157
7-determine physical properties of fluid at t
avg.
= 907.5 F°
Cp
mix
= 0.754 Btu/lb F°
K
mix
= 0.07 Btu/ft
2
F°hr
M
mix
= 2.42 * 0.03 = 0.0726 lb/ft hr
8- Re = (63.15 * 4.5 * 3600) / (0.0726 * 12) = 1174276.86
P
r
= (0.754 * 0.0726) / 0.07 = 0.782
hr F ft
Btu
h
h
i
i
°
=
=
2
333 . 0 8 . 0
185 . 333
5 . 4
07 . 0 * 12
* ) 782 . 0 ( * ) 86 . 1174276 ( * 027 . 0
9- h
w
= 324 / 0.237 = 1367 Btu/ft
2
F°hr
10- R
i
= (4.5 / 4.026) * (1 / 333.185) = 0.00335
R
0
= 1 / 9.3246= 0.1072
R
w
= (4.5 / 4.026) * (1 / 1367) = 0.000818
R
t
= 0.00335 + 0.1072 + 0.000818 = 0.1114
U
shield
= 1 / 0.1114 = 8.975 Btu/ft
2
F°hr
11- A
sh
= 3 * 28.981 = 86.943 ft
2
12- Q
shield
= 8.975 * 86.943 * 640.53 = 499814.158 Btu/hr
13- Check of flue gas temperature above shield bank
H
a
,
shield
= [(4721071.361 + 499814.158) / 4721071.361] * 10790
= 11932.324 Btu/lb
By H
a,shield
=11932.324 Btu/lb and excess air=15%
From fig.(3) Berman
T
sh
=1475 F°
O.k. ≃ (BWT - 210) = 1448.76 F°
Ch.8 Design
158
1448.76
∆T
max
=548.76
Step 5:- convection section
1-Q'
c pure
=1725370 - 499814.158 = 1225555.842 Btu/hr
2-
° =
÷
= A F T
lm
44 . 307
150
76 . 548
ln
150 76 . 548
3-try 3 fins/in with each 3/4in high
*0.05in thick (A
t
=7.33 ft
2
/ft)
1021
871
∆T
min
=150
4-fin bank free area
=
2
7138 . 6
12
3 * 75 . 0 * 05 . 0 * 2
12
5 . 4 8
* 1 . 4 * 6 ft =
(
¸
(

¸

÷
÷
5-G
flue gas
= 8569.863 / 6.7138=1276.464 lb/ft
2
hr
6- Determine physical properties of flue gas at
T
avg.
=(1448.76 + 1021) / 2= 1234.88 F°
M= 0.1 lb/ft hr, Cp= 0.268 Btu/lb F°, K= 0.037 Btu/ftF°hr
7-Re= (1276.464 * 4.5) / (12 * 0.1) = 4786.74
8- From fig. (7) by Re= 4786.74
J= 0.013
Flue gas
fluid
900
CATALYTIC REFORMING
159
9-
hr F ft
Btu
h
°
=
|
.
|

\
|
=
2
3
2 0
578 . 5
037 . 0
268 . 0 * 1 . 0
464 . 1276 * 268 . 0 * 013 . 0
10-From fig. (8) by KT= 1.35 ,H= 0.75 in and h
0
= 5.578
Btu/ft
2
F°hr
ξ
fin
= 84%
11- h
o(eff.)
=
)
12
5 . 4
)
12
5 . 4
33 . 7 ( 84 . 0 (
33 . 7
578 . 5 × H
+
× H
÷ × ×

h
o(eff.)
= 4.829
hr F ft
Btu
O 2
12- R
o
= (1 / 4.829) = 0.2071
R
i
= (7.33 / 1.054) * (1 / 333.185) = 0.02087
R
w
= (7.33 / 1.054) * (1 / 1367) = 0.005087

R
t
= 0.2071 + 0.02087 + 0.005087 = 0.23305

U
conv.
= (1 / 0.23305) = 4.291
hr F ft
Btu
O 2
13- A
conv.
=
2
0056 . 929
44 . 307 291 . 4
842 . 1225555
ft =
×
14- Surface area per convection row = 6 * 4.1 * 7.33 = 180.318
ft
2
Ch.8 Design
160
15- Number of finned rows = (929.0056 / 180.318) = 5.15

Number of finned rows = 6 rows
Step 6 :- Stack design:
Size stack for mass velocity of 0.8
2
sft
Lb
at 125% of design gas
flow
Cross-sectional area =
2
72 . 3
8 . 0 3600
863 . 8569 25 . 1
ft =
×
×
∴ Stack diameter (D) =
ft 176 . 2
72 . 3 * 4
=
H
Assume average gas temperature in stack = 1021 – 75 = 946 f
°
Assume stack-exit gas temperature = 871 f
°
Draft under arch = 0.05 in
At t
avg.
= 1553.76 f
°
in shield-bank of flue gas,
∴ ρ
flue
=0.007 lb/ft
3
Shield-bank loss = 3 * 0.2 * 0.003 * (1.2 * 0.332)
2
* (0.33
/0.007)
∴ Shield-bank loss = 0.0147 in
At t
avg.
=1234.88 f
°
in convection of flue gas,
∴ ρ
flue
= 0.0088 lb/ft
3
Fin-bank loss = 6 * 1* 0.003 * (1.25 * (1276.464/3600) )
2
*
(1276.464/(3600*0.0088) ) = 0.14247 in
At t
avg.
= 946 f
°
in stack of flue gas,
∴ ρ
flue
= 0.025 lb/ft
3
CATALYTIC REFORMING
161
Stack-entrance loss = 0.5 * 0.003 * (0.8)
2
* (0.8/0.025) =
0.03072 in
Damper loss = 1.5 * 0.003 * (0.8)
2
* (0.8/0.025) = 0.09216 in
At t
avg.
= 871 f
°
in stack exit of flue gas,
ρ
flue
= 0.03 lb/ft
3
Stack-exit loss = 1 * 0.003 * (0.8)
2
* (0.8/0.03) = 0.0512 in
Subtotal = 0.0147 + 0.14247 + 0.03072 + 0.09216 + 0.0512 +
0.05
Subtotal = 0.38125 in
Convection-section draft gain=
in 04145 . 0
9 . 1694
1
540
1
69 . 14 3 . 4 52 . 0 =
(
¸
(

¸

÷ × × ×
The required stack draft = 0.38125 – 0.04145 = 0.3398 in
Stack draft gain/ft
in 00871 . 0
1406
1
540
1
69 . 14 * * 1 * 52 . 0 =
(
¸
(

¸

÷ =
Stack fractional loss
in 00196 . 0
176 . 2 211000
1406 ) 8 . 0 (
2
=
×
×
=
Net stack effect/ft = 0.00871 – 0.00196 = 0.00675 in
Stack height required = (0.3398 / 0.00675) = 50.34 ft
Ch.8 Design
162
Step 7:- Fluid pressure drop:-
1- For ( Convection + Shield ) :-
N
passes,shield
= 6 / 3 = 2 passes
N
row
= 3 + 6 = 9 rows
L
e
= 2 * 9 * (4.1 + 1.5) + (2 * 9 – 1) * 50 * (4.026 / 12) =
385.975 ft
2- For ( Radiation ) :-
N
passes,rad.
= 24 / 3 = 8 passes
L
e
= (8 – 1) * 50 * (4.026 / 12) + 8 *15.672 = 242.8 ft
3- For ( Crossover ) :-
L
e
= 2 * 4.1 + 3* 30 * (4.026 / 12) = 38.395 ft
4- L
e,total
= 385.975 + 242.8 + 38.395 = 667.17 ft
5- By t
avg
= (871 + 1010) / 2 = 940.5 f
°
of fluid ,
sp.gr = 0.03, and µ= 0.0726 lb/ft hr
6-
364 . 1050586
0726 . 0 12
3600 15 . 63 026 . 4
Re =
×
× ×
=
7- f = (0.117 / (1050586.364)
0.25
) = 0.00365
8-
026 . 4 03 . 0 4 . 62
17 . 667 ) 15 . 63 ( 00365 . 0 00517 . 0
2
× ×
× × ×
= AP
∆P = 6.662 psi
9- ∆P
act.
= 1.25 * 6.662 = 8.33 psi
CATALYTIC REFORMING
163
Reactor Design
Ch.8 Design
164
r -
dX
C
F
V C
τ
A
o
o
o
X
0
A
A
A
A
A
p
}
= =
|
|
|
.
|

\
|
}
+
=
A
o
X
0
A
A
n
A A
1 - n
A ) X - (1
dX ) X (1
C k
1
Reactor Design
Assumptions to ease Design Procedure
1. The reactor is an ideal plug flow reactor.
2. The reactor is iso-thermal, as heat is constantly supplied.
3. The reactor is a one-phase reactor and neglecting the
presence of catalyst, for its very small and negligible
volume compared to the volume of voids.
4. Feed is pure ethyl cyclohexane with recycle hydrogen and
is only subjected to the dehydrogenation reaction due to
the high rate of this reaction and its high equilibrium state
which lead to that the reaction nearly goes to equilibrium
in the first reactor.
5. Optimum conversion is as high as 60%.
Derivation of the Plug-Flow Reactor Formula
Where;
C
Ao
= concentration at XA=0 (mol/m
3
).
V = volume of reactor without catalyst.
F
Ao
= molar flow rate in (mol/hr).
X
A
= conversion at the end of reactor.
-r
A
= rate of disappearance of reactant A
k = rate constant of dehydrogenation reaction. (50 hr
-1
)
CATALYTIC REFORMING
165
0 X
0 X 1 X
A
A A
V
V - V
=
= =
CH
2
- CH
3
CH
2
- CH
3
1 n
C k r
1
A A
=
= ÷
) X - 1 (
) X 1 ( ) X 1 (
C k
1
2
A
A A
0.6
0
A
p
0
o
A A

+ + ÷
=
(
¸
(

¸
+
= 1 -
) X - 1 (
1
k
1
2
A
A
o
o
o
o
A
A
A
A
p
C
F
) 1 ( 0.105 V
) 1 ( 0.105
F
V C
A
A

+ =
+ = =
n = order of reaction.
ε = fractional volume change =
+ 3 H
2
Then Performing the integration, and substituting with (n = 1)
Setting:
Conversion X
A
= 0.6 and
Rate constant k = 50 hr
-1
( Calculated Analytically )
………………. (*)
Ch.8 Design
166
A
798
30 x V
273 x 1000
22.4 x 1 x 221119 2
=
2
2 2
1
1 1
T
V P
T
V P
=
Data Given and Calculated
Naphtha Feed Mw. = 112 (C
8
H
16
)
Naphtha Density = 755 (56 °API)
Hydrogen recycle = 8000 scf H
2
/bbl naphtha
= 0.186 mol H
2
/kg naphtha
Naphtha Feed = 60,000 lb/hr = 18288.2 kg/hr
= 217717 mol/hr
Design Procedure
Recycle H
2
= 0.186 x 18288.2 = 3402 mol H
2
/hr
F
Ao
= 3402 + 217717 = 221119 mol/hr ………………….(1)
For basis of 1 hr, and isothermal reactor
n
XA=0
= 221119 mol
n
XA=1
= 3402 + 4 x 217717 = 874271 mol
221119
221119 - 874271
n
n - n
0 XA
0 XA 1 XA
A = =
=
= =

= 2.95 ………………………………………………(2)
* Volume at X
A
=0 (T=798 °K and P=30 atm)
CATALYTIC REFORMING
167
Hence, V = 482.61 m
3
Hence, C
Ao
= (221119/482.61) = 458 mol/m
3
……………(3)
From (1), (2), (3), I n (*)
V = 0.105 ( 1 + 2.95 ) ( 221119/458) = 200 m
3
Using the assumption of L = 3D for the reactor
200 m
3
= (3π /4) D
3
D = 4.3 m
L = 12.9 m
Notes
The reactor volume seems to be very large for :
 The massive flow rate of naphtha.
 The small assumed M.wt of 112 of naphtha feed that led to
the high no. of moles in the gaseous phase which led to the
high volume of feed.
If the presence of hydrogen in the feed is neglected, the volume
of the reactor would be 150 m
3
and ( D = 4 m , L = 12 m )
Ch.8 Design
168
CATALYTIC REFORMING
169
Tower design:
Design data:
Component Flow
rate
lb
mole
/hr
X
f
X
d
X
b
H
2
0.0462 0.0000743 0.0004125 0.000
C
1
16.910 0.02719 0.15098 0.000
C
2
36.108 0.05807 0.32293 0.000
C
3
40.904 0.06578 0.36521 0.000
i-C
4
4.164 0.0067 0.037179 0.000
n-C
4
6.650 0.01070 0.051817 0.000867
i-C
5
16.470 0.02648 0.04234 0.02269
n-C
5
11.060 0.01770 0.02966 0.01518
C
6
+
489.50 0.7872 0.000 0.96126
summation 621.81 1.000 1.000 1.000
Flow rate of naphtha = 621.81 Kg
mol
/ hr
Feed API = 50 ~ 53˚
Yield = 83% by vol.
Feed temperature =164
o
C.
Top temperature = 86
o
C .
Bottom temperature = 243
o
C.
Top pressure = 1 atm
Bottom pressure = 2 atm .
Ch.8 Design
170
Design steps :
Step (1)
F= 621.81 Kg
mol
/ hr.
Total Material Balance :-
F = D+B
Individual Material Balance on the component :-
FX
f
= DX
d
+ Bx
B
.
621.81 ( 0.0000743 ) = D ( 0.0004125) + 0
D= 112.00117 Kg
mol
/hr
B=509.8088 Kg
mol
/ hr.
Step(2):
Light key is ( n-C
4
).
Heavy key is (i-C
5
).
Feed enters at boiling point ;-
q = 1
Feed properties :
Composition
Boiling
Pt. (°F)
P
i
°
(psia)
Heat of
vaporization
KJ / Kg.
o
i
C
3
-43.474 1000 425.5 2.564
i-C
4
11.048 800 365.56 2.0513
n-C
4
31.352 650 385.79 1.667
i-C
5
82.4 390 342.1 1
n-C
5
97.16 290 357.1 0.744
C
6
+
244.04 50 292.6 0.1282
CATALYTIC REFORMING
171
By using underwood's shortcut method to calculate the
minimum reflux ( R
min.
)
1-q = E
R
min
+ 1 = E
Where :-
x
if
= The values for each component in the feed.
x
id
= The values for each component in the distillate.
o = the relative volatility of component (i) with
respect to the heavy key component.
q = the feed thermal condition .
u = the underwood's constant.
Solution :-
u =1.268
R
min
= 1.1
Calculation of the minimum number (N
min
) of
theoretical plates by the Fenske equation :-
X
dLk
X
bHk
log
X
dhk
X
bLk
N
min
=
o
Lk
log o
Hk
N
min
= 17.6
R
op
=1.2 R
min
, R
op
= 1.32
n
i=1
o
i
x
if
o
i
- u
n
i=1
o
i
x
id
o
i
- u
Ch.8 Design
172
To calculate theoretical number of plates :
By using Gilliland correlation relating number of
stages to reflux ratio :
Y= 0.608295-1.1893X+0.332227X
2
+0.532489X
3
-0.347484X
4
Where:
X=(R
opt
-R
min
)/ R
opt
= 0.16667
Y=(N
t
-N
min
)/(N
t
-1) = 0.4935
If take plate efficiency q =50%
N
theor
=18.2 plate .
N
act
= N
thoer
/ q = 18.2/ 0.5 = 36 trays
By Gilliland–Eduljee method :
Y= 0.75-0.75X
0.5663
= 0.4783
N
theor
=19.365 plate .
If take plate efficiency q =50%
N
act
= N
thoer
/ q = 19.365/ 0.5 =39.27= 40 trays
Step (3) :
To calculate the tower diameter and tower height :
(1)Tower height (Z):
Z = no. of trays * H / 12 + 2*5
H = 24 in
Z = 40 * 24/12 + 2 * 5 = 90 ft.
2) Tower diameter (D) :
P =latm , T
D
=86
o
C.
V
D
= 359 * ( 460+86 )/(460+32)* 1/1
V
D
= 398.4 ft3 /lb
mol
V
D
= 398.4 * 259.84=103520 ft
3
/ hr.
L =RD
V = D (R + 1 ) = 259.84 ft
3
/hr.
µ
L
=48.1 Ib / ft
3
µ
v
= 0.8 Ib / ft
3
V
c.s
=K ( (µ
1
- µ
v
) /µ
v
)
1/2
K = 0.16 from (Fig 2)
CATALYTIC REFORMING
173
V
C.S
= 1.23 ft./sec.
V
C.S Design
= V
C.S Max.
/ 1.15 = 1.07 ft./sec.
A = V/v = 26.879 ft.
2
D = (4A / t )
½
= 5.85 ft.
standard D= 6 ft
Sieve Tray design :
Given data :
D = 6 ft. , H = 24 in. , L = 1650 Gpm
From (Fig 3)
Type of flow is double pass.
Advantages of sieve tray :
(1)lower pressure drop than bubble cap tray
(2)performance and design is more simple
(3) stability condition is achieved on each tray
[1] Down flow area :
A
df
/ A
T
= 20%
A
dc
/ A
T
= 10%
A
dc1
/ A
T
= 0.05
A
T
= t/4 D
2
A
T
= 28.274 ft
2
A
dc1
= 0.05 * 28.274 = 1.4137 ft
2
L
w1
/ D = 0.59
d
wl
/D = 0.097
L
wl
= 42.48 in , d
wl
= 6.984 in
A
dc2
/A
T
=0.45
A
dc2
= 28.274 (0.45) =12.7233 ft
2
L
W2
/ D = 0.997 ,d
W
/D = 0.461
L
w2
=0.997*6*12=71.784 in
d
W
=0.461 (6) *12=33.192 in
d
w2
= D - 2d
w
d
w2
= 4* 12 – 2 (33.192) = 5.616 in
Ch.8 Design
174
[2] Effective area :
assume :
o =2 in, x = 5in , y = 3in
D
n
' = D - 2 o
=12*6-2(2)
D
n
' = 68 in
A
n
' = t/4(D
n
)
2
=3631.68 in
2
d
wl
' = d
wl
+ y-a
d
wl
'= 6.984 +5-2
d
wl
' = 9.984 in
d
wl
'/D
n
' = 9.984/68 = 0.1469
From Ludwig Fig (5-4)
A
dcl
' /A
n
' = 11.5%
A
dcl
' = 0.115(3631.68) =417.64 in
2
=2.9 ft
2
A
dcs
' /A
n
' = 0.45
d
w
' / D
m
' = 0.461
d
w
' = 0.461 (68) =31.348 in
d
w2
' = D
n
' – 2 (d
w
' )
= 68 - 2(31.348) = 5.304 in
L
w2
' = 0.997 (68) = 67.796 in
d
w3
' = d
w
' +
1
/
2
d
w2
'
= 31.348 +
1
/
2
(5.304)
d
w3
'= 34 in
d
w3
'/A
n
' = 0.5 from Ludwig - fig (8-48)
A
dc3
' /A
n
'= 0.5
A
4
= A
n
' * 2 ( A
dc3
' / A
n
' - A
dc2
' / A
n
' )
A
4
= 0.1 (3631.68) =363.168 in
2
A
eff
=A
n
'-2A
dcl
' - A
4
' -2 (L
w2
' * x)
A
eff
= ((3631.68)-2 (417.64)-363.168 -2 (67.796*2))
A
eff
= 2162.408 in
2
=15.0142 ft
2
[3] Liquid distribution area :
A
dis
= 2(Lw
1
*5/12)+2(LW
2
*5/12)
=2(3.54 * 5)+2(67.796 * 5)
A
dis
= 890.36 in
2
= 6.183 ft
2
Distribution area percent: 21.867%
CATALYTIC REFORMING
175
[4] end westage area :
A
west
= A
T
– A
dc
– A
liq
– A
eff
= 28.274 – 0.2 *28.274 -6.183 -15.01422
A
west
= 2.822 ft
2
[5] Check on residence time (T
R
):
T
R
= (A
d.c
* H * 37.4)/L
T
R
= (5.655 * 24 * 37.4 ) / (1650/2)
T
R
= 6.152 sec > 5 sec
[6] Hole size (do) and spacing ( c ):
d
o
= 3/16 in
2
c =2.5 d
o
[7] Tray thickness (t) :
t = 1/4 in
2
[8] % of hole area ( ) :
assume | =12.8 % ( very small diameter)From ludwig fig (5-5)
[9] Height of weir(hw) :
Assume h
w
= 1 in
h
ow
= 0.092((L/2)/l
w2
)
2/3
h
ow
= 0.4867 > 1/4 in liq so, it’s good liquid distribution
assume h
Ls
= 1.75 in
[10] Minimum hole velocity ( Fsmin) "weeping" :
1) d
o
/t = 0.75
from (Fig. 5-6)
c
o
= 0.837 in.
2) calculate dry pressure drop (h
dt
) :
h
dt
= 0.003 f
s
2
* (µ
w
/ µ
l
) ((1-|
2
) / c
o
2
)
= 5.476 * 10
-3
f
smin
2
3) effective head (h
e
) :
assume h
e
= 1.7
4) total wet pressure drop on tray (h
t
) :
h
t
= h
dt
+ h
e
Then by using - Fig(5-7) F
s min
= 16
Ch.8 Design
176
[11] Max ... Hole velocity ( Fs max ) " Flooding ":
1- assume F
s max
> 16
where F
s max
at H
d
=1/2 (H+h
w
).
2- H
d
= H
t
+ h
1s
+ h
du
h
hu
= 0.56 ((L/2) / 449 (Ad))
2
h
du
= 0.031 in
H
d
= h
t
+ 1.8
3- assume h
e
= 1.5 in
4-h
dt
= 5.476*10
-3
F
2
s max
F
s max
= 47 at H
d
= 1/2 (24+1) = 12.5
[12] Design hole velocity - (Fs design ):-
F
s design
= ( F
s min
+ F
s max
) /2
F
s design
= 31.5=32
V
o design
= F
s
/ µ
v
1/2
= 32/0.8
1/2
= 35.78 ft/sec
[13] Number of holes available on the tray :-
V=N*(π /4)*(d
o
2
/144)*v
0
N= 2360 holes
From fig available no of holes =2860 holes
Excess no of holes =2860-2360=500 hole
Excess area =500/4.62 =108.225 in
2
[14] Total wet pressure drop (hi) :-
F
sdesign
= 32 , h
e
= 1.2
h
dt
= 5.476 * 10
-3
f
s
2
h
t
= h
dt
+ 1.5
= 6.81 in. liq
[15] Pressure drop for tray (∆ p) :
∆ p = ( h
t
* µ
L
) / (12*144)
= 0.189 psi < 0.2 psi
CATALYTIC REFORMING
177
Pump Design
Ch.8 Design
178
Pump Design:
Here we will design the pump which pumping feed at the first
of the catalytic reforming process.
DEFINITION OF SYMBOLS USED IN DESIGN:-
V
f1
: inlet absolute velocity ft / sec
V
f2
: outlet absolute velocity ft / sec
U
1
: inlet tangential velocity ft / sec
U
2
: outlet tangential velocity ft / sec
V
r1
: Relative inlet velocity ft / sec,
V
r2
: Relative outlet velocity fl / sec
V
W2
: Residual portion of outlet tangential velocity ft / sec
D
1
: inlet diameter. in standard
D
2
: outlet diameter . in standard
B
1
: Blade inlet width .
B
2
: Blade outlet width .
H : Head . Ft
N
s
: specified speed . r.p.m
N : impeller speed . r.p.m
Q : flow Rate . G.P.M.
HP : Hoarse power required .
¢ : Flow ratio , (0.15-0.3)
u : speed ratio . · 0.25°
o : Blade outlet angle . < 90°
u : Blade inlet angle . ( 20 - 45° )
| : Absolute outlet angle . ( 10-30° )
q
over
: over all efficiency .
q
mano
: manometric efficiency.
q
mec
: mechanical efficiency .
Data: -
m
f
= 60125 Lb/hr
API = 61.5
T = 40 C

= 104

f
Total dynamic head = 49 m
= 161 ft
CATALYTIC REFORMING
179
Design steps:-
from kern charts by T = 104

F , API = 61.5 find specific gravity
=0.71
density = 0.71 * 62.4 = 44.3 Lb / ft
3
Q= mass flow rate / density
= 60125 / 44.3 = 1357 ft
3
/hr
= 1357 * 7.48 / 60 = 169.2 G.P.M
Step(1) :calculation of specific speed(N
s
)
- it should to be in the range (500-3000)
- assume N= 2900 r.p.m in the range of (1450-2950).
- N
s
= N *(Q)
0.5
/ (H)
0.75
= 2900* (169.2)
0.5
/ (161)
0.75
= 834 r.p.m (in the range so it is ok)
Step(2): calculation of manometric efficiency (q
man
)
from chart(1.1) by using NS = 834 r.p.m , Q = 169.2 G.P.M
find
overall
= 64.5%
-assume
mech
from range (70% - 90%) take it = 75 %
-
man
=
overall
/
mech
*100
= 64.5 / 75 * 100
= 86 %
tep(3): alculation of inlet and outlet diameter of
plate (D
1
,D
2
)
-assume (n) from range (0.1-0.4) take it = 0.1
- n= B
1
/D
1
so B
1
=0.1 D
1
- assume (D
2
/D
1
) from range (1.5 – 3) take it = 2.7
- so D
2
= 2.7 D
1
-assume ( Ψ ) from range (0.1-0.3) take it =0.15
- V
F2
= Ψ * (2 * g * H)
0.5
=0.15 * (2 * 32.2 * 161)
0.5
= 15.28 ft / sec
V
F
= V
F1
= V
F2
= 15.28 ft / sec
- Q = t* B
1
*D
1
* V
F1
Ch.8 Design
180
1357/3600 = t* (0.1 D
1
) * D
1
* 15.28
D
1
= 0.28 ft
= 3.36 in
D
2
=2.7 * 0.28
=0.756 ft
=9.027 in
Step(4) : Calculation of inlet and outlet width of
impeller (B
1
,B
2
)
- Q = t* B
2
* D
2
* V
F2
B
2
= 1357 / (t* 0.756 * 15.28 * 3600 )
= 0.01 ft
= 0.125 in
- B1 = 0.1 * 0.28
=0.028 ft
=0.336 in
Step (5) : Calculation of inlet and outlet tangential
velocity (U
1
,U
2
)
- U
1
= (t* D
1
* N) / 60
= (t* 0.28 * 2900) / 60
= 42.52 ft / sec
- U
2
= (t* D2 * N) / 60
= (t* 0.756 * 2900 ) / 60
= 114.8 ft / sec
Step (6) : calculation of inlet and outlet wirl
velocity (V
W1
, V
W2
)
- V
W1
= zero
- V
W2
= (H * g) / (U2 * q
man
)
= (161 * 32.2) / ( 114.8 * 0.86)
=52.5 ft /sec
CATALYTIC REFORMING
181
3.1416*(D2²-D1²)
Step (7): calculation of pump's angles
a) absolute outlet angle calculation () :-
- | = tan
-1
( V
F2
/ V
W2
)
= tan
-1
(15.28 / 52.5)
=16.23
o
( < 20
o
) so it is ok .
b) plate angle at outlet calculation ( ) : -
o = Tan
-1
(V
F2
/ (U
2
– V
W2
))
= Tan
-1
(15.28 / (114.8 – 52.5))
= 13.8
o
(< 90
o
) so it is ok .
c) plate angle at inlet calculation ( ) : -
u = Tan
-1
V
F1
/ U
1
= Tan
-1
(15.28 / 42.52 )
= 19.8
o
in range (20
o
- 45
o
) nearly satisfy.
Step (8): check on design
a)speed ratio( ) must be in range (0.95 – 1.25 ) : -
- | = U
2
/ (2 g H)
1/2
=114.8 / (2 * 32.2 * 161)
=1.127 in range (0.95 - 1.25) so it is ok .
b) N
MIN
< N
ASSUMED
: -
Nmin= 120 * q
man
* V
W2
* D
2
= 2645 r.p.m ( < 2900 ) so it is ok .
Step(9): calculation of horse power required(HP)
HP = ¸ Q H / 75 q
overall
*3600
= 5 HP (standardized)
Ch.8 Design
182
Compressor design
CATALYTIC REFORMING
183
Compressor design
Here we will design the compressor which compresses air for
regeneration.
Data given: -
suction pressure (P
1
) = 14.7 psia
final pressure (P2) = 205 psia
suction temperature (T
1
)= 85 ˚F
air flow rate m
air
= 5100 lb / hr
pressure drop of inter cooler (Δ P)= 5 psia
cooling water temperature (T
w
) = 90˚F
Design steps:-
Step (1): Calculation of compression ratio (R
Ct
)
R
Ct
= P
2
/P
1
= 205/14.7
= 13.9 >> 5
So we must divide the compressor to multi stage.
Step (2): calculation of number of stage (n)
R
ci
= (R
ct
)
(1/n)
= (13.9)
0.5
= 3.72 (in range (3 - 5) so it is ok)
So there are two stages.
Step (3): Calculation of discharge pressure
a)Discharge pressure for the first stage(P
12
) : -
P
12
= (R
ci
* P
1
) + (Δ P / 2)
= (3.72 * 14.7) + (5 /2)
=57.2 psia
Ch.8 Design
184
b) Inlet pressure for the second stage (P
22
): -
P
22
= P
12
– Δ p/2
= 57.2 – 5
= 52.2 psia
R
CI
= P
12
/ P
1
R
c2
= P
2
/ P
22
= 57.2 / 14.7 = 205 / 52.2
=3.91 =3.92
CHECK: is ok
Step (4): Calculation of outlet final temperature
from table (12.1) find k for air k
air
= 1.4
T
F
= T
1
* R
C
(K-1)/K
= (85+460) * 3.9
(1.4-1)/1.4
= 804 ˚R = 344˚F (<350 ˚F) SO IT IS OK
Step (5): Calculation of capacity at actual condition
(Q
a1
, Q
a2
)
Q
s
= 5100 / 0.0766
= 66580 SCF/hr
= 1.6 MMSCFD
a) for first stage :-
Q
a1
(at 14.4 Psia, T1=85˚F) = 1.96314 *10
-3
*Q
S
* (T
i
+460)
= 1.96314 *10
-3
*1.6 (85+460)
= 1.71MMSCFD
b) for second stage :-
Q
a2
(at 14.4 Psia, T =100˚F) = 1.96314 *10
-3
*1.6 *
(100+460)
=1.76 MMSCFD
CATALYTIC REFORMING
185
Step (6): calculation of Brake horse power
from figure (7 -2 ) by known (Rc =3.9, K= 1.4 ) find
BHP/MMCFD=88
a) For first stage:-
(BHP)
1
=Q
a1
* BHP/MMCFD (@14.4 Psia, T=85˚f)
= 1.71 * 88
=150.5 HP
b) For second stage:-
(BHP)
2
= Q
a2
* BHP /MMCFD (@14.4 Psia, t = 100˚f)
=1.76 *88
= 154.9 HP
total Brake horse power = (BHP)
1
+(BHP)
2
= 305.5 BHP
standardized (BHP)
total
= 350 HP
BHP)
1st
= BHP)
1
* BHP)
st
/BHP)
t
= 150.5 *350 /305.5
= 173
BHP)
2st
= BHP)
2
* BHP)
st
/BHP)
t
= 154.9 * 350 /305.5
= 177
Step (7): Cylinder selection of size for each stage
PDEV = HP * 10
4
/ (BHP/MMCFD)(P
i
– 0.5)
a) for first stage:-
PDEV)
1
= 173 *10
4
/ 88(14.7 - 0.5)
= 1385 CFM
from table (7 – 1) single stage horizontal type try to use
cylinder of PD = 1410 CFM
EV % = 100 – R
c
– V
pc
(R
c
1/k
– 1)
= 100 – 3.9 – 24 (3.9
1/1.4
– 1)
= 56.65 %
PDEV)
1st
= 1410 * 0.5665
= 800 CFM
Ch.8 Design
186
b) for second stage : -
PDEV)
2
= 177 *10
4
/ 88(52.5 - 0.5)
from table(7 – 1) single stage horizontal type try to use
cylinder of PD = 410 CFM
EV% = 100 – 3.9 – 14.5 (3.9
1/1.4
– 1)
= 72.3 %
PDEV)
2st
= 410 * 0.723
= 297 CFM
PDEV 297 CFM; so we can use it.
No. of
stage
Cycle
type
No.
of
cycle
P.D EV% R.P.M Dia Max
PSI
S,L
First
stage
horizontal 1 1410 56.65% 300 20 35 13
Second
stage
horizontal 1 410 72.3% 450 12 20 7
CATALYTIC REFORMING
187
Tank Design
Ch.8 Design
188
Tank design
Here we will design the tank which used to storage reformate.
Data given: -
m
p
= 56000 lb / hr
API = 44.94
T = 104 ˚F
Design steps: -
from kern chart by known (API = 44.56, T = 104 ˚F). find
specific gravity of reformate = 0.783
density = 0.783 * 62.4 = 84.86 lb / ft
3
so Q = mass flow rate / density
= 5600 / 84.86
= 1146.13 ft
3
/ hr
assume production capacity = 30 day
V = 1146.13 * 24 * 30
= 825,228.4 ft
3
= 825,228.4 / (3.281)
3
= 23,364 m
3
>> 1000 m
3
( so we wil design large tank)
Step(1) : calculation of suitable dimensions of tank (D
, H )
1)- calculate D/H)
OPT
:-
D/H)
OPT
= 4 C
1
/ (C
2
+C
3
+ C
4
+ C
5
)
C
4
= C
5
= zero
C
1
= C
3
= 2C
2
D/H)
OPT
= 8 / 3
2)- calculate the hieght of tank(H):-
V=(t * D
2
* H ) / 4
H= ( 825,228.4 * 4) / (t * (8/3)
2
)
(1/3)
=52.87 ft
standrized (H) by find the aproximately number which
can divide into (6,8).
CATALYTIC REFORMING
189
H
st
= 54 ft (which can divide into 6 and give 9)
so the number of courses = 9
3)- calculate the diameter of tank(D) :-
D= ((4 * V ) / (t * H ))
0.5
=((4 * 825,228.4) / (t * 54))
0.5
= 139.5 ft
D
st
= 140 ft
4)- calculation of actual volume(V
act
) : -
V
act
= (t * D
st
2
* H
st
) / 4
= (t * 140
2
* 54) / 4
= 831,265.42 ft
3
5)- check ((V
act
– V
given
)/ V
act
) < 10% :-
= ((831,265.42 -825,228.4) /831,265.42) *100
= 0.73 % <<< 10%
(SO IT'S OK)
Step(2) : - design of shell courses (t
n
) :-
t
n
= 0.0001456 * D
st
* ( H – n ) (n from 1 to 9 )
n 1 2 3 4 5 6 7 8 9
H (ft) 6 12 18 24 30 36 42 48 54
T
st
(in) 0.25 0.25 0.35 0.47 0.60 0.72 0.84 0.96 1.03
Ch.8 Design
190
∑ t
n
= 0.25+ 0.25 + 0.35 + 0.47 + 0.6 + 0.72 + 0.84 + 0.96 +1.03
= 5. 47 in
Step(3): volume of steel(V
steel
)calculation
V
steel
= t * D
st
* 6 * ( ∑ t
n
/12)
= t * 140 * 6 * ( 5.47 / 12 )
= 1202 .9 ft
3
Step (4): Volume of Bottom &Roof (V
bot
, V
roof
)
Calculation
V
bottom
= t * D
st
2
/(4 * 4 * 12 )
= t * 140
2
/ (4 * 4 * 12 )
= 320.7 ft
3
V
roof
= 2 * V
bottom
………….. (rough estimation)
= 2 * 320.7
= 641.4 ft
3
CATALYTIC REFORMING
191
References
Speight, J.G., The Chemistry and Technology of Petroleum, Fourth
Edition, CRC Press, Taylor & Francis Group, New York, 2007.
Pierre Leprince, French Institute of Petroleum, Petroleum Refining-
Conversion Processes, Editions TECHNIP.
Serge Raseev, Thermal and Catalytic Processes in Petroleum Refining,
Marcel Dekker, Inc, New York, 2003.
Robert A. Meyers, Handbook of Petroleum Refining Processes, Third
Edition, McGraw-Hill Handbooks.
George J. Antons, Abdullah M. Aitani, and Jose' M. Parera,Catalytic
Naphtha Reforming, Marcel Dekkar,Inc, New York.
Ludwig, Applied Process Design for Chemical and Petrochemical Plants.
Mustafa Awad, University textbook.

CATALYTIC REFORMING

Table of Contents

Ch.1 Basic Principles …………………………………………..…… 1 1.1 1.2 1.3 1.4 1.5 Introduction …………………………………..………………… 2 The Problem of Antiknock Quality ……………………..……… 2 Octane Number …………………………………...…………….. 2 Composition Effect on Octane Number ………………….…….. 3 Reforming ………………………………………………………. 6 1.5.1 Thermal Reforming …………………..…………………. 6 1.5.2 Catalytic Reforming ………………………..…………… 7 1.6 Feed Treatment By Hydrogen……………………………………. 11 1.6.1 Hydrofining ……………………………..………………. 12

Ch.2 The Catalytic Reforming Process …………………………... 14 2.1 Introduction ………………………………………………..….. 2.2 Feed to Catalytic Reforming ………………………………….. 2.3 Product from Catalytic Reforming ……………………………. 2.3.1 The Typical Yield …………………………………….... 2.3.2 Reformate Composition ………………………………... 2.3.3 Reformate Specification …………………….…………. 2.4 Catalytic Reforming Techniques ………………..…………….. 2.4.1 Fixed-Bed Technology ……………………………..….. 2.4.2 Moving-Bed Technology …………………………...….. 2.4.3 Fluid-Bed Technology ………………………………..... 15 16 17 18 19 20 22 24 34 41

Ch.3 Process Chemical Reactions and Thermodynamics ………. 43 3.1 Introduction ………………………………………………..….. 3.2 Process Reactions …………………………………………..…. 3.2.1 Dehydrogenation of Naphthenes …………………...….. 3.2.2 Isomerization of Paraffins and Naphthenes ………...….. 3.2.3 Dehydrocyclization of Paraffins ………………….……. 3.2.4 Hydrocracking and Dealkylation ………………….…… 3.3 Relative Reaction Rate ………………………………………... 3.4 Heats of Reaction …………………………………………..…. 44 44 44 45 45 45 47 50

II

CATALYTIC REFORMING

Ch.4 Catalytic Reforming Catalyst ………………………………. 51 4.1 Introduction …………………………………………...………. 4.1.1 Classification of Catalyst ………………………….….... 4.1.2 Main Types of Catalyst ……………………………..…. 4.1.3 General Catalyst Characterization and Properties ……... 4.2 Types of Catalytic Reforming Catalyst ……………………...... 4.2.1 Platinum on Chlorinated Alumina ……………………... 4.2.2 Bimetallic …………………………………………….... 4.3 Effect of Platinum content of Catalyst ………………………... 4.4 Catalyst Preparation ………………………………………….... 4.4.1 Optimization of the Formation …………………..…….. 4.4.2 Unit Operations ………………………………..………. 4.5 Reaction Mechanisms ……………………………………...….. 4.5.1 Hydrogen Action ……………………………….…….... 4.5.2 Sulfur Action ……………………..……………………. 4.6 Catalyst Deactivation ………………………………………….. 4.6.1 Characterization of Coke ……………………...……….. 4.6.2 Effects of Reaction Conditions on Coking Deactivation . 4.6.3 Mechanism of Coke Formation ………………...……… 4.6.4 Poisoning of Naphtha Reforming Catalyst …………….. 4.7 Catalyst Regeneration …………………………………………. 4.7.1 Effect of the Type of Process on Cycle length ………… 4.7.2 Catalyst Regeneration Steps ……………………..…….. 4.7.3 Factors Affecting Coked Catalyst Reactivity ………….. 4.7.4 Regeneration of coked Catalyst ………………….…….. 4.7.5 Regeneration of Sulfur-Contaminated Catalyst …….….. 4.8 Procedure of Regeneration ……………………………………. 4.8.1 Pre-Shutdown ………………………………………….. 4.8.2 Shutdown ………………………………………….…… 4.8.3 Carbon Burn ………………………………………….... 4.8.4 Oxidation ………………………………………………. 4.8.5 Cool Down ……………………………………..………. 4.8.6 Nitrogen Purge …………………………………………. 4.8.7 Reduction ………………………………………………. 4.8.8 Sulfate Removal ……………………………………….. 4.8.9 Start-Up ……………………………………………..…. 52 52 54 54 57 57 58 60 61 61 62 68 69 71 73 73 74 78 80 87 87 87 87 87 91 92 92 92 92 93 93 93 93 94 94

Ch.5 Catalyst Reforming Parameters ……………………...…….. 95 5.1 Introduction ……………………………………………...……. 96 5.2 Temperature …………………………………………...………. 96
III

Tank Design ………………………………………………….CATALYTIC REFORMING 5.1 8..5 8..8 Design …………………………………………………. 118 Ch.. Furnace Design ……………………………………………….6 Hazard Assessment ………………………………………… 105 Ch...…… Stabilizer Design ………………………………………….4 5..7 Plant Design ……………………………………………….3 8. 123 126 143 163 168 177 182 187 References ………………………………………………………… 191 IV .……… Hydrogen to Hydrocarbon Ratio ………………………. Heat Exchanger Design ……………………………….2 8..4 8.6 Reaction Pressure …………………………………….5 5.… Feedstock Properties …………………………………………. Space Velocity ……………………………………………..…….. 98 99 101 102 Ch.…… 122 8... Reactor Design ………………………………………….……..….3 5. Pump Design ………………………………………………… Compressor Design ………………………………………….8 Material Balance …………………………………………….7 8.6 8.

CATALYTIC REFORMING .

3 OCTANE NUMBER The antiknock property of a gasoline is generally expressed as its octane number. Dehydrogenation. Most of the catalytic reforming reactions favor high temperatures. The used catalyst for catalytic reforming processes is the platinum supported on a silica or silica-aluminum base for fixed bed processes and non-precious metal oxide catalysts for fluid and moving bed processes.Ch. The gasoline which occurs in the crude oil is too poor in the antiknock quality to be used alone as a fuel in the modern automobile engines that are designed on using high compression ratios. But this increase in performance goes together with an increase in knocking and detonation. consequently enhancing the antiknock quality of gasoline. the more power the engine can produce. detonate or ping during service. 1. Knocking occurs in the combustion chamber in the cylinder of motor engines. Hence when straight-run gasoline (Naphtha) is used directly in engines. and low space velocities. The more the fuel-air mixture is compressed. 1. compression ratios of engines are increased to deliver more power. and Dehydrocyclization which convert the low octane number components in naphtha into very high octane number components. low pressures.1 BASIC PRINCIPLES 1. Two types of reactors are used in the catalytic reforming process: the fixed-bed reactor and the moving-bed reactor. it will knock causing a lose in power and a loud noise. Catalytic Reforming involves some reactions such as Isomerization. This number is the percentage of iso-octane in a blend with nheptane that produces the same amount of knocking produced by the . this knocking is a result of the sudden combustion of the gasoline-air mixture in the cylinder. With the increase of loads and duties on engines over years and the subsequent development of automobile engines.1 INTRODUCTION The problem of low octane ratings of naphtha is solved by increasing the contents of isomers and aromatics in its composition.2 THE PROBLEM OF ANTIKNOCK QUALITY A very important property of an automobile gasoline is its resistance to knock.

Comparing the different hydrocarbon series. ASTM has standardized octane number test methods into Research Octane Number (RON). while iso-paraffins and naphthenes have higher octane numbers than the corresponding normal paraffins. then research octane number is the meant measurement. 1. The octane number of the iso-paraffins increases with the increase of branching of the chain. Normal paraffins have the least desirable knocking characteristics and they become progressively worse as the molecular weight increase. (RON) is produced using normal road conditions. to increase the octane number of gasoline.1) shows the octane numbers of several hydrocarbons.CATALYTIC REFORMING tested gasoline. . Such a transformation process is called the Reforming Process. while (MON) is produced using sever or high-speed conditions on the testing equipment. aromatics – except for Benzene – are the hydrocarbons with the highest octane numbers. Olefins have markedly higher octane numbers than the corresponding paraffins and aromatics usually have very high octane numbers. the paraffinic and naphthenic contents in gasoline should be transformed into aromatics and isoparaffins. Worth mentioning here is that when octane number is reported or assigned to gasoline without definition. Table (1. Hence.4 COMPOSITION EFFECT ON OCTANE NUMBER Extensive studies of octane numbers of individual compounds have brought to light some general rules. and Motor Octane Number (MON) tests. unless stated otherwise. The arithmetic average [(RON+MON)/2] is increasingly used nowadays.

.3-Dimethylbutane n-Heptane 2-Methylhexane n-Octane Olefins 1-Pentene 1-Octene 3-Octene Naphthenes Methylcyclopentane Ethylcyclopentane 1. RON 113 122 19 83 89 96 0 41 -19 91 29 73 107 75 96 99 124 120 145 146 106 99 90 117 Another solution for the low antiknock problem of gasoline was used in 1922 which was the use of TEL (Tetra Ethyl Lead). RON for some pure hydrocarbons.Ch.1-Dimethylcyclopentane Aromatics Benzene Toluene o-Xylene m-Xylene p-Xylene Oxygenates Methanol Ethanol 2-Propanol (MTBE) Table (1.1 BASIC PRINCIPLES Pure Hydrocarbons Paraffins n-Butane i-Butane n-Hexane 2-Methylpentane 2. TEL increases the octane number greatly when added to gasoline in small quantities.2-Dimethylbutane 2.1).

The ethers may be produced at the refinery by reacting suitable alcohols such as methanol and ethanol with branched olefins from the fluid catalytic cracker. using the same acidic catalysts. methyl-t-butyl ether (MTBE) -made by etherification of iso-butene with methanol. Where olefin levels are restricted. such as iso-butene and iso-pentene.became the predominant oxygenate used to meet reformulation requirements for adding oxygen to mitigate emissions from gasoline-powered vehicles. Environmental issues involving MTBE have made it more desirable to dimerize isobutene from the catalytic cracking unit rather than etherify it. MTBE.butyl Alcohol Ether (5 or more C atoms) Other oxygenates 3 5 10 10 7 15 10 Table(1. Nowadays lead-free gasoline is used in most countries around the world and as a substitute additive for TEL to the gasoline.CATALYTIC REFORMING However.2). the extra blending octane boost of the di-iso-butylene can be retained. Oxygenates Maximum. under the influence of acid catalysts. the di-iso-butylene can be hydrotreated to produce a relatively pure iso-octane stream that can supplement alkylate for reducing olefins and aromatics in reformulated gasoline. and TAME are now used to increase the octane number of gasoline. . in many countries the amount of added lead has been decreased gradually by strict regulations in order to pave the way for completely preventing its use for its harmful effect on man's health and environment. oxygenates such as alcohols.2) shows the Maximum allowable contents of some oxygenates. Where olefin levels are not restricted. over years. In the mid-1990s. Fortunately. Oxygenates allowed on Gasoline. iso-butene dimerization may be achieved with minimal modifications to existing MTBE plants and process conditions. Volume % Methanol Ethanol Iso-propyl Alcohol Iso-butyl Alcohol Tert. Table (1.

the higher the octane number of the product but the yield of reformate is relatively low. In carrying out thermal reforming. reforming converts (reforms) gasoline into higher-octane gasoline. The remainder of the reformed material leaves the top of the tower to be separated into gases and reformate. with pressures from 400 to 1000 psi. The quenched. is heated to 510 to 595 °C (950 to 1100 °F) in a furnace much the same as a cracking furnace. reformed material then enters a fractional distillation tower where any heavy product is separated.5 REFORMING Reforming is essentially a treatment process designed to improve a gasoline octane number and may be accomplished in part by an increase in the volatility -reduction in molecular size. 1958). The equipment for thermal reforming is essentially the same as for thermal cracking. olefins. it is cooled or quenched by the addition of cold naphtha. A general rule is the higher the reforming temperature. molecular size is reduced. such as a 205 °C (400 °F) end-point naphtha or a straight-run gasoline. Thermal reforming is in general less effective than catalytic processes and has been largely supplanted. As the heated naphtha leaves the furnace. as reforming is also a thermal decomposition reaction.1 BASIC PRINCIPLES 1. 1. In thermal reforming.Ch.or chiefly by the conversion of n-paraffins to iso-paraffins.1 Thermal Reforming Thermal reforming was naturally developed from thermal cracking. For . a single-pass operation was employed at temperatures in the range of 540 to 760 °C (1000 to 1140 °F) and pressures in the range 500 to 1000 psi. the reactions resemble the reactions that occur during gas oil cracking.5. Octane number improvement depended on the extent of conversion but was not directly proportional to the extent of cracking-per-pass. that is. and aromatics and the conversion of naphthenes to aromatics. The process is carried out either thermally or catalytically. and olefins and some aromatics are produced. The amount and quality of reformate is dependent on the temperature. The higher octane number of the product (reformate) is due primarily to the cracking of longer chain paraffins into higher-octane olefins. a feedstock. The nature of the final product is of course influenced by the source (and composition) of the feedstock. Cracking converts heavier oils into gasoline. but higher temperatures are used (Nelson. As it was practiced.

olefinic gases produced by cracking and reforming can be converted into liquids boiling in the gasoline range by heating them under high pressure. both processes operate in much the same manner as thermal reforming and produce similar products. and iso-butane [(CH3)2CH. Except for the gaseous components in the feedstock.CH3] in the C4 fraction. the process is called naphtha-gas reversion or naphtha polyforming. and other reactions take place.CH2. butylene (CH3.CH=CH.CH2. Thus.5.CH=CH2 or CH3. the naphtha and gases flow through separate lines in the furnace and are heated independently of one another. As the resulting liquids (polymers) have high octane numbers. In gas reversion. In naphtha reforming. When the C3 and C4 fractions are passed through a thermal reformer in admixture with naphtha. catalytic reforming converts low-octane gasoline into high-octane gasoline (reformate). However. Before leaving the furnace. high conversion is not always effective as coke production and gas production usually increase. Modifications of the thermal reforming process caused by the inclusion of hydrocarbon gases with the feedstock are known as gas reversion and polyforming.4% of 56 octane reformate. 1.7% of 83 octane reformate. polymerization. These are propylene (CH3.CATALYTIC REFORMING example. which is associated with propane in the C3 fraction. Although thermal reforming can produce reformate with a research octane number in the range of 65 to 80 . when reformed at 555 °C (1030 °F) the yield is 68. the C3 and C4 gases are premixed with the naphtha and passed together through the furnace. both lines join to form a common soaking section where the reforming.CH3). which are associated with butane (CH3. a gasoline with an octane number of 35 when reformed at 515 °C (960 °F) yields 92. they undergo chemical reactions that result in a small yield of gasoline.2 Catalytic Reforming Like thermal reforming. they increase the overall quantity and quality of gasoline produced in a refinery.CH2.CH=CH2). When the C3 and C4 fractions are subjected to the temperature and pressure conditions used in thermal reforming. These processes are essentially the same but differ in the manner in which the gases and naphtha are passed through the heating furnace. The gases most susceptible to conversion to liquid products are olefins with three and four carbon atoms.CH3) and iso-butylene [(CH3)2C=CH2].

not olefinic) materials. As a result of the very high temperatures. The process uses a precious metal catalyst (platinum supported by an alumina base) in conjunction with very high temperatures to reform the paraffin and naphthene constituents into highoctane components. which reduces the surface area available to contact with the hydrocarbons. the reforming reactions are endothermic. catalytic reforming produces reformate with octane numbers of the order of 90 to 95.1 BASIC PRINCIPLES depending on the yield. Hydrocarbon naphtha that contains substantial quantities of naphthenes is also a suitable feed. coker naphtha) can be processed after treatment to remove olefins and other contaminants. The resulting product stream (reformate) from catalytic reforming has a RON from 96 to 102 depending on the reactor severity and feedstock quality. involving structural changes in the charge stock. which may be supported on alumina or silica–alumina. The dehydrogenation reactions that convert the saturated naphthenes into unsaturated aromatics produce hydrogen. but other byproduct low-octane naphtha (e. Depending on the catalyst. essentially pure carbon) on the catalyst. The hydrocarbons are reheated by direct-fired furnaces between the subsequent reforming reactors. which requires that virtually all the sulfur must be removed from the heavy naphtha through hydrotreating before reforming. The catalytic reforming process consists of a series of several reactors. As a result. Overall .. Catalytic reforming is conducted in the presence of hydrogen over hydrogenation-dehydrogenation catalysts. Catalytic reformer feeds are saturated (i.Ch... . and  naphthenes are converted to aromatics. in the majority of cases the feed may be a straight-run naphtha. The catalytic reforming process was commercially nonexistent in the United States before 1940. which operate at temperatures of approximately 480 °C (900 °F). thermal reforming is now somewhat obsolete. The process is really a process of the 1950s and showed phenomenal growth in the 1953–1959 period. a definite sequence of reactions takes place.e.e. the catalyst becomes deactivated by the formation of coke (i. Several different types of chemical react ions occur in the reforming reactors:  Paraffins are isomerized to branched chains and to a lesser extent to naphthenes. Sulfur is a poison to the reforming catalyst.g. which is available for distribution to other refinery hydro-processes.

The product issuing from the last catalytic reactor is cooled and sent to a high-pressure separator where the hydrogen. depending on the feedstock and reaction conditions.g.1).. Figure (1. two (or more than one) reactors are used in series. . and then passed through fixed-bed catalytic reactors at hydrogen pressures of 100 to 1000 psi. and  The remaining portion represents excess hydrogen available for other uses.CATALYTIC REFORMING Catalytic reforming is usually carried out by feeding a naphtha (after pretreating with hydrogen if necessary) and hydrogen mixture to a furnace where the mixture is heated to the desired temperatures 450 °C to 520 °C (840 °F to 965 °F).1) shows the relation between reformate yield and its octane number. The on-stream cycle of any one reactor may vary from several hours to many days. Sometimes as many as four or five are kept on-stream in series while one or more is being regenerated. ammonia). Normally. or for manufacture of chemicals (e. Reformate Yield and its Octane Number. The excess hydrogen is vented from the unit and used in hydrotreating. Figure (1. as a fuel.rich gas is split into two streams:  One stream goes to recycle where it is mixed with the feed. The liquid product (reformate) is stabilized (by removal of light ends) and used directly in gasoline or extracted for aromatic blending stocks for aviation gasoline. and reheaters are located between adjoining reactors to compensate for the endothermic reactions taking place.

Fixed-bed processes use predominantly platinum-containing catalysts in units equipped for cycle.1 BASIC PRINCIPLES The commercial processes available for use can be broadly classified as the moving-bed. Under the high-hydrogen partial pressure conditions used in catalytic reforming. builds up to a high concentration in the recycle gas. Hydrogen reactionshydrogenation. sulfur compounds are readily converted into hydrogen sulfide. hydrocracking of paraffins to yield two lower paraffins occurs. which. for example. unless removed. or no regeneration. The addition of a hydrogenation–dehydrogenation catalyst to the system yields a dualfunction catalyst complex. The continuous catalyst regeneration (CCR) configuration is the most complex configuration and enables the catalyst to be continuously removed for regeneration and replaced after regeneration. dehydrocyclization. and fixed-bed types. Sulfur is generally removed from the feedstock by use of . The semi-regenerative process is the simplest configuration but does require that the unit be shut down for catalyst regeneration in which all reactors (typically four) are regenerated. the product contains appreciable amounts of unstable unsaturated compounds. and olefin polymerization take place on the acid catalyst sites. Although subsequent olefin reactions occur in thermal reforming. The fluid-bed and moving-bed processes use mixed non-precious metal oxide catalysts in units equipped with separate regeneration facilities. diethanolamine. fluid-bed. occasional. and hydrocrackingtake place on the one catalyst. Hydrogen sulfide is a reversible poison for platinum and causes a decrease in the catalyst dehydrogenation and dehydrocyclization activities. and cracking. In the presence of catalysts and hydrogen (available from dehydrogenation reactions). The olefins are hydrogenated with or without isomerization. Catalyst regeneration involves burning off the coke with oxygen. Olefins that do not undergo dehydrocyclization are also produced. The benefits of more complex configurations are that operating severity may be increased as a result of higher catalyst activity but this does come at an increased capital cost for the process. There are several types of catalytic reforming process configurations that differ in the manner that they accommodate the regeneration of the reforming catalyst. isomerization. The cyclic configuration uses an additional swing reactor that enables one reactor at a time to be taken off-line for regeneration while the other four remain in service.Ch. In the first catalytic reformers the hydrogen sulfide was removed from the gas cycle stream by absorption in. dehydrogenation. so that the end product contains only traces of olefins.

but feeds such as coker naphtha may contain around 50 ppm nitrogen and removal of this quantity may require high-pressure hydrogenation (800 to 1000 psi) over nickel–cobalt–molybdenum on an alumina catalyst. which readily give aromatic gasoline. The yield of gasoline of a given octane number and at given operating conditions depends on the hydrocarbon types in the feed. The end point of the feed is usually limited to about 190 °C (375 °F). which depend on the more difficult isomerization. high-naphthene stocks. Mild processing conditions are employed so that only the more . Dehydrogenation is a main chemical reaction in catalytic reforming. require more severe conditions and give lower gasoline yields than the naphthenic stocks. Paraffinic stocks. and hydrocracking reactions.CATALYTIC REFORMING a conventional desulfurization over a cobalt–molybdenum catalyst. catalytic reforming processes are unique in that they are the only petroleum refinery processes to produce hydrogen as a by-product. An excess of hydrogen above whatever is consumed in the process is produced. hydrocracking. An additional benefit of desulfurization of the feed to a level of <5 ppm sulfur is the elimination of hydrogen sulfide (H2S) corrosion problems in the heaters and reactors. Straight-run materials do not usually present serious problems with regard to nitrogen. and as a result. 1. thus extending its operating life. partially because of increased coke deposition on the catalyst as the end point during processing at about 158 °C (278 °F). and hydrogen gas is consequently produced in large quantities. and this neutralizes acid sites on the catalyst and thus represses the activity for isomerization. The hydrogen is recycled through the reactors where the reforming takes place to provide the atmosphere necessary for the chemical reactions and also prevents the carbon from being deposited on the catalyst. are the easiest to reform and give the highest gasoline yields. For example. Limiting the feed end point avoids redistillation of the product to meet the gasoline end-point specification of 205 °C (400 °F). Organic nitrogen compounds are converted into ammonia under reforming conditions.6 FEED TREATMENT BY HYDROGEN Nondestructive or simple hydrogenation is generally used for the purpose of improving product quality without appreciable alteration of the boiling range. and dehydrocyclization reactions. however. dehydrocyclization. maximum.

is removed by steam. Most processes employ cobalt– molybdena catalysts which generally contain about 10% of molybdenum oxide and less than 1% of cobalt oxide supported on alumina. Reactor operating conditions range from 205 to 425 °C (400 to 800 °F) and from 50 to 800 psi. depending on the application. Unstable compounds which might lead to the formation of gums. cobalt–molybdenum–alumina. The catalyst is not usually regenerated. and the finished product leaves the bottom of the stripper tower. It can be applied to lubricating oils. formed by the hydrogenation reaction. . After passing through the reactor. may be a mixed-phase reaction.Ch. Nitrogen. or insoluble materials. naphtha. Higher-boiling feedstocks. nickel oxide– silica–alumina. are converted to more stable compounds. hydrogen sulfide. The feedstock is heated in a furnace and passed with hydrogen through a reactor containing a suitable metal oxide catalyst.6. the treated oil is cooled and separated from the excess hydrogen which is recycled through the reactor. such as cobalt and molybdenum oxides on alumina. and platinum–alumina. together with hydrogen in the presence of catalysts such as tungsten–nickel sulfide. respectively. 1. Hydrotreating. while the hydrogen pressures are about 500 to 1000 psi. The treated oil is pumped to a stripper tower where hydrogen sulfide. vacuum. sulfur.1 Hydrofining Hydrofining is a process that first went on-stream in the 1950s and is one example of the many hydroprocesses available. and maximum sulfur removal require higher temperatures and pressures. high sulfur content. and gas oils. or flue gas. and water. The reaction generally takes place in the vapor phase but. and oxygen compounds undergo reaction with the hydrogen to remove ammonia. it is replaced after about one year’s use.1 BASIC PRINCIPLES unstable materials are attacked.2). and depend on the kind of feedstock and the degree of treating required. Figure (1. is carried out by charging the feed to the reactor. The temperatures employed are in the range of 260 to 345 °C (500 to 655 °F).

Petroleum Refining Processes. (From OSHA Technical Manual.CATALYTIC REFORMING Figure (1.) . Section IV.2). A distillate hydrotreater for hydrodesulfurization. Chapter 2.

Ch.2 The Catalytic Reforming Process .

even lower pressures were achieved: 3 bar.CATALYTIC REFORMING 2. the catalyst was being regenerated after a few months of operation. During 50s and 60s. catalysts were improved allowing lower operating pressures of about 30 bar. These modification didn't stop in the past and will . It was a semi-regenerative process.in the late 60s . In the late 80s.  Minimum vapor pressure to avoid vapor lock problems. The hydrogenation reaction favors lower operating pressures to enhance the production of aromatics from naphthenes.when storing and shipping caused by unstable olefinic compounds. the third major modification occurred when the continuous regeneration was introduced in the catalytic reforming units.  Minimum tendency to produce smoke or smog and low carbon deposition into cylinder caused by high boiling fractions in the gasoline composition. Cyclic regeneration was introduced by EXXON using the same type of catalyst ( Pt/chlorinated Al2O3 or Pt on silica alumina ). That was before the use of bimetallic catalysts . These continuous modifications of catalysts caused the operating conditions be more sever.which allowed lower operating pressures. In the early 70s. higher RON and space velocity and an effort to get better yield. They used catalysts with alumina as a support and chromium or molybdenum oxides as active elements and were implemented in fixed or moving bed reactors. This catalyst allowed the operation to be carried out at pressures of approximately 70 bar. But a great turning point happened in the beginning of 50s when UOP developed the "Platforming" process based the use of a platinum catalyst on chlorinated alumina. A large number of catalytic reforming processes were operational during the II World War. This allowed pressures of approximately 10 bar.1 INTRODUCTION The catalytic reforming process is designed to transform the low octane number constituents in the gasoline composition into very high octane rating aromatics in the range of 6 to 10 carbon atoms.  Minimum capacity to form gums . This process aims to enhance the properties of gasoline to satisfy some basic specifications such as:  Maximum Octane Number by increasing aromatic and isomer contents.

But values lower than 100 ppm are found in a few particular crudes (Hassi Messauod. visbreaking or coking gasolines can be sent to reforming which are characterized by – in comparison with SR feeds – a high olefin and acid sulfur content and larger amounts of nitrogen compounds. depending on the origin of the crudes. Table (2. The average molecular weigh is about 115. These SR feeds contain limited amounts (a few ppm) of nitrogen in the form of amines.Ch. arsenic are found in some crudes. or oxygenated compounds in the form of phenol or carboxylic acid. Heavier feeds than the heavy naphtha causes formation of carbon deposits on the catalyst and partially deactivate it. then it may be necessary to increase the amount of feed processed in reforming. it is clean since it is free of sulfur and nitrogen compounds because the use of hydrogen in the hydrocracking process works as a hydrotreating process. by using cuts distilling in the same range of SR naphtha which is produced from conversion units and have low octane number. In some cases. Sulfur is present in the feed in the range of 500 and 350 ppm.2 The Catalytic Reforming Process continue in the future with more and more sever operating conditions and producing gasoline with higher specifications.160 °C). mercury and. For instance. Its is characterized by significant olefins and aromatics concentrations as well as by the presence of molecules containing heteroatoms such as S or N. For instance.90 °C) tends to crack forming butane and light gases causing a lose in yield.1) gives the composition of two typical feeds. which are representative of straight run gasolines (SR) coming from atmospheric distillation of crude. hence it is not economical. for example). Light naphtha (C5+ . traces (<1 ppm) of metals or metalloids can be found in the feed. The RON is low: 50 for the paraffinic feed and 66 for the naphthenic feed. more seldom. Hydrocracking gasoline is another feed. If the "Octane Barrel" requirements can't be met by reforming heavy naphtha (90 . 2. centered around C8. . The reason for the use of heavy naphthas as feeds for Catalytic Reforming is that the ease of cyclization and isomerization reactions in the process increases with the increase of carbon atoms. FCC gasoline is another possible feed . but such a feed is mainly made up of cyclopentane-structure naphthenes and isoparaffins.2 FEED TO CATALYTIC REFORMING The typical feed to the catalytic reforming process is the heavy straightrun gasolines (HSR) or naphthas (90 °C to 160 °C).

Figure (2. Paraffins from the feed and from olefins saturation are essentially isomerized to iso-paraffins and. to some extent. S (weight ppm) Naphthenic (Nigeria) 66 119 350 29. In addition to the reformate. As a result of the reactions taking place during the process.3 61.3 PRODUCT FROM CATALYTIC REFORMING As stated before. reformates consist – mainly – of branched paraffins and especially aromatics. cyclized to the corresponding naphthenes.CATALYTIC REFORMING Paraffinic (Arabian Light) RON Av. . most of which have fewer than 10 carbon atoms. the main objective of any reforming process is to increase the octane number by increasing the aromatic content in the gasoline.85 50 114 500 66.85 8. the reactions produce considerable amounts of gases such as Hydrogen.8 11. Ethane. Mw. Propane and (i + n) Butanes. The composition of two typical feeds. Methane.4 Paraffins Naphthenes Aromatics Table (2.1). Naphthenes are then dehydrogenated to aromatics. 2.8 21. Aromatics of the feed are essentially left without change. Olefins are saturated to form paraffins by hydrogenation.1) shows the total changes taking place in the reformer to produce the desired aromatics and isoparaffins.

ethane propane and butanes.5 Table (2. In the last few decades the importance of the production of hydrogen.0 82.1 4. The desired products account for 85% weight and the ones with lower added value represent less than 5% weight (methane and ethane).2 6. RON = 98 P = 15 bar.Ch. Typical yields on a Middle Eastern feed. Products H2 CH4 C2H6 C3H8 (i + n) C4H10 C5 + % wt/feed 2.2 The Catalytic Reforming Process Figure (2. has risen gradually with pressures going down to 10 bar and less as a result of improving catalysts.1). 2.5 1. but also a little amount of methane. . hydrogen.1 The Typical Yield As mentioned before.2) gives an average product distribution from a paraffinic feed on a bimetallic at 15 bar and RON = 98. Table (2.3. Total changes to produce iso-Paraffins and Aromatics. catalytic reforming produces C5+ gasoline.7 3. beside C5+.2).

3. This is because the C6.13 0 0.gr = 0.76 iP P 0.4 0.35 0.08 0 0 1.76 0.3) shows a typical analysis for a low pressure reformate.66 10.CATALYTIC REFORMING 2.85 S ≤ 0. Analysis for a low pressure reformate ( % wt ). but increasingly it is limited to C7.55 69.69 2.83 33.04 0. Table (2. High pressure reformates contain few olefins.01 0. O: olefins.02 28.07 1.98 8. The reformate is basically made up of C6 to C10 aromatics. The aromatics concentration is directly related to the desired research octane number. as indicated in figure (2. especially C5.88 5. However.35 0. The RON is related to the aromatics concentration as indicated in figure (2. It should be noted that to achieve RON = 98.2). since the RON is the fixed parameter for the run.44 0. It is important also to note that reformates don't contain any sulfur (S ≤ 0. C8 and C9.28 21. These olefins lower the MON of gasolines and often make hydrogen purification more complicated.1 ppm. The octane rating in a reformate is generally provided by C7 to C10 aromatics and by light iso-paraffins. Number of carbon atoms 4 5 6 7 8 9 10 11 Total nP 0. there are more and more olefins.3).42 4. RON = 98 sp.57 100 nP: normal paraffins.34 0 0 0 0.5 1. iP: branched paraffins. A: aromatics Table (2.08 4.28 0.2 Reformate Composition Olefins and naphthenes concentrations are lower than 1% wt except for low pressure reformates which approach 1% wt.13 22.26 0.16 26.57 1.16 0.02 21.51 1.46 5.77 O N A Total 2.37 1.91 1.16 0.1 0. N: naphthenes.57 3.3 0. in modern units running at low hydrogen partial pressure. .11 0.19 0.93 2.35 25. the aromatic content should be close to 70% wt. P: total paraffins.34 14.97 8.07 0 7.92 6. C7 and C8 isoparaffins are not very branched and so they have a low RON.3).17 3.1 ppm).

4) lists the main administrative specifications in effect for Eurosuper in the first of January 2000. Figure (2.2). Relationship between the RON and % aromatics in the reformate.2 The Catalytic Reforming Process 2.3. the mandatory presence of oxygenated compounds (oxygen content ≥ 2% wt). . Developments are expected with respect to the maximum allowable sulfur (≤ 50 ppm).Ch. Also expected is a reduction in the end point in order to lower the heavier aromatics concentration along with a limit on high volatility C4-C6 olefin concentrations. whose effect on ozone production has been demonstrated.3 Reformate Specifications Table (2. and a more stringent limit on total aromatics (≤30% wt).

CATALYTIC REFORMING Figure (2.8 Sulfur max (ppm) 150 Lead (g/l max) 0. Properties Values RVP (kpa) max 60 Distillation (% vol min) at 100 °C 46 at 150 °C 75 Benzene (% vol max) 1 Aromatics (% vol max) 42 Olefins (% vol max) 18 Oxygen content (% wt max) 2. but mainly to prevent large-scale formation of naphthalene derivatives which color the reformate and cause rapid catalyst deactivation. The end point is limited. Main Specifications for Eurosuper (January 2000).005 Table (2. .5) shows the ASTM distillation analysis for the same low pressure reformate discussed above. to comply with the corresponding gasoline specification.4).3). Olefin content in the reformate. usually to around 205 °C. Table (2.

and in Germany. by nitration. The catalysts of chromium and molybdenum oxide could not compete with platinum catalysts and were gradually abandoned. The continuously improved performances were the result of modified process conditions with the corresponding modifications in the unit design and the use of bi. The high octane rating of the reformed gasoline.and poly-metallic catalysts. including the processes in moving bed or fluidized bed.1 ppm. which was necessary during World War II for the production of trinitrotoluene. the evolution of the UOP process ‘‘Platforming. despite improvements achieved over the years. discovered by Moldavschi and Kamusher in 1936.’’. the process was used especially for producing toluene.4 1.Ch.1 Table (2. They used a catalyst of molybdenum or chromium oxide on alumina.gr = 0. Distillation characteristics of a low pressure reformate.85 S ≤ 0. under the name of Hydroforming. under the name of D.D. the efficiency of the process. The first catalytic reforming unit using platinum catalyst on Al2O3 support was built by Dutch Refining in 1949.4 CATALYTIC REFORMING TECHNIQUES The first commercial units of catalytic reforming were built practically simultaneously in the United States. At the time. in November 1940.2 The Catalytic Reforming Process % distilled IBP 5 10 20 30 40 50 60 70 80 90 95 EP % distilled % residue % losses °C 56 83 92 103 113 121 128 135 142 150 160 168 194 98. 2. RON = 98 sp. As an example.5).H. and the broad availability of feedstock (naphtha) contributed to make Platforming in a .5 0.

The fixed bed could be operated whether cyclic or semi-regenerative.S. the process was capable of satisfying the increasing market requirements in the conditions of the gradual prohibition of the leaded gasoline. In January 1990. placing it in second place in the production of gasoline.278 2.380 2.CATALYTIC REFORMING relatively short period of time.850 480 850 470 12.654 329 640 404 11. These different types of configurations are going to be discussed in details in the following sections.6). In addition.746 429 790 429 12.700 2. after catalytic cracking with 539.I. the position of catalytic reforming increased strongly for the production of aromatic hydrocarbons. the premier process for high octane gasoline. .450 2. The evolution of reforming capacities from 1990–2010 is shown in Table (2. Fixed-bed type. through continuous improvements. Fluid-bed type. Latin America Middle East Africa Total a 1990 4.5 million tons/year.700 1. Moving bed is only operated continuously.500 3.9 million tons/year (excluding the former Eastern Block). according to the time required to regeneration.100 690 15. Region North America Western Europe Pacific Rim and South Asia Eastern Europe and C.420 2.268 1.017 1.163 2000 4.360 1.273 1998 4. 3. the worldwide Platforming capacity was 373. 2. Table (2. Moving-bed type.386 2.050 1.090 naa naa 311 530 8.400 600 1. Evolution of Reforming Capacity from 1990–2010 (thousands bpsd). feedstocks for the petrochemical industry.487 2.440 Not Available.6).333 2. At the same time. It provides almost all the world’s need for xylenes.810 2010 4.766 1995 4. The different technologies basically involve three configurations: 1.

the cost of recycle hydrogen compression became a non-negligible item.which have simple internals and therefore less costly . The evolution toward continuous reforming and the implementation of continuous catalyst circulation imposed the radial type of low-pressure drop reactor once and for all. which involves the regeneration of a part of the catalyst after its deactivation (occurs in days). with no shutdown of the unit.4.Ch. Reactors are built of low-alloy carbon steel that can withstand hydrogen corrosion and oxidizing atmosphere during regeneration and oxychlorination operations.2 The Catalytic Reforming Process 2. in which the spent catalyst is replaced without regeneration in the end of its life (months). the pressures used were greater than 50 bar and reactor pressure drop had little influence in comparison with total pressure drop. The fixed bed configuration has two different types of runs:  Non-regenerative.were chosen to implement the process at these times.4. Figure (2. This is why axial reactors . .4) shows the two types of reactors.  Semi-regenerative. which involves the total regeneration of all the catalyst after finishing the running period (usually years).  Regenerative (Cyclic). while the feed is passed over it until the time of regeneration.1 Fixed-Bed Technology This is the oldest technology. pressure drop in the reactors became significant in relation to the total pressure drop. Radial reactors made their appearance some time in the seventies at the same time of the appearance of the bimetallic catalysts that allow operation at pressures lower than 25 bar. with the unit being shutdown during regeneration. during switching the operation to a substitute (swing) reactor. The fixed bed configuration implies that the catalyst is fixed in its location in the reactor.1. 2. Here.1 Type of reactors In the beginning. In addition. The trend toward a total pressure of 3 bar left no other choice.

4. but it is expensive and lacking in flexibility. Reactor types. 15 . 2. catalytic reforming involves mostly endothermic and equilibrated reactions whose rates differ by a factor of 50.2 Reactor Configuration As mentioned earlier.30% (R2) and 55 . Each ( furnace + reactor ) group takes reaction rates into account.5) shows a simple reactors layout. The figure also shows the variation in temperature in the reactors: significant drop in R1. smaller drop in R2 and finally less variation in R3. Figure (2. while F3 is small but R3 is large. Differences in rate between cyclohexane dehydrogenation. cyclopentane hydroisomerization-dehydrogenation and paraffin dehydrocyclization as a ratio is approximately 50/5/1. The aromatics concentration rises gradually. Catalyst distribution among the three reactors is usually around 15% (R1). A set of isothermal reactors with a heat input could have been the solution.60% (R3). the final is a series of 3 or 4 ( furnace + reactor ) groups depending on the type of feed: 3 for paraffinic feeds and 4 for naphthenic feeds. . As a result.CATALYTIC REFORMING Figure (2.4). where the endothermicity of dehydrocyclization is partially offset by the exothermicity of cracking. F1 is large and R1 is small.1. since the two reaction rates are comparable. The choice of adiabatic reactors in conjunction with furnaces was eventually made.

R3.Ch. Variation in temperature in reactors R1.5): A. F3) and reactor (R1. B. Furnace (F1. R2. F2. R2. Variation in effluent composition (paraffins-naphthenes-aromatics) in the reactors. R3) layout.2 The Catalytic Reforming Process Figure (2. C. .

The advantages of operating at a higher severity.1. 2. which blocks the metals and produces ammonia.  The catalyst becomes rapidly deactivated in the absence of hydrogen. and needs to be dried. For this reason.3 Non-Regenerative Process The non-regenerating system was used in the first type of catalytic reforming unit. the units are not provided with the means for regenerating the catalysts. oxygen. On contrary of. eliminated in the purification section.e. The coked catalyst is replaced and sent off-site for regeneration.and sulfur-containing compounds and metals. i. Ancillary units are designed to allow optimum use of catalysts and to offset some of their drawbacks:  The catalyst is sensitive to impurities: nitrogen-. The reactor configuration is the same as described earlier in the previous section.4.. Figure (2.4 Semi-Regenerative (SR) Fixed Bed Process This type of process is given its name because catalyst regeneration causes the unit to be shut down at the end of the run. so high hydrogen partial pressure is created (H2/HC > 8 for monometallic catalysts) by compressing and recycling part of the hydrogen produced during the reaction. The feed can be further treated on molecular sieves to knock out the few ppm of residual water and also on a sulfide compound trapping agent. The semiregenerative system provides a total duration of catalyst utilization of about 7–10 years and even longer. non-regenerative process which send the spent catalyst offsite to be regenerated outside the system. at lower pressure led to switching the non-regenerative units to semi-regenerative ones. dehydrochlorinated and desulfurized on specific . The feed is purified by hydrotreating. It may contain some impurities : water. hydrogen sulfide and water. a feed purification section must be provided. hydrochloric acid and sometimes H2S. Operation at high pressure (above 35 bars) ensured a catalyst life of over 10 months when using as feed a naphtha with final boiling point between 192–205 °C.4. Consequently. Deactivation is considerably reduced by hydrogen. the ‘‘Platforming’’ of UOP. The necessary equipments are added for the regeneration of catalyst without its removal from the system.1.6) shows a semiregenerative process flow scheme.CATALYTIC REFORMING 2.

The operation of the unit can be cyclic. The regeneration of the catalyst is carried out at short time intervals. the four reactors are of the same size and are located in position R1. Here. ultra-cooling. on average 5-15 days. is coupled. was carried out by using an extra reactor. separation systems of varying degrees of complexity will be implemented to get relatively pure hydrogen and high gasoline recovery: a simple separating drum. occasionally when regeneration becomes necessary. this means a lower pressure in the reaction system. Depending on the operating pressure. The regeneration of the catalyst without stopping the operation of the unit allows for a higher severity than that in the semi-regenerative system. In .2 The Catalytic Reforming Process adsorbers.  Finally. The reactor of the last step is regenerated more often. to avoid shutting down units. In general.Ch. This line up requires installation of a regeneration system and doesn't always allow the regenerated catalyst to be restarted in optimum conditions.5 Regenerative (Cyclic) Process An initial solution. or to a higher yield of reformate for a given octane rating. the catalyst produces light C1 to C4 hydrocarbons in addition to hydrogen. That also allowed the use of higher reactor inlet temperatures that may reach 550 °C.1. Such operation can lead to octane ratings higher by approximately 5 units than the semi-regenerative system. 2. which leads to a higher octane rating at equal yield. The first plant of this type was patented in 1953 and built in 1954 under the name of ‘‘Ultraforming’’ by Standard Oil of Indiana (Amoco). Such installations are mainly used during start up but not only. or in a swinging mode where the spare reactor (swing reactor). etc. a mode of operation in which one of the reactors is constantly under regeneration. re-contacting purification systems. With a complex valve system. the additional reactor occupies a central position on the platform of the industrial plant in order to shorten the length of the connecting lines. and they are separated from the reformate in a stabilization section.4. R3 alternatively. R2. In many designs. three reactor can be running while the fourth is being regenerated.

After 4 to 16 h on process cycle. the regenerative system represented 22% of the total capacity of catalytic reforming units operated in the United States.1.1 Hydroforming The hydroforming process made use of molybdena–alumina (MoO2– Al2O3) catalyst pellets arranged in fixed beds. Worldwide at the end of 1982. Naphtha feed was preheated to 400 °C to 540 °C (900 °F to 1000 °F) and passed in series through the two catalyst cases under a pressure of 150 to 300 psi. Compared with the semi-regenerative units. The hydroformer had four reaction vessels or catalyst cases.6. The air also re-oxidized the reduced catalyst (9% molybdenum oxide on activated alumina pellets) and removed sulfur from the catalyst. In January 1984. Figure (2. The material leaving the final catalyst case entered a four-tower system where fractional distillation separated hydrogen-rich gas. This was done by burning carbon deposits from the catalyst at a temperature of 565 °C (1050 °F) by blowing air diluted with flue gas through the catalyst.4. 2. Gas containing 70% hydrogen produced by the process was passed through the catalyst cases with the naphtha. a product (reformate) suitable for motor gasoline and an aromatic polymer boiling above 205 °C (400 °F).7) shows a schematic flow of EXXON Powerformer. the other two were on the process cycle.CATALYTIC REFORMING 1956. while the ‘‘Powerforming’’ units had a total processing capacity of 220. hence the process is known as fixed-bed hydroforming.000 m3/day. with a total processing capacity of 84. the process ‘‘Powerforming’’ was patented and built by EXXON. there were 39 ‘‘Ultraforming’’ units in use. two of which were regenerated.6 Commercial Processes 2. their investment is about 10– 15% higher. .4. the catalyst was regenerated.1.000 m3/day.

2 The Catalytic Reforming Process Figure (2.Ch. . Semi-regenerative process flow scheme.6).

7). Powerformer flow scheme (Exxon). .CATALYTIC REFORMING Figure (2.

8). pellets of alumina containing chlorine and about 0. Such a system was developed by Chevron in the ‘‘Reniforming’’ process. Figure (2. it uses a Pt-Re catalyst that allows operating at low pressures.6. Further heat is added to the naphtha between each of the catalyst cases in the series.Ch. for the protection of the catalyst against compounds of S.2 The Catalytic Reforming Process 2. 2. The first unit of this type was built in 1953. The prepared naphtha feed is heated to 455 °C to 540 °C (850 °F to 1000 °F) and passed into a series of three catalyst cases under a pressure of 200 to 1000 psi. For motor gasoline manufacture. N. must be scrubbed free of its hydrogen sulfide content. The catalyst is composed of 1/8 in.3 Platforming The first step in the platforming process. was patented by Houdry in 1951.6. The distinction is that the purification is made by adsorption. which is cycled through the catalyst cases. The guard reactor used the same catalyst as the main reaction system. before the classical reaction system.1.4.2 Houdriforming The introduction of an additional reactor followed by a stripping column.5% platinum. is current practice. The material from the final catalyst case is fractionated into a hydrogen-rich gas stream and a reformate stream. is the preparation of the naphtha feed.1. Otherwise. and O. The heavy naphtha passes through an adsorber before being mixed with recycle hydrogen. the hydrogen-rich gas produced by the process .4. The subsequent practice of hydrotreatment of the feed to catalytic reforming eliminated the need for such a solution. . As sulfur adversely affects the platinum catalyst. the naphtha feed is distilled to separate a fraction boiling in the 120 °C to 205 °C (250 °F to 400 °F) range. As suggested by the name of the process. the naphtha fraction may be treated to remove sulfur compounds. The purification of the feedstock within the unit before the reactors.

Platforming Process. on a blockout basis. The cyclic process assures a continuous supply of hydrogen gas for hydrotreatment operations and . and silica–alumina (SiO2–Al2O3) composition.7).8).CATALYTIC REFORMING Figure (2. It is possible to regenerate the catalyst. but it is usual to replace the spent catalyst with a new catalyst. A guard bed catalytic hydrogenation pretreating stage using the same Houdry catalyst as the Houdriformer reactors is available for high-sulfur feedstocks. Each pound of catalyst reforms up to 100 bbl of naphtha before losing its activity. Other fixed-bed processes include Catforming. Thus. the plant need not be shutdown to regenerate the catalyst. Reforming takes place in several (usually four or five) reactors and regeneration is carried out in the last (swing) reactor. Lead and copper salts are also removed under the mild conditions of the guard bed operation. Regeneration to prolong catalyst life is practiced on a block-out basis with a dilute air in-stream mixture. In addition. in which the catalyst is platinum (Pt).6. figure (2. is based on frequent regeneration (carbon burn-off) and permits continuous operation.4 Powerforming The cyclic Powerforming process.1. if necessary. 2.4. alumina (Al2O3). Houdriforming is a process in which the catalyst may be regenerated. which permits relatively high space velocities and results in very high hydrogen purity.

Choice between the semi-regenerative process and the cyclic process depends on the size of plant required. The glycol solvent in the aromatic extraction section is designed to extract low-boiling highoctane iso-paraffins as well as aromatics.2 The Catalytic Reforming Process tends to produce a greater yield of higher octane reformate .9). The effluent coming out of each reactor goes through a furnace before entering the next one.6 Magnaforming The ‘‘Magnaforming’’ system. and higher space velocities are used.6. 2.1 Reactor Configuration Although the moving bed was used on MoO3/Al2O3 type catalyst before 1940. where three or four reactors are located one on top of the other.6. Since in the latter and especially the last reaction steps the danger of coke formation is higher.1.5 Rexoforming Rexoforming is a combination process using platforming and aromatic extraction processes in which low-octane raffinate is recycled to the platformer. 2. 2.2. its use on platinum-alumina catalysts came into being only in the early seventies. so that the ratio reaches normal values in the latter reaction steps. Operating temperatures may be as much as 278 °C (508 °F) lower than conventional platforming. built by Engelhard Corp. and the octane number needed in the product.4. type of feedstocks available. figure (2.Ch. The catalyst moves downward by gravity .2 Moving-Bed Technology 2. UOP put a continuous regeneration system on the market. This is followed by the injection of additional hydrogen-rich recycle gases. The advantage of the system is that it favors the aromatization and the dehydrocyclization in the first two reaction stages as a result of the reduced (H2/hydrocarbon) ratio that displaces the thermodynamic equilibrium in the desired direction.4..4. is characterized by a small hydrogen/feed molar ratio in the first two reaction steps. A balance is struck between hydrocyclization and hydrocracking. excessive coke and gas formation thus being avoided.4. the (H2/hydrocarbon) ratio is increased to prevent this occurrence.1.

CATALYTIC REFORMING

from R1, to R2 then R3, loaded with coke, by a lift to the top of the regenerator. It goes through the regenerator by gravity then sent back to the top of R1. The rest of the unit flow scheme is very close to the fixed bed process. The technology developed by IFP uses the conventional SR reformer layout of "side by side" reactors. The catalyst at the bottom of each reactor is raised by lifts to the top of the following reactor. From the last reactor it goes to the regenerator, figure (2.10), and then back to the top of the first reactor. UOP regeneration is continuous, while IFP's can be either continuous or batch.

2.4.2.2 Advantages of the Moving Bed
The introduction of moving bed technology has had the following effects:  Reformates are produced with a very high octane number even from difficult feeds and without any run duration problems.  Units are operational all year round, regularly producing the hydrogen that modern refineries constantly need.  Catalysts are less stable over time but more selective, making it possible to improve yields.  Recycle rates are lower, thereby improving yields and reducing operating costs.  Operating pressures are significantly lower and this is highly favorable for the reformates and the hydrogen yields. Generally, as shown in figure (2.11), pressure has gone from P = 35 bar and H2/HC = 7 to P = 3 bar and H2/HC = 2 with yield gains of nearly 10 points for C5+ and over 1% for hydrogen.

Ch.2 The Catalytic Reforming Process

Figure (2.9), Continuous regeneration reformer (UOP: "CCR" Platforming).

CATALYTIC REFORMING

Figure (2.10), Continuous regeneration reformer (IFP: Octanizing). Catalyst circulation regenerator.

The catalyst regeneration system consists of four interdependent zones: primary combustion. until the catalyst exits the last reactor where it is lifted to the top of the regenerator. final combustion. 2. and calcination. Both solutions involve the addition of extra moving-bed equipments to narrow the gap between the fixed.4. The first solution is called "Dualforming" and the second is called "Dualforming Plus". This is useful for systems with circulating catalyst such as Dualforming.3. Various types of reforming units.2. and Octanizing.2 The Catalytic Reforming Process Figure (2.11). IFP also developed two solutions for the problem of revamping the existing old semi-regenerative processes.10).Ch. The agent of transport is hydrogen between reactors and nitrogen between the reactor and the regenerator. as shown in Figure (2. The catalyst discharged at the bottom of a reactor is conveyed by a stream of gas. For the production of aromatic hydrocarbons. Procatalyse offers the bimetallic catalyst CR201 in the form of spheres with high resistance to attrition. . Dualforming Plus.4.2. Procatalyse offers the catalysts AR401 and AR405.and the moving-bed techniques. oxychlorination. through lift lines and is introduced at the top of the next reactor and so on.1 IFP "Octanizing" Process The French Institute of Petroleum developed a process with integral circulation of the catalyst named "Octanizing".3 Commercial Processes 2.

partially coked catalyst in the reactors is continuously replaced with catalyst that has been freshly regenerated in an external regenerator (CCR section) to maintain a low average coke for the reactor catalyst. The CCR Platforming unit uses a UOP-patented reactor stack. continuous high-selectivity and high-activity characteristics associated with new catalyst can be achieved at significantly higher severities than with the SR Platforming process. This configuration eliminates the need to lift the catalyst between reactors.4. In contrast. a SR Platforming unit operates at a severity that steadily builds coke up on the catalyst surface over the length of a cycle (6 to 18 months). figure (2. catalyst is lifted only twice during each cycle: from the bottom of the reactor stack to the top of the regenerator and then from the bottom of the regenerator back to the top of the reactor stack. In the CCR Platforming unit. and yield remains constant at fresh catalyst levels.9). Eventually. used in the IFP "Octanizing" unit. The first UOP Platforming unit went on-stream in 1949. and this flow simplifies catalyst transfer and minimizes attrition. Catalyst transfer rates have been designed from as low as 91 kg/h (200 lb/h) to as .3. This increasing market demand required refiners to operate their Platforming units at ever higher severity.CATALYTIC REFORMING 2. The catalyst transfer requires no operator intervention. with a modern CCR Platforming unit. the catalyst is regenerated approximately every 3 days. For example. and the need to regenerate catalyst at shorter and shorter intervals became a serious limitation of the SR Platforming units. yields decline.2. The Platforming process has since become a standard feature in refineries worldwide. The catalyst flows gently by gravity downward from reactor to reactor. at which point the unit is shut down and the catalyst regenerated. improvements in the catalyst and process could not keep up. UOP developed the CCR Platforming process. Historical Background In the years following the invention of Platforming. Reactor Configuration In a conventional SR Platforming unit. the reactors are configured side-by-side. which leads to a great simplification of the process. it will be discussed in some details. to overcome this limitation. Throughout the cycle. Thus. For this reason. The reactors are stacked one on top of another to achieve a compact unit that minimizes plot area requirements. the need for high-octane gasoline blend components and the demand for aromatics for petrochemicals steadily increased. In the CCR process.2 UOP "CCR" Platforming Process The Platforming® process is a UOP®-developed and -engineered catalytic reforming process in widespread use today throughout the petroleum and petrochemical industries.

Thus. Catalyst flows to the regeneration tower.000 BPSD. Improvements are continuously being made in the CCR regeneration section design. The regeneration and reactor sections of the unit are easily isolated to permit a shutdown of the regeneration system for normal inspection or maintenance without interrupting the Platforming operation. .  52 units operating at state-of-the-art reactor pressure of 75 lb/in2 gage.1 million barrels per standard-day (BPSD).  4. and African naphthas and hydrocracked stocks with capacities ranging from 150 to 60.5% of all CCR Platforming units ever started up still operating. The catalyst flows by gravity from the last reactor into an integral (to the reactor) catalyst collector vessel. UOP Commercial Experience UOP has designed more than 730 Platforming (both SR and CCR) units around the world with a total feedstock capacity of more than 9. where the catalyst is reconditioned. CCR System The ability to continuously regenerate a controlled quantity of catalyst is the most significant innovation of the CCR Platforming unit.Ch.S.000 BPSD CCR Platforming unit operating capacity.000. As of mid-2002.  99. UOP introduced the CycleMax® regenerator in 1995 which combines new innovations with the best aspects of previous CCR designs at lower cost. The catalyst is then lifted by either nitrogen or hydrogen lifting gas to a catalyst hopper above the regeneration tower.2 The Catalytic Reforming Process high as 2721 kg/h (6000 lb/h). The feedstocks range from benzene-toluene (BT) cuts to fullrange. Research octane numbers run from 93 to 108 over a wide range of catalysts. depending on the capacity and the operating severity of the Platforming unit. the reactors are continuously supplied with freshly regenerated catalyst. UOP unparalleled commercial experience included:  171 UOP CCR Platforming units operating around the world. and product yields are maintained at fresh catalyst levels. In addition to its atmospheric and pressurized regenerators. lean Middle East naphthas and rich U. The UOP CCR Platforming process is the most successful reforming process offered by any licenser. Regenerated catalyst is then returned to the top of the reactor stack by a transfer system similar to that used in the reactorregenerator transfer.  31 more UOP CCR Platforming units in design and construction.  82 units operating at or below 100 lb/in2 gage reactor pressure.

The process is built around a new type of catalyst called RZ-100.0%) on alumina catalyst.3. continuous regeneration with a separate or integrated reactor is practiced to maintain catalyst activity by coke and sulfur removal. Figure (2.and under-reforming operations. A molybdena (Mo2O3. activated with platinum.3 UOP "RZ" Platforming RZ Platforming is the latest development in UOP long tradition of reforming process improvements. Operating conditions in the reactor are about 200 to 300 psi and 480°C to 950°C (900°F to 950°F). The ability of the RZ Platforming process to convert light paraffinic feeds and its flexibility in processing straight-run naphtha fractions provide many options for improving aromatics production and supplying highly desired hydrogen.3 Fluid-Bed Technology In catalytic reforming processes using a fluidized solids catalyst bed.12) shows the RZ Platforming Process. is used. . not materially affected by normal amounts of arsenic.CATALYTIC REFORMING 2. resulting in more selectivity in the conditions needed for optimum yield of the desired product.2. or sulfur. Fluidized-bed operation with its attendant excellent temperature control prevents over. 2. The RZ process is ideally suited for use in aromatics production facilities especially when large amounts of benzene are required. iron. nitrogen. RZ-100 is a zeolitic catalyst.4.4. that gives the highest obtainable yields of benzene (B) and toluene (T) from naphtha feedstocks. 10. Cracked or virgin naphtha is charged with hydrogen-rich recycle gas to the reactor.

Ch. . The UOP "RZ" Platforming Process.12).2 The Catalytic Reforming Process Figure (2.

CATALYTIC REFORMING .

The rates of reaction vary considerably with the carbon number of the reactant. and examples of the individual reactions are shown in Figure (3. and cracking. This reaction takes place rapidly and proceeds essentially to completion.3 Process Chemical Reactions And Thermodynamics 3. 3. these multiple reactions occur in series and in parallel to one another. isomerization. is favored by high reaction temperature and low pressure. Because this reaction proceeds rapidly and produces hydrogen as well as aromatics. .1 Dehydrogenation of Naphthenes The principal Platforming reaction in producing an aromatic from a naphthene is the dehydrogenation of an alkylcyclohexane. and catalyst type. Figure (3.1). naphthenes are the most desirable component in the Platforming feedstock. The reactions are promoted by two kinds of active sites on the catalyst. Therefore. The generalized reaction network is illustrated in Figure (3. and is promoted by the metal function of the catalyst. operating conditions. acidic and metallic. dehydrocyclization.1).Ch.2). The extent to which each of the reactions occurs for a given Platforming operation depends on the feedstock quality.1 INTRODUCTION Platforming reactions can generally be grouped into four categories: dehydrogenation.2. Because the Platforming feed is made up of many paraffin and naphthene isomers. Generalized Platforming reaction network. The reaction is highly endothermic.2 PROCESS REACTIONS 3. multiple reforming reactions take place simultaneously in the Platforming reactor.

The reaction involves ring rearrangement. The paraffin isomerization reaction occurs rapidly at commercial operating temperatures. Dehydrocyclization is favored by low pressure and high temperature and requires both the metal and acid functions of the catalyst. the remaining aromatics become concentrated in the product.2. Because branched-chain isomers have a higher octane than straight-chain paraffins.CATALYTIC REFORMING 3. the reaction is similar to paraffin cracking. thereby increasing product octane. and thus ring opening to form a paraffin is possible. 3. Paraffin cyclization becomes easier with increasing molecular weight of the paraffin because the probability of ring formation increases.2.3 Dehydrocyclization of Paraffins The most-difficult Platforming reaction to promote is the dehydrocyclization of paraffins. As paraffins crack and disappear from the gasoline boiling range. . Thermodynamic equilibrium. Examples are converting ethylbenzene to toluene and converting toluene to benzene. Dealkylation of aromatics includes both making the alkyl group (a side chain on the aromatic ring) smaller and removing the alkyl group completely. Dealkylation is favored by high temperature and high pressure. Partially offsetting this effect is the greater likelihood of the heavy paraffins to hydrocrack. slightly favors the isomers that are more highly branched.2 Isomerization of Paraffins and Naphthenes The isomerization of an alkylcyclopentane to an alkylcyclohexane must take place before an alkylcyclopentane can be converted to an aromatic. and the net liquid product is reduced. 3. Isomerization reactions are promoted by the acid function of the catalyst. however.4 Hydrocracking and Dealkylation In addition to naphthene isomerization and paraffin cyclization reactions. hydrogen is consumed. respectively. the acid function catalyzes paraffin hydrocracking. Paraffin hydrocracking is favored by high temperature and high pressure. However. making this reaction undesirable. If the alkyl side chain is large enough. This reaction consists of molecular rearrangement of a paraffin to a naphthene.2. this reaction improves product octane.

3 Process Chemical Reactions And Thermodynamics Figure (3.2). Generalized Platforming Individual Reactions.Ch. .

The feedstock is a rich BTX naphtha with a paraffin.67 for methylcyclopentane at low pressure.81 for dimethylcyclopentane. In contrast.3 to 3. As the naphtha feed passes through the catalyst bed. The relative ease of isomerization to an alkylcyclohexane increases with increasing carbon number. only a small fraction of normal hexane is converted to aromatics. Because the hydrocracking rate for hexane is at least 3 times greater than the dehydrocyclization rate for hexane. Reactions of naphthenes in the feedstock show significant differences between the alkylcyclopentanes and the alkylcyclohexanes. For example.CATALYTIC REFORMING 3. naphthenes. the naphthene concentration approaches a low steady-state value. paraffin conversion is nearly linear across the reactor bed. a substantially greater conversion of normal heptane to aromatics occurs than for hexane. By the reactor outlet. Therefore. 34. one carbon atom higher. In contrast. The high rate of conversion of cyclohexanes is shown by the rapidly decreasing concentration of naphthenes in the first 30 percent of the catalyst volume. which represents the naphthene intermediary present in the paraffin dehydrocyclization reactions. The conversion of hydrocarbon types as a function of position in the catalyst bed for a moderate-severity Platforming operation is shown in Figures (3. This ratio increases to 0. Figure (3. and aromatics (PNA) content of 42. The competing reaction is decyclization to form paraffins.3). the ratio of alkylcyclopentane isomerization rate to total alkylcyclopentane reaction rate is 0. The rate of heptane dehydrocyclization is approximately 4 times that of hexane. and 24 wt %.6). the alkylcyclohexanes dehydrogenate rapidly and nearly completely to aromatics. The alkylcyclopentanes react slowly and follow two competing paths.4) illustrates the conversion of the three reactive species in the Platforming feedstock.3 RELATIVE REACTION RATE The primary reactions for the C6 and C7 paraffins proceed at vastly different rates. respectively. The relative rates of conversion are markedly . The remaining naphthene conversion occurs at a slower rate and is indicative of cyclopentane conversion and dehydrocyclization of paraffins through a naphthene intermediate. The desired reaction is isomerization to an alkylcyclohexane followed by dehydrogenation to aromatics. total aromatics concentration increases and the concentration of naphthenes and paraffins decreases as they undergo conversion Figure (3.

3). .Ch. which have a greater probability of isomerizing from a five. 90 percent of the cyclohexanes are converted.5) shows the relative reaction rate of cyclopentanes by carbon number. paraffins have the lowest reactivity and selectivity to aromatics and are the most difficult components to process in a Platforming unit. heavier components convert more easily and selectively to aromatics than do the lighter components. Cyclopentanes are much less reactive than cyclohexanes. In summary. but conversion is only 15 percent for cyclopentanes and 10 percent for paraffins. The relative ease of conversion associated with increasing carbon number for alkylcyclopentanes and paraffins explains why higher-boiling-range feedstocks are easier to process. the conversion of paraffins. Heavier components. Hydrocarbon Type Profiles. As a general rule. Figure (3. convert more readily than do the lighter components. As with the cyclopentanes. they still produce a significant amount of nonaromatic products. Alkylcyclohexanes are converted rapidly and quantitatively to aromatics and make the best reforming feedstock.3 Process Chemical Reactions And Thermodynamics different. The most-difficult reaction.to six-carbon ring. the heavier paraffins convert more readily than do the lighter paraffins. In the first 20 percent of the catalyst. Although alkylcyclopentanes are more reactive and selective than paraffins.6). is characterized by carbon number in Figure (3. Figure (3.

Cyclopentane conversion by carbon number. . Reactant-Type Conversion Profiles.CATALYTIC REFORMING Figure (3. Figure (3.4).5).

where a combination of paraffin dehydrocyclization and hydrocracking takes place. Table (3.1). and catalyst. the net heat effect in the reactor may be slightly endothermic or exothermic. Paraffin Conversion by Carbon Number.Ch.3 Process Chemical Reactions And Thermodynamics Figure (3. depending on processing conditions.4 HEATS OF REACTION Typical heats of reaction for the three broad classes of Platforming reactions are presented in table (3. In commercial Platforming units. 3. The dehydrocyclization of paraffins and dehydrogenation of naphthenes are endothermic. Heats Of Reactions. feed characteristics. .6).1). In the final reactor. as indicated by the large negative-temperature differentials observed. the majority of these reactions take place across the first two reactors.

CATALYTIC REFORMING .

many attempts were made to find a better performing system of catalyst. By time.Ch. An example of the empirical classification is given in Table (4. Most of the reforming catalysts are based on well-dispersed platinum on an alumina promoted by halogen. Nowadays the reforming process is generally carried out over bi-functional catalysts which consist of one or more metals. usually chlorine.1).1 INTRODUCTION Platinum-based reforming catalysts are used in the late of 1940. in 1960.1 Classification of Catalyst 4. On the other hand there are the active elements responsible for heterolytic or ionic activation of hydrocarbons (insulating oxides). Sn. most commonly platinum or platinum combined with rhenium or tin or iridium. their performance was improved by the addition of some metals such as Ge.1 Empirical Classification It distinguishes. and Ir.1.4 Catalytic Reforming Catalyst 4.1. on the one hand. and the possibility of operating at lower pressure. dispersed on an acidic support. These additions have given the catalyst a better selectivity. the active element causing homolytic or radical activation. a better stability of performance over time. Re.1. 4. Since 1970. .

.2 Explicative Correlations They relate catalytic properties of active elements alone or associated with the intrinsic properties of the active solid or with the interaction properties that the solid exhibits with the reaction medium.1.CATALYTIC REFORMING Table (4. sometimes only as traces. Active phase catalyst properties can be radically modified by adding promoters.1. The Empirical Classification of Catalyst. especially with the properties characterizing.1). absorption and adsorption. 4.

2. . Supported catalysts : The active phases of refining catalysts are usually consists of an active phase dispersed on an oxide support under control on a previously shaped oxide support.3.5% platinum and a promoter dispersed on a chlorinated γ alumina support. For Example: Catalytic cracking catalysts. 3. Catalysts resulting from unit operation : Combining shaping and the addition of an active phase or precursor salts. 4. In contrast to bulk catalysts the use of a pre-shaped oxide allows control of its genesis and especially the optimization of its textural.3 General Catalyst Characteristics and Properties 4. in gasoline and kerosene sweetening.1. structure.3. and heterogeneous oligomerzation catalysts.Ch.4 Catalytic Reforming Catalyst 4.1.1 Catalyst Activity Expresses reactant transformation rate under given operating conditions in several different ways. especially the operating temperature which can be relatively low. They are added in trace amounts in the reaction medium.1. mechanical and morphological properties.1 Basic Characheristics Three basic features characterize the catalyst's action: 4. For Example: catalytic reforming catalyst made up of approximately 0. homogeneous catalysts : Are produced from organo-metallic complexes interacting with an appropriate solvent medium. For Example: Claus catalysts.1.2 Main Types of active phases of Catalyst There are four types of active phases of catalysts: 1.good activity means a high reaction rate with two possible advantages:either a small amount of catalyst can be used or operating conditions can be less severe. 4. Bulk catalysts : Are exclusively made up of active phase.1. They are used especially in light olefin oligomerization for motor fuel production.

off site regeneration.1 Structural Properties The quality of sites dispersed on the active surface. is determined by the characteristics of the accessible active phase (structure.1.3.2.2 Textural Properties These properties govern the possibility of reactant access (by diffusion) to the above-mentioned sites as well as the possibility of evacuating the reaction products outside by diffusion. Actual use in the unit is sometimes a critical period. 4. etc. stability.1 Mechanical Properties during its lifetime the catalyst is exposed to a number of different mechanical constraints (production.3.2 Intrinsic Characteristics 4. Catalyst texture is determined by the total specific surface area. etc. 4.1.3 Non-Catalytic Characteristics 4.1. which governs catalysis as such. utilization in the unite.).3. 4. local chemical composition. These characteristics in turn determine the intrinsic characteristics of the accessible sites (nature.2. defects).1. the active specific surface area (expressed in per cent of accessibility for dispersed metals). the accessible pore volume. especially when the catalyst circulates.1. .3.3.) with the resulting breakage.3. unloading. storage.3. and the interconnectivity of the pore network. reloading. strength.3 Catalyst Stability Defined as the period during which its activity and selectivity remain unchanged. loading into the reactor. transportation. 4.CATALYTIC REFORMING 4.1. unit start up and shut down which cause settling.3.1. High selectivity allows a good yield of the required product to be achieved and reduces side reactions to a minimum.2 Catalyst Selectivity Characterizes the aptitude to activate reactant transformation towards the required product among all those that could be formed.1. abrasion and attrition. density.1.

4.Ch.3. 4.3.3 Morphology of Catalyst (shape and granulometry) Depends on where it is used. thereby promoting the heat transfer.1.3. If the catalyst is to function as a heat carrier (in catalytic cracking for example) it should have maximum heat capacity: the heat energy stored during coke combustion will be returned during the reaction. .1. good thermal conductivity allows temperature gradients to be limited in the catalyst grain and bed.2 Thermal Properties When reactions are highly endothermic or exothermic. Ex:-a spherical shape is recommended for entrained or bulleting fluid beds and rings are used when minimum pressure drop is required. thereby offsetting its endothermicity.4 Catalytic Reforming Catalyst Resistance to mechanical degradation is therefore an important property and should be monitored.3.

The amount of platinum is on a downward trend.6% wt. The average pore diameter is approximately 10nm.2). approximately 1. chlorinated at approximately 1% wt. Table (4.2 mm in diameter. iron etc. 4.5 to 0.2 to 2. the specific area ranges from 150 to 250 m2/g. The alumina used are very pure and the alkaline metals. usually ranging between 0. alkaline earths. always account for less than 500 ppm on new catalysts and usually less than 100 ppm.2) gives its main characteristics. Table (4.2 and 0. and the pore volume from 0.CATALYTIC REFORMING 4. . Main Characteristics of Pt/Al2O3.8 cm3/g.2.. The base is γc alumina. the catalyst is implemented in the form of beads ( fixed and moving beds) or extradites ( fixed bed).1 Platinum on Chlorinated Alumina A few hundred tons of this type of catalyst are still being used in the world.2 TYPES OF CATALYTIC REFORMING CATALYST All current catalysts are derived from platinum on chlorinated alumina as introduced by UOP in 1949.

An interaction between two metals. rhenium.Ch.2 Bimetallic They consist of platinum associated with another metal (iridium. although the effects differ. indium. change in selectivity and especially for high concentrations of iridium. the effect is highly positive.2. tin or germanium). modification of coking resistance. values lower than 100 m2/g of platinum will be obtained and the catalyst will be approximately three times less active. . A gram of platinum well dispersed on the surface of an alumina will represent an area of approximately 260 m2 and will have maximum hydrogenating or dehydrogenating activity. 4. This is why these elements have been selected for numerous industrial catalysts. The effects of different metals on performance have not been publicly quantified. whose properties and chemistry are widely different. However. and a significant effect on activity. Dispersion D is define by the ratio between the real area and the theoretically possible area per gram of platinum. since there is no non-proprietary literature available. The theoretical area can be achieved on industrial catalysts. The following properties are involved: stability of dispersion over time. it can be stated that the different elements do have a positive effect. rhenium and iridium on the evolution in the platinum surface over time as compared with platinum alone. The use of Pt/Re is now most common in semi-regenerative processes and Pt/Sn in moving beds. each platinum atom should be accessible to the reactants and therefore should be in unit amounts of the smallest size possible. In all cases. Catalyst properties can be adapted to the unit's operating conditions. it is crucial to make the most of the small amount of platinum (cost of platinum = $15/g) on the catalyst. As such.4 Catalytic Reforming Catalyst In addition to the properties of the support and the amount of platinum.1) illustrates the influence of elements such as tin. Figure (4. If on the contrary non-optimum operations are carried out during catalyst implementation. must be achieved on the scale of the nanometer and this is the manufacturers' secret.

The bimetallic catalyst. . here platinum-rhenium. Sn and Ir.1). Figure (4. The other "second metals". give the same type of effects.2) shows the variation in octane number in a constant temperature test versus time. proves incomparably more stable than the monometallic one. In these operating conditions-feed end point very high and test duration short-deactivation is related only to coke formation and/or coke toxicity with respect to activity. Effect of Different Metals on Platinum Sintering Under Hydrogen Pressure.CATALYTIC REFORMING Figure (4.

4. which is undesirable.4 Catalytic Reforming Catalyst Figure (4.Ch.At higher levels there is some tendency to effect dimethylation and naphthene ring opening.3 EFFECT OF PLATINUM CONTENT OF CATALYST Platinum content of the catalyst is in the range (0. . .and bi-metallic Catalysts. Compared Stability of mono.8 % wt pt) are used for sever operations such as the production of 100 octane number gasoline from feeds with only moderate naphthene contents.2).3 – 0. As the platinum content of catalyst is reduced.Platinum is extremely expensive. . . -The latest development is the use of bimetallic catalyst which incorporated other metals (Rhenium and Tin) in addition to platinum this catalyst can operate at lower hydrogen partial pressure than can the normal platinum catalyst without deactivation.The high platinum catalysts (0. it's resistance to deactivation is also reduced.6 – 0. while at lower levels the catalyst tends to be less resistance to poisons.8 % wt).

a simplified approach to the reaction mechanism is used to identify the limiting steps and the possible inhibiting effects. At the same time. To the extent possible. Step 3 Design an operating mode.CATALYTIC REFORMING 4. the intrinsic characteristics of the active phase (and/or the support) . Finally to implement it. the activity and selectivity of an initial catalytic formula have been established and performance stability has proved satisfactory. The catalyst formula under study can now be considered valid and a number of correlations can be established linking its catalytic properties. Then the evolution of the active phase (and/or the support) should be assessed in the reaction medium and if possible its stationary state should be characterized. Step 4 Determining basic catalyst properties in addition to the test reaction in order to validate the result.4 CATALYST PREPARATION There are two methods for catalyst preparation: 4. The most critical are singled out and the key preparation unit operations are listed. the textural and structure properties that can be correlated to performance are identified. Step 2 Aims to identify which initial reactants include or prefigure the desired active phase. Step 5 Once an initial result has been obtained and the active phase has been characterized. the .1 Optimizing the formulation Step 1 The choice of active phases is based on experience (empirical or scientific correlation). In particular. physicochemical and mechanical properties. the required catalyst qualities are ranked: catalyst. on the basis of published data and initial kinetic experiments.4. it is used to define the level of diffusional limitations. At this stage.

.The choice being made between different possible manufacturing methods.4. then the pretreatment conditions in the reactor and the stabilization conditions in the reaction medium. The resulting manufacturing technique will be based on a sequence of unit operations.2 Unit Operations The aim is to produce a catalyst at the lowest possible cost.4 Catalytic Reforming Catalyst preparation conditions.Ch. with the desired surface area and porosity. 4. This will result in a representative pre-industrial sample which will be tested in a large pilot unit. consisting of the required active agents. Figure (4. external morphology and necessary mechanical properties for the process technology under consideration. The number and sequencing order of these operations must be optimized to minimize the manufacturing cost and obtain the most high-performance and reproducible product possible.3) describes the sequence of main unit operation. As soon as laboratory formulation has been optimized and the catalysis results have been validated in a continuous pilot on a real feed. it will be possible to scale up the operating mode to produce a pilot test batch of catalyst (10 to 50 liters) and then to begin optimizing the operating conditions of the future production process.

.CATALYTIC REFORMING Figure (4.3). The Sequence of Unit Operations.

the gel is dried. their properties. Zeolite containing Tellurium is very selective for the dehydrocyclization of n-hexane to benzene but is rapidly deactivated.1 wt b) The gel is filtered c) The correct quantity of halogen ( as HCL or HF ) solution is added d) The Platinum is then added in the form of Chloroplatinic acid solution treated with H2S e) After mixing.  Economic imperative (cost of the shaping process).4. fixed.Ch. but are sensitive to poisoning by sulfur compounds. pelleted and calcined at about 500 C°.2. 4.1 Shaping supports and catalysts The choice of the catalyst shaping process is generally the result of a compromise after asset of constraints has been studied. K-Ba-1 are highly selective for the dehydrocyclization of n-hexane and nheptane. plasticity). 4.  Preparing catalyst.2 Preparing catalyst Catalyst can be prepared by precipitating an a) Alumina hydro gel by reaction of ammonium hydroxide with Al chloride and washing the gel until the chloride content is less then 0. Activity and selectivity performances similar to these of platinum on zeolite were obtained by replacing the latter zeolite with a support based on mixed aluminum and Mg oxide obtained by the decomposition of hydro-talcite.2. circulating or fluid bed).4.  The intrinsic characteristics of the solid that is to be shaped (crystallinity. Especially K-1.  Preparing supports. chemical reactivity. particularly with respect to:  The characteristics of the catalytic process (Catalyst slurry.  Catalysts impregnated on supports. .4 Catalytic Reforming Catalyst The following will be examined by way of examples:  Shaping supports and catalysts.

2.2 Influence of alumina acidity The increased acidity caused by the fixation of halogen on the surface of an alumina.Mechanical properties suited to the process technology. The acidity promoted in different ways according to the halogen used (F or Cl). silica.Ion exchange properties.) They are characterized by: 1.4.CATALYTIC REFORMING 4.N-Al2O3 :. silica-alumina or titanium oxide.2.  Economic feasibility that allows significant production. High chemical purity. They can also contain some zeolite (mordenite. . grain size distribution and texture suited to the process chemistry: .3.Al2O3 4. ZSM5. Y zeolite.2.4. and a. transition alumina.is obtained by calcinations above 250-300 o C of alumina tri-hydrate bayerite in air or in vacuum of gibbsite. . 2. The type of acidity seems to depend on fixed chloride content and the chloride precursor used.1 The methods for preparing the hydrates a) Acidification of sodium aluminates b) Neutralization of an aluminum salt c) Hydrolysis of an aluminum alcholate The two main alumina supports used in catalytic reforming are two transition alumina N & Y Al2O3 :1.3 Preparing supports: Properities Refining catalyst supports consist of alumina.3. Aluminas represent a large group including alumina hydrates.Y-Al2O3 :. 2.Surface acid-base properties. . Morphology.is obtained by calcinations of bohmite in air 4. etc.4.

but its diffusion is slowed down in the meso.4. The three characteristics of the method are:  Its exothermicity (heat of adsorption). to activate for isomerization of both paraffins and naphthenes. For example : 1. During the operation of solution equidistribution.4 Catalysts impregnated on a support This can be done by two ways: 4. The solution penetrates very rapidly by means of capillary forces (a few minutes).2. The Young-Laplace law: ∆p= (2γ/rp) cos θ (γ: surface tension. the active phase precursor becomes deposited.2.  The duration of impregnation.In the case of gasoline production from a paraffinic feed. the hydrocracking should be minimized to avoid loss of yield by lowering the acid activity.4. Under such pressure the support particles can burst.  The high pressure developed in the pores. then subsequent maturation and drying. . since part of the air initially present is trapped by the liquid and compressed.Ch. the acid activity can be obtained by means of halogens (F or Cl) or silica incorporated in the Alumina base. 2. θ: junction angle of the meniscus. but balance between these two activities.and micro pore network by dissolution and diffusion of the trapped air. is most important in a reforming catalyst. 4.4 Catalytic Reforming Catalyst The catalyst must have an acid activity.In the case of gasoline production from a naphthenic feed. r p:pore radius) Shows that pressure can reach several hundred bars in the mesopores with rp<10nm.4. gradually filling it (in a few minute to a few hours). The solution penetrates the pore network.1 Impregnation Without Interaction The support is simply wetted by the precursor solution (by spraying or immersion).

Impregnation with Interaction. This is the case for anionic and cationic exchanges. of the acid –base type for example.4).  Interaction can consist in formation of a chemical bond between the precursor and the support: the interaction is then a grafting..CATALYTIC REFORMING 4.for PtCl62. Later on. In this way it is possible to fix silicon or tin from tetrabutoxy tin in a hyper dispersed form.2.2 Impregnation with interaction The support is immersed in an excess of solution containing the precursor salt. Figure (4.4).4. The salt interacts with the surface as shown in figure (4. The support-anchored hyper dispersed phases are obtained after drying and thermal activation.  Precursor-support interaction can also be ionic in nature. A competitor ion(Cl. thermal activation releases the organic fragments and forms the surface oxide molecule. NH4+ for Pt(NH3)42+)is generally added to the reaction medium in order to control exchange kinetics and get homogeneous distribution of active elements in the grain in a hyper dispersed form. .4.

Table (4. either on the metal or on the acid part of the support.4 Catalytic Reforming Catalyst 4. Reactions Mechanisms. cyclization or cracking and are then desorbed. an operation where gaseous hydrocarbons are in contact with the catalyst solid. the reaction occurs on the surface of the solid as long as temperatures remain lower than 550 °C.3). and  An acid function provided by the alumina.Ch.3):  A hydrogenating-dehydrogenating function provided by the platinum. The adsorbed species change by isomerization.5 REACTION MECHANISMS The platinum on chlorinated alumina catalyst has two functions. table (4. Note that there is naturally also adsorbed hydrogen. On the catalyst surface there are a large number of adsorbed species that are dehydrogenated to a greater or lesser extent. . thermally activated homogeneous phase reactions can take place. In catalytic reforming. Above this.

except for hydrogenolysis and hydrocracking. there is a maximum whose ordinate and abscissa depend on the hydrocarbon pressure. Note that. It is involved in the reactant and product adsorption.5). benzene is formed twice as fast as hexanes.5. depending on PH2. . it is formed five to six times faster with platinum and platinum-rhenium and 12 times faster with platinum-tin. As illustrated in figure (4.desorption equilibrium and as a product of equilibrium reactions.1 Hydrogen Action Hydrogen is not involved as a reactant in most reactions.1 Product Yield and Quality The impact of hydrogen on reformat quality is related mainly to the presence of more or fewer residual naphthenes.CATALYTIC REFORMING 4. or to C6 paraffin which have a lower RON.6) shows the variation in methyl-cyclopentane conversion.5. Hydrogen is involved in generating unsaturated species on the catalyst surface (it limits formation of overly unsaturated species that could develop solely into coke and would block part of the catalyst). which can go up to more than 1% when the process is run at pressure lower than 5 bar.1. figure (4. It limits the conversion of certain hydrocarbons. versus hydrogen pressure for three different catalysts: platinum. but also by the fact that it is adsorbed on the catalyst. However. the principle effect is the presence of olefins.1. As an example. platinum-tin and platinum-rhenium. 4.2 Effects on Reaction Kinetics The kinetics of heterogeneous reactions is generally very complex and this is particularly true for the dehydrocyclization reaction.5. 4. either to benzene which has a high RON. while at 7 bar. thereby blocking certain sites that are no longer available to activate reactions. At a hydrogen pressure of 25 bar. this with the variation in dehydrocyclization rate of nheptane at 470°C versus the hydrogen pressure PH2 for different hydrocarbon partial pressures.

5).Ch. . Influence of hydrogen pressure on the selectivity of Methylcyclopentane conversion. Figure (4. Dehydrocyclization Rate vs.4 Catalytic Reforming Catalyst Figure (4.6). Hydrogen Pressure.

the high activity resulting from the addition of Iridium allows some degree of sulfur in the feed . It therefore limits the average concentration in intermediates likely to develop into coke. The time is seen to increase very quickly as the molar ratio H2/heptane rises at constant total pressure.7). has two principles effects: .(Pt-Re/Al2O3).5% wt in figure (4. Figure (4.It was observed in these experiments .3 Effect on Coking Hydrogen influence polyunsaturated species concentrations on catalysts. thus improving the stability of the catalyst. . an increase in sulfur conc. In such cases:. For instance.7). it was found that sulfur on Rhenium restricts the formation of graphitic coke.For the reforming of industrial naphtha it was found the sulfur has an effect on aromatic yield when its concentration in the feed stock exceeds 0.CATALYTIC REFORMING 4.2 Sulfur Action Sulfur influences the performance of mono and bimetallic reforming catalyst. Effect of Hydrogen Pressure on Coke Formation Rate.5.1.5. the time required to lay down an amount of coke on a catalyst is determined. 4. 1.(Pt-Ir /Al2O3).03 wt %.

Declined the accelerated catalyst activity.1 The different options .4 9.5.2.6 8.4 Catalytic Reforming Catalyst 1. involving high severity processing conditions is related to the formation of Pt-S complex of lower reactivity than the original Platinum species to reactions such as coking.7-9.7 . the activity can be prolonged.Sulfur introduced with feed has a stabilizing effect on the overall activity.The sulfiding of Pt/Al2O3 catalyst increase the thermal stability but decrease the activity for dehydrogenation of cyclohexane. .052 C5 and lighter 9 9.If the catalyst is presulfided.Ch.3 7.6-8. 2.6 Sulfur 0.7-10. age 9.026 0. Initial inhibition of aromatics formation. indicated that the beneficial effect on catalyst stability. 4.These result show that the sulfur acts to enhance the acidity and inhibit the dehydrogenation activity of catalyst. .In studying the reforming of naphtha and pure hydrocarbons. And this is due to an adsorption phenomenon in which only a fraction of the available platinum sites are deactivated by Pb adsorption and the identity of those deactivated sites changes constantly because of the dynamic nature of sulfur adsorption.026 0. . . .The presence of sulfur reduces the pt life span of catalyst. Catalyst.

CATALYTIC REFORMING 4. It is obvious that reducing the rate of coking formation would represent a desirable improvement. 4.2 Composition and structure of coke The composition of coke calculated by analysis of coke combustion products to determine the H/C ratio.1.6 CATALYST DEACTIVATION In the oil refinery.6. and many reforming units operate under high pressure in order to increase the life time of the catalyst. In fact. Deactivation in the reforming process is attributed to coke formation and deposition. Measuring the amounts of oxygen consumed and carbon dioxide produced during temperature-programmed oxidation figure (4.6. on the contrary. . 4. the thermodynamics are such that it would be desirable to work at high temperature and low pressure. three-dimensional deposition appear from the onset of coking. the deactivation of the catalyst by carbonaceous deposits is an important technological problem.1 Quantitative analysis and localization of coke This can do by the combustion under oxygen of coked catalysts. The coke localized on metallic particle and support. particularly at a time when production of leadfree gasoline is requiring more severe operating conditions (higher temperature and lower pressures). such operating conditions favor coke formation. for reforming reactions of naphtha's.1 Characterization of Coke Coke deposit on bifunctional catalyst is characterized by: 4.1.6.8). However. this show the heterogeneity of the coke distribution on the catalyst. It was found that the coke is not deposits in the form of a monolayer but.

4 Catalytic Reforming Catalyst Figure (4.9). Typical influence of pressure on stability. Temperature-Programmed combustion of a coked Pt/Al2O3 catalyst (A) CO2 production.2 Effects of reaction conditions on coking Deactivation 4. Figure (4.9) shows that although deactivation is relatively slow at 50 bar.6. space velocity From thermodynamic view.2. however.6. catalysts are unstable under such operating condition.8).1 Hydrogen and hydrocarbon pressure. (B) O2 consumption. it would be best to operate reforming units at the lowest possible hydrogen pressure. . Figure (4.Ch. 4. it becomes very fast under 10 bar of hydrogen pressure.

CATALYTIC REFORMING

4.6.2.2 Temperature of the reaction
Temperature is the operating variable used for activity maintenance in an industrial unit and therefore it is important to know its influence on coke fouling. On platinum single-crystal surface its shows that the morphology of the carbonaceous deposit appears to vary continuously from two-dimensional at low reaction temperature (<277°c) to three-dimensional for higher temperature than about 327°C. Thus is the range of reforming temperature s, coke deposits will be always three-dimension. The amount of coke increase with increasing temperature and this evolution can be explained by the effect of high temperatures on the number of unsaturated products which are coke precursors. The evaluations capable explain by the effect of high temperatures on the number of unsaturated products which are coke precursors. Increasing temperature also accelerates the graphitization process of coke, its shows that the fraction of reversible coke (partially hydrogenated) decrease as the temperature and amount of coke increase. The coke grows mainly on the support with increasing temperature and that is more dehydrogenated. Increasing temperature not change the location of coke (on the metal or on the support) because the catalytic activity of the metal for constant coke conversion is comparable on the different samples, what ever the coking temperature. Table (4.4).

Table (4.4), Effect of the coking temperature on the characteristics of coke. a coking with cyclopentane at atmospheric pressure; H2/H.C ration 2.33. b Relative activity in benzene hydrogenation.

Ch.4 Catalytic Reforming Catalyst

4.6.2.3 Nature of hydrocarbons in feed
Reforming feed stocks very widely in their boiling range and hydrocarbon type distribution (paraffin's, aromatics and naphthenes) depend on their origin, generally, heavier cuts produce more coke. It was state that for cuts around 204°C end boiling point there is (1.6-2.3 %)in cycle length per °c increase in feed end, whereas at end boiling point are 216°c the decease in cycle length (2.1-2.8%) per °C, but the cut's with the lowest boiling range have a high content of cyclopentanic compounds are great coke producers. Hydrocarbons such cyclopentane, n-dodecane turned out to be very good coke precursors. Adding low amounts of di-cyclic aromatics to n-paraffin (n-hexane, n-heptane) increase catalyst aging significantly. Figure (4.10) is studied the coke fouling on Pt/Al2O3 catalyst for different hydrocarbon have 6 carbon atoms. Methyl cyclo pentane >3-methyl pentane > n-hexane >2-methyl pentane >benzene > cyclo hexane.

Figure (4.10), Coke deposition on Pt/Al2O3 for various H.C at 500 °C.

Effect of n-paraffin, on deactivation found that coke deposition and catalyst deactivation is minimum for n-heptane, but aromatics with paraffin chain tendency to produce coke increase. For naphthenes if the ring has five carbon atoms, coke formation and catalyst deactivation higher than six carbon atoms rings.

CATALYTIC REFORMING

The coke deposition increase in order cyclopentane < cyclopentene <cyclo pentadiene, which is the coke agent responsible for the deposition of coke. In case of bi functional catalyst the coke deposition occurs mainly on the acidic sites of support.

4.6.2.4 Effect of sulfur on the coking reaction
Sulfur compounds are recognized as poisons for reforming catalysts and they can cause a complete loss of activity. In order to avoid deactivation, sulfur concentrations need to be less than 1 ppm in feed. But on the other hand sulfur is not totally unwanted because a low concentration of sulfur in feed or during start-up of units can reduce excessive hydrogenolysis at beginning of run and improve the catalyst stability. The presence of sulfur implies a higher reaction temperature for the same performance, figure (4.11), and therefore a higher coke fouling rate.

Figure (4.11), Rate of deactivation versus sulfur content of the feed. Monometallic Pt/Al2O3 at approximately 500 °C.

4 Catalytic Reforming Catalyst 4.2.6 Effect of deactivation on the performance of reforming catalyst The stability of activity and selectivity of catalyst over a period of time is dictated by the nature of deactivation. 4. . and therefore two mechanisms of coke formation have to be proposed.6.3Dimethylbutene Isomerization Table (4. Initial toxicity of coke (in g. Table (4.5 Effect of carbon deposits on reforming reactions We can say coke deposits are poison that can alter the selectivity of bifunctional catalyst. which may by sintering of the catalyst activity or poisoning/coking caused deposition of the feed stream impurities or the formation of some surface residue (coke) by other side reactions.5).6.2.3 Mechanism of Coke Formation Coking of bi-functional catalyst results from accumulation of coke on the metal and on support. of deactivated catalyst per g. Reagent n-heptane Reaction toxicity 430 300 125 360 110 720 700 750 30 Dehydrogenation Cracking Isomerization Coke formation Methylyclohexane Dehydrogenation Coke formation Toluene Dealkylation coke formation 3.6.Ch. of deposited coke) at 430°C. as they show different toxicities according to the reaction taken into consideration. 4.5) shows that dealkylation of toluene most sensitive to coke.

1 On Metal Sites There are two typical models for coke production: 4.6.6.3. For large platinum crystallites increase the rate of coke deposition because of the ability to give higher stabilization for adsorbed cyclopentadiene precursor produced during the reaction.2 The second mechanism Suggests that the routs of coke deposition are based on polymerization reactions with the formation of different types of carbonaceous deposits on the metal surface.1.CATALYTIC REFORMING 4.1 The first model Involves a series of fragmentation reactions and successive dehydrogenation reaction which lead to the formation of carbon atoms.1. this cyclo pentane can lead to naphthalene or heavier poly aromatics compounds through the following sequence of the reaction: .2 On acid sites It's assumed that coke arise from the polymerization of dehydrogenated intermediates generated by the metallic function. this atoms are partially hydrogenated intermediate may combine to form more graphitic and more toxic coke deposits. 4. 4.3. In case of coking reaction with cyclo pentane.6.3.3.6.

The poison becomes adsorbed on the active sites of the catalyst causing either a temporary or permanent decrease in the all over activity. The most common type of catalyst poisoning is caused by any impurity that is either present in the gas stream or formed by some process during reactions. The importance of poison molecules in the inhibition of the reforming-type reaction is shown in table (4.4 Catalytic Reforming Catalyst 4. Poisoning of naphtha reforming catalysts occur typically as result of inadequate use of naphtha pretreatment conditions. because of the essentially irreversible adsorption of poison compounds on the metal surface. In most cases. The poison formed by some process during reactions.6) This shows the initial . the life of naphtha reforming catalyst may be reduced to a few months or weeks into the presence of only small concentration of poison contaminants in the feed.Ch.6. regenerations usually impossible or impractical.4 Poisoning of Naphtha Reforming Catalyst Catalyst poisoning is on of the most severe problems associated with the operation of commercial catalysts. In commercial practice.

Metal impurities most commonly named as poisons of reforming catalysts are arsenic. mercury.4. copper. in high concentrations in the hydrocarbon feed. have been found to have an adverse effect on the catalytic properties of the catalyst. It was found that they have a strong affinity for platinum that results in an irreversible poison effect as result of the formation of stable chemical compounds with platinum.1 Poisoning by Sulfur Compounds Sulfur is known to adsorb strongly at very low gas phase concentration and can remain as a very stable adsorbed species under different reaction condition. the level should be maintained well below 1 ppm. Sulfur present as impurities in the naphtha feed stock in concentrations of organic sulfide of up to 1500 ppm.6. 4.1 The sulfur limits in each catalyst  Monometallic pt/Al2O3. sulfur compound. and the toxicity depends on the number of geometrically blocked metal atoms. Catalyst poisoning typically results from strong chemisorption of sulfur compounds on the surface of the metal. In case of catalytic reforming. The quantity of poison absorbed on the metal sites cannot be readily measured.  Catalysts containing higher Re/Pt ratio.  Bimetallic catalyst (Pt-Re/ Al2O3). It is only possible to know the quantities of impurities injected or deposited on the whole catalyst. sodium. and lead. sulfur concentration in the feed must be kept below 20 ppm. maximum sulfur of 0.5 ppm is allowed.CATALYTIC REFORMING toxicities of different compounds obtained for hydrogenation of benzene on a pt/Al2O3 catalyst.6. Poisoning due to nitrogen compounds are known to inhibit principally the acid function of the catalyst.1. are more sensitive to sulfur compound.4. It seems that the adsorption of a poison deactivates the surface on which it adsorbed. . 4.

Initial Toxicities of various compounds on Pt/Al2O3 catalyst. .6).4 Catalytic Reforming Catalyst Table (4.Ch.

However. 4. for Pt-Ir/ Al2O3.4. It was found that for n-heptane reforming with 0. Initial inhabitation of aromatic formation and accelerated catalyst activity decline. . 2. The high activity resulting from the addition of iridium allows some degree of sulfur in the feed.8% sulfur.1.6.12) shows the effect of sulfur on reforming of naphtha feed. it was found that sulfur on rhenium restricts the formation of graphitic coke. it's improving the stability of the catalyst. Figure (4.12). These results show that sulfur acts to enhance the acidity and inhibit the dehydrogenation activity of the catalyst. The inhibition of the catalyst activity appeared to be a reversible reaction.CATALYTIC REFORMING In case of the bimetallic t-Re/ Al2O3 catalysts.2 Increasing sulfur concentration has two principal effects 1. dehydrocyclization is reduced and hydrocracking is increased. Effect of sulfur on Reforming of naphtha feed at constant catalyst life. Figure (4.

indicating that acid sites are more involved in these reactions. The concept of selective and nonselective poisoning on reforming reactions working with Pt/Al2O3.).3 The effect of varying concentration of sulfur on the activity and selectivity of platinum reforming catalyst They found that sulfiding of Pt/Al2O3 catalyst increases the thermal stability but decreases the activity for dehydrogenation of cyclo-hexane.4.4. The figure (4. Figure (4. Atomic sulfur is a selective poison that reduces the rate of hydrogenolysis of cyclopentane more than that of hydrogenation of benzene.11) shows clearly the importance of the effect of sulfur on catalyst deactivation rate expressed as inlet reactor temperature necessary to achieve a constant reformate quality as a function of operating time. and dehydrocyclization are adversely affected.13) shows the effect of nitrogen content on catalyst aging . They inhibit principally the acid function of the catalyst. a (demanding reaction. On the other hand.2 Poisoning by Nitrogen Compounds Nitrogen compounds are generally present in the form organic compounds that decompose into ammonia at reforming conditions. It is clear that nitrogen compounds have a little effect on the dehydrogenation reaction. they have the same effect in the different reaction studies: hydrogenation of benzene (nondemanding reaction) and hydrogenolysis of cyclopentane. hydrocracking.Ch.6. Isomerization. but to some extent they can alter the metallic properties of the platinum.4 Catalytic Reforming Catalyst 4.they found that certain poisons such as H2s and SO2 are nonselective.6.1. On other hand. 4.

arsenic.13).14).CATALYTIC REFORMING Figure (4.3 Poisoning by Metals Deactivation of naphtha reforming catalysts by metal contaminates has received little attention and only a few fundamental investigation has been reported it is known that the metallic poisons are rarely eliminated by regeneration. Studies carried out using lead showed this effect. copper and iron. The effect of nitrogen content on catalyst aging. One of the most affected reactions is dehydrogenation. It is known that platinum metal can be activated by metallic ions such a mercury. lead.4. bismuth. . and as a consequence all necessary precaution need to be taken to prevent them from coming into contact with the catalyst. figure (4. 4.6.

14). From the results it is clear that metal contamination generally causes a decrease in the dehydrogenation and dehydrocyclization functions.4 Catalytic Reforming Catalyst Figure (4. An increase in arsenic concentration on catalyst to 0. Similarly. Poisoning by copper and iron. 4. . Poisoning of dehydrogenation by lead.5 wt% decreases dehydrogenation activity. small amounts of iron and copper can accelerate the deactivation in the dehydrocyclization reaction figure (4.02 wt % on the catalyst have little effect on reforming reaction.6.15).4.15). Figure (4.Ch.3.01-0.1 Effect of arsenic on Pt/AL2O3 They found 0.

b. Semi-regenerative: the operation may last several thousand to more than 10.7. 2. Fully regeneration :(swing. Characterization of coked catalyst.3 Factors affecting coked catalyst reactivity 1.2 Catalyst Regeneration Steps 1.7.5 wt% decreases dehydrogenation activity. The chemistry and the nature of carbon deposition and the 3. Restoration of the acid function and metallic dispersion by chlorination.4 Regeneration of Coked Catalyst 4.02 wt % on the catalyst have little effect on reforming reaction.01-0. It's already known that high hydrogen pressures lower the concentration of coke precursors. Reduction with hydrogen.1 Regeneration with Hydrogen Hydrogen is found to have a significant impact on hydrocarbon reaction over the naphtha reforming process. c. Passivation by sulfiding. 4.7.CATALYTIC REFORMING 4. 4.7 CATALYST REGENERATION They found 0. Coke structure which is dependent on the nature of catalyst and reaction conditions. which comprises: a.4.7. An increase in arsenic concentration on catalyst to 0. b. Catalyst rejuvenation. 4.reactor type) or continuous (moving bed reactor type) cycle may last only a few hundred hours or even less. Elimination of coke by controlled burning 2.7. 4.1 Effect of the Type of Process on Cycle Length a.000hours before it's interrupted for regeneration. thereby .

Ch. .The presence of an optimum surface chloride concentration in the regeneration of Pt / Al2O3 catalysts by H2 was found to be an important parameter.4 Catalytic Reforming Catalyst keeping the coke rates low. This because the strong dehydrogenation reactions involved in coking are restricted by the presence of hydrogen. .Hence a large part of the coke which is destroyed by hydrogen treatment is deposited on the support. one being easily removed by hydrogen (Reversible coke) and the other less readily removed (irreversible coke). Figure (4.For bi-functional catalysts. whereas the slow removal of coke occurs by catalytic hydrogasification.These phenomena can be explained by either the mobility of carbonaceous deposits on the catalyst surface or the hydrogen mobility.15) is for the hydrogen cleaning of platinum surfaces.15). . The mechanism showed in figure (4. a small amount of the coke is deposited on the metal where the majority is accumulated on the alumina. Model of carbon removal by hydrogen. . coke levels controlled by hydrogen cleaning. . This mechanism is based on the distribution of two types of coke on metal sites. On the metal surface. The cleaning action of hydrogen occurs by catalytic hydrogenation.

The higher the metal-to-acid ratio. The metallic activity is totally regenerated but a large amount of coke still remains on the catalyst at 430°C at 20 hrs.7. Comparing the pt/Al2O3 catalysts with different metal-to-acid ratios. the lower the burning temperature. The burning of coke start with the coke deposited on the platinum because of the catalytic action of platinum and because the deposit is richer in hydrogen. But the carbonaceous deposits become more and more dehydrogenated showing that more hydrogenated compounds are eliminated first.7. The last part of the coke to be burned is the most distant from the metal and the coke poorest in hydrogen.4. with burning at lower temperatures when more platinum is present.C residues. .1.2 The effect of time of H2 treatment on the amount of coke remaining on the catalyst: It was found that increasing the time of treatment result in decreasing coke content.4.4.5 wt% Cl shows a complete regeneration during static and dynamic H2 spillover from Pt alumina which restores the catalyst surface freeing it from H. Also Pt deceases the oxidation temperature of graphite.CATALYTIC REFORMING A catalyst with about 0. it is accepted that pt catalyzes the burning of the coke.7. 4.2 Regeneration with oxygen Regeneration in presence of oxygen can be complicated by the fact that metal sintering can be promoted at high temperature. 4.1 The effect of the nature of bi-functional catalysts on their regeneration by H2: The carbon remaining decrease and the activity of the catalyst for benzene hydrogenation increases with the temperature of hydrogen treatment. The burning then spreads to the carbon on the support by the action of oxygen spillover.1. 4.

TPO of alumina samples mixed with platinum –alumina after coking with naphtha during 6 hr. the oxidation starts at lower temperatures and the temperature peak is also at lower temperature.16) shows that when Pt is present.For the catalyst which have less than 50% Re : The regeneration occurs at the same temperature as for pt/ Al2O3 (500C) 2. . The less polymerized deposit would oxidize at a lower temperature. 2. The effect concentration of Rhenium in pt Re/Al2O3catalyst on the regenerative behavior: 1. The acceleration of coke burning in the presence of pt can be explained by: 1. Figure (4. Figure (4. Although the amount of carbon is the same. 3.16).Travels by spillover along the support (Al2O3) to the coked alumina particles.4 Catalytic Reforming Catalyst Greater amounts of Pt are present. the coke is less polymerized because of the Pt-catalyzed hydrogenation of coke precursors occurring during the reaction. The presence of Re decrease of spillover cause it's not capable of promoting spillover.Ch. eliminating the coke by burning at lower temperature than that of the gaseous oxygen.Oxygen is adsorbed on Pt in an activated form.For Re is above 50% : The coke would not burn off until much high temperature was reached.The activated oxygen spills along the pores of the coked alumina.

the iron sulfide is oxidized into metal oxide (fe2O3) and sulfur trioxide (SO3) . When the sulfur content of the catalyst exceeds 1000 ppm. Oxidation and reduction studies of the formation and elimination of sulfated on Pt/Al2 O3 catalysts indicate the oxidation eliminated the sulfur.5 Regeneration of sulfur. sulfur cause the formation of iron sulfide from the reactor materials . deposited on the metal . a special procedure has to be employed during the regeneration to diminish the sulfation of the support .The (SO3) formed reacts with the alumina to form the thermally very stable alumina sulfate. Sulfur can be removed either after oxy-chlorination or before catalyst regeneration by this procedure: 1.contaminated catalysts When naphtha reforming catalysts are contaminated with sulfur.When carbon removal takes place.The formed hydrogen sulphide is eliminated from the gas by washing with an aqueous sodium carbonate solution. the sulfate is reduced to H2S. In the presence of sulfate ions. The Pt-Re/Al2O3 regeneration was found to . 4.When performed after oxy-chlorination: This is in order to increase the Al sulfate reduction and limit the loss of chloride from the catalyst.CATALYTIC REFORMING 4.It consists of reduction of the sulfur species under hydrogen at about (500°C) . Stated that during reduction at 500 ˚C. a chlorinated compound is injected during the operation. 3. 2.7.It is recommended that the procedure be continues until the hydrogen sulphide concentration is lower than 2 ppm.Where the reduction at 300 ˚C cannot convert sulfates to H2S. a special regeneration procedure to remove the sulfur is followed before any attempt to burn the coke. 4. escaping with the exist gases of the reformer . however the oxidized sulfur compounds were strongly held on the support. diminishing the surface hydroxyl concentration.5. for at least l hour. operating temperatures have to be increased of rapidly to maintain the octane number constant until the sulfate removal step is employed.1 Effect of sulfur on catalyst performance In industrial units.7.

c.2 Shutdown 1. 4. Maintain corrosion control (caustic or carbonate circulation through the air cooler – separator). 0. theses sulfite are converted to H2S during reduction.3 Carbon Burn 1. 4. Maximum pressure consistent with air supply and equipment. 3. Nitrogen blankets the unit. Maintain chloride addition at 20: 1 mole ratio of water: chloride at the inlet of reactor 1. Lower reactor inlet temperatures to 400˚C (750 ˚F ). 4. 2. 4. Reduce reactor inlet temperatures to 454˚C (850˚F) then stop charge to the unit. Maximum recycle circulation consistent with equipment.8.8 PROCEDURE OF REGENERATION 4. 4.8. d.1 Pre-shutdown 1-Prepare auxiliary regeneration equipment.6 to 0.Ch. 400˚C (750˚F ) reactor inlet temperatures and 454˚C (850˚F ) maximum reactor outlet temperatures . Hold carbon burn conditions until the reactor outlet temperatures have remained at their base levels for four hours. 2-Ensure that all necessary chemicals and materials are available. Remove residual liquid hydrocarbons. 3.8. b.4 Catalytic Reforming Catalyst be more complicated if sulfate and sulfite species were present on the alumina surface during calcinations.8 mole % oxygen at the compressor discharge 2. . Also hold 30: 1 mole ratio of water: chloride at the inlet of the last reactor when the last reactor is being burned in parallel. Conditions of carbon : a.

6 Nitrogen purge 1. 4. 4.1 mole % at the compressor discharge. Begin maximum gas circulation. and declined to a low level (less than 50 ppm). Flash and drain separator: Drain all low points thoroughly before stopping heater firing.3 mole % and the carbon dioxide level is less than 0. 3.4 Oxidation 1.CATALYTIC REFORMING 4. 3.8.8. Hold a 20: 1 mole ratio of water: chloride for eight hours.5 Cool down 1. Stop chloride injection. Maintain 5 mole % oxygen in the circulating gas throughout the cool down. 4. 2.8. purging all lines. 2. Purge in reverse from the first reactor inlet unit the oxygen level is less than 0. b. 4. 4. Hold purges until the sulfur dioxide level has peaked. Pressure the unit to a minimum of 7 kg / cm2 absolute (100 psia) with grade hydrogen. Hold required reactor outlet temperatures for one hour. 2.7 Reduction 1.3 mole % and the carbon dioxide level is less than 0. Purge forward from the first reactor inlet until the oxygen level is less than 0.8. Purge 10 catalyst volumes of hydrogen through the plant. 3. Continue gas circulation until all reactor outlet temperatures are below 204 ˚C (400 ˚F).1 mole % at the compressor suction. Conditions of oxidation: a. 3. Stop heater firing continues maximum gas circulation. Increase inlet temperatures at 55 0 C / hour to 427 0C ( 1000F / hours to 800 0 F ) for all catalysts except R – 30 series which will be 480 0C (900 0F) . . 510˚C (950 ˚F) reactor inlet temperatures. 5 mole % oxygen in circulating gas. 2. Measure the sulfur dioxide level in the purge gas.

6. Re-establish the conditions of the carbon burn . Start naphtha charge at 371 0C (700 0F ) reactor inlet temperatures . 2.5 to 8. 7.8. continue with the procedure through the oxidation .0 kg/cm2 absolute (100 psia ) hydrogen partial pressure and all reactor effluent hydrogen sulfide concentrations are below 5 ppm .8. start chloride injection at 20:1 mol ratio water: chloride. and startup steps as outlined 4. 3. Pressure to 8. Depressurize and nitrogen purge the unit . complete the regeneration through step G – 4 of the Reduction. 3. After we holding required reactor outlet temperatures for one hour . During the heat – up. step D – 2. reduce heater firing and begin cooling to 371 0C ( 700 0F ) reactor inlet temperatures in preparation for cut in. flush and drain the separator. At the 510 0C (9500F) conditions of step G-4 of reduction. Continue gas circulation until all reactor outlet temperatures are below 400 0C ( 7500 F ) . The reduction may also be done with catalyst reformer hydrogen of 75% minimum purity. Follow programmed chloride addition. Hold the reactor temperatures at reduced levels until the water and sulfur specification are met.4 Catalytic Reforming Catalyst 5.8 kg/cm2 (125 psia) minimum hydrogen partial pressure. 4.0. Maintain 510 0C (950 0F ) and 7. water should be frequently drained from the separator and system low points and the circulating gas hydrogen sulfide content should be monitored. maintain a circulating water pH of 7. cool down . When 5 ppm hydrogen sulfide concentration is reached at all reactor outlets. when the proof burn is complete . 4. step C . purge reduction . If a sulfate removal step is to be used. . The oxidation hold period. and reduce heater firing. 2.9 Start-up 1.Ch. stop chloride injection. 4. 6. 5.8 Sulfate Removal 1. can be shortened to four hours.

CATALYTIC REFORMING .

reaction temperature. In fact temperature is the only operating variable he can use to adapt changes in feed quality or to produce reformats of different quality.1 INTRODUCTION Catalytic reformers are designed for flexibility in operation. toluene. space velocity. Reformers are generally designed with three or more reactors in usually series each of them contain different quantity of catalyst so there are changes of temperature as feed flow through the catalyst from one reactor to another. T (SOR) or start of run temperature is the reactor inlet temperature. feedstock properties. Reaction temperatures are chosen to balance the advantage of increased reformats quality (research octane number) and disadvantage of increased deactivation rate as temperature increased.5 Catalytic Reforming Parameters 5. and xylenes (BTX). whether for motor fuel production or to produce aromatics such as benzene.1). which yields the required octane number at full capacity at the beginning of the run. The variables.2 TEMPERATURE The operator has very little freedom to act on an industrial unit in normal operation. reaction pressure and hydrogen to hydrocarbon mole ratio. the reforming catalyst must respond to change in unit operating condition.Ch. 5. which affect the performance of the catalyst and change the yield and quality of reformat are. and its related to the RON under certain condition is shown in figure (5. To meet these drastically varying demands. .

2).1). Platinum catalyst alone or bimetallic Pt-Re catalyst will allow the required octane number to be achieved at the same starting temperature but the variation will be much faster with monometallic catalyst. Also temperature variation curve with time depends on the severity of an operating and naturally on the catalyst quality. Variation in temperature during a run.2). . As shown in figure (5. Variation in octane number versus TSOR.CATALYTIC REFORMING Figure (5. Figure (5.

C ratio used. until the end of the run as shown in figure (5. Monometallic catalyst shows a drop in yield as soon as the temperature rises. 5. In the first reactor there are negative (∆T) due to the dehydrogenation reaction that take place in this reactor.Ch.Reformers have three or more reactors usually in series and the pressure is different in each reactor. Variation in C5+ during the run.3).5 Catalytic Reforming Parameters Yield doesn’t vary in the same way.3). It is preferable to use the average reactor pressure. While bimetallic C5+ selectivity remains the same. for estimating yields and cycle length.3 REACTION PRESSURE The reformer units in 1950 typically operated in the pressure higher than that operated nowadays . . Figure (5. But positive (∆T) observed in last reactor due to the hydrocracking that takes place in this reactor as dehydrogenation is endothermic reaction but hydrocracking is exothermic reaction. if it is available. Another important parameters is (∆T) across each reactor which give indication about the reaction occur as well as the H2/H.

5. The disadvantages of increasing pressure are:  increased catalyst coking. Decreasing pressure increase the production of aromatics and hydrogen by dehydrogenation of naphthenes and dehydrocyclization of paraffins and reducing hydro cracking as shown in figure (5. The advantage of increasing H2/H.C ratio is the hydrogen react with coke precursors.4 HYDROGEN TO HYDROCARBON RATIO In catalytic reformers hydrogen is recycled in order to maintain a certain ratio of H2/H. removing them from the catalyst before they form significant amount of polycyclic aromatics and deactivation the catalyst also reduce .C and high partial pressure.  shorter cycle length.7 to 83. Influence of P and the feed on C5+ yield.4).  reduce the product yield and. Notes At 100 RON there is an increase in percent yield of reformat from 79.5 by a reduction in pressure from 300 to 100 psig.CATALYTIC REFORMING The pressure under which reforming take place affect on yields and cycle length.4). Figure (5.

5). Notes By reducing H2/H. it affect on the catalyst life due to increasing density to form coke.C ratio from 5 to 4 shorten cycle length about 20%.6 respectively.5 Catalytic Reforming Parameters catalyst deactivation rate.Ch. By reducing H2/H.C=4 as shown in figure (5. . However.C ratio it affects aromatization and increases hydro cracking.C. Catalyst stability versus H2/H. Monometallic catalyst in seventies worked at high ratio (7-8) to achieve stability comparable to the modern catalyst with H2/H.75 and 3. A lower hydrogen partial pressure favors dehydrogenation of naphthenes and dehydrocyclization of paraffins.5). The disadvantage of increasing H2/H. Figure (5.C from 8 to 4 and 4 to 2 the carbon on catalyst is increased by a factor of 1.

increased hydro cracking and reducing reformat yield.6) show that beginning with space velocity=2 to 3 requires raising the reactor inlet temperature by 8 degree centigrade to maintain reformat octane number.CATALYTIC REFORMING 5. in contrast a drop of 1. As below 1. Aromatization and isomerzation aren’t affected by changes in space velocity because these reaction approach equilibrium even at high space velocity. . Influence of Space Velocity on Octane Number. LHSV = volume per hour of reactor charge / vol. Modern reformers usually operate between from 1.0 to 2.5 allow the inlet temperature to be lowered by 6 degree centigrade.0 h-1 undesired side reaction. These values may vary little depending on the operating condition and catalyst used. The choice represents a compromise between allowable hydro cracking and desired dehydrocyclization.0 h-1 (LHSV). Figure (5. WHSV = weight per hour of reactor charge/weight of catalyst. of catalyst.6).5 SPACE VELOCITY It is a measure of the contact time between the reactants and the catalyst and expressed as liquid hourly space velocity or weight hourly space velocity. Figure (5.

Pb and Cu must be kept at low concentration. Initial boiling points are too low. cat-cracked.  Water and chlorine compounds as they alter the acidity of the support. so concentration must be maintained at less than about 1 PPM by hydro-treating before reforming. The temperature T (SOR) increases if the initial boiling points are low. indicating the presence of a lot of C6. The third is increasing the tendency to polymerize and form coke on the reforming catalyst.  Metal such as As. the feed properties are parameters which can significantly influence the performance of the catalyst such as:  Straight run naphtha generally constitutes the major feedstock for reformers.5 Catalytic Reforming Parameters 5. these stocks contain substantial amount of mono-olefins.Ch.  Sulfur in the feed poisons the metal and organic nitrogen compounds. The run duration is shortened by low initial boiling points due to the higher operating temperature. Feedstock containing an appreciable concentration of unsaturated hydrocarbons such as thermal cracked. High endpoints reduce benzene production. First. and their concentration must be carefully controlled to maintain the proper catalyst acidity. of the catalyst. in a reformer reactor. olefins hydrogenate. which can form ammonia. cause a large amount of benzene to be produced. because they deposit on the Pt component and deactivate it.1) summarizes the effects of cut points on the different variables. Table (5. consuming hydrogen that might be needed for hydrotreating other stocks. Since light paraffins are hard to convert.6 FEEDSTOCK PROPERTIES In reforming operation. but can . In addition to being high in sulfur and nitrogen. Second. the desired octane will be achieved only by production more C7+ aromatics. coker and pyrolysis naphtha must usually be hydro-treated before reforming in order to prevent undue hydrogen consumption in the reformer and excessive catalyst deactivation. These olefinic species are undesirable in reformer feed for several reasons. resulting in lower octane reformat. and by high end point due to the presence of coke precursors. hydrogenation of olefins markedly lowers their octane numbers. poisons the acid function.

Influence of P and the feed on C5+ yield.1). higher naphthenes give higher amount of yields. Table (5. Figure (5. Figure (5.7). Influence of IBP and EP at constant space velocity and RON. which it run cause rapid catalyst coking.CATALYTIC REFORMING cause substitute naphthalene to be produced.7) show that the difference between the amount of naphthenes on the yields. .

2) to have a possible yield with a possible quality with different type of catalyst (monometallic and bimetallic catalysts). Table (5. .2).5 Catalytic Reforming Parameters Operating pressure for present day processes is summarized in table (5. Operating conditions for present-day processes.Ch.

CATALYTIC REFORMING .

Labels and Other Forms of Warning: All portable containers of hazardous chemicals must have a large. Material safety data sheet (MSDS): Chemical manufacturers.Ch. they must include following information: • Chemical and common name • Ingredient information • Physical and chemical characteristics • Physical hazards . importers and distributors are required to provide MSDSs to purchasers of hazardous chemicals. Although format of MSDS can vary. including during spills and maintenance • Emergency and first-aid procedures • Date of MSDS preparation and last revision • Emergency contact of manufacturer or distributor .potential for reactivity. readable label or tag which states: • Name and address of manufacturer • Name of chemical • Numerical hazard warning or other appropriate warning supplied by manufacturer Labels can be color coded according to following: • Orange Carcinogen Hazard (ie benzene) • Red Chemical Burn Hazard (ie acids. fire and/or explosion • Health hazards • Symptoms of exposure • Primary route of likely entry into body on exposure • OSHA permissible exposure levels • Precautions for use • Waste disposal • Protective measures and equipment. bases) • Yellow Toxic Vapor Hazard (ie H2S) • White All Others B.6 Hazard Assessment Hazard [1] Chemical and catalyst handling: A.

lowered pulse. If other persons are present. Loss of consciousness and suspension of respiration quickly follow. keep victim in fresh air and keep quiet.CATALYTIC REFORMING [2] Hydrogen sulfide poisoning: Hydrogen sulfide is both an irritant and an extremely poisonous gas. Many natural and refinery gases contain more than 0. A-Acute hydrogen sulfide poisoning: Breathing air or gas containing more than 500 mol-ppm H2S can cause acute poisoning and may be fatal. send one for a physician. After victim recovers. odor to breath and nausea. Any unit processing gases containing H2S can be operated safely. If possible. Others should rub patient's arms and legs and apply hot water bottles. If breathing has not stopped. Speed in beginning artificial respiration is essential. there is still risk of edema (excess accumulation of fluid) of lungs which may cause severe illness or death in 8 to 48 hours. Men have been revived after more than four hours of artificial respiration. . After patient is revived. Secure a physician and keep patient quiet and under close observation for about 48 hours for possible edema of lungs. artificial respiration must be started at once. and remain under observation for 48 hours for appearance of edema of lungs.10 mol-percent H2S. C. put him to bed. Do not give up. irregular breathing. he should be kept quiet and warm. Current OSHA permissible exposure limits are 20 mol-ppm ceiling concentration and 50 mol-ppm peak concentration for maximum ten minute exposure.First aid treatment of acute hydrogen sulfide poisoning: Move victim at once to fresh air. provided ordinary precautions are taken and poisonous nature of H2S is recognized and understood. If victim has become unconscious and breathing has stopped. B-Symptoms of acute hydrogen sulfide poisoning: Symptoms of acute H2S poisoning are muscular spasms. blankets or other sources of warmth to keep him warm.

must wear fresh air masks and work in pairs so that one may effect a rescue or call for help should other be overcome. G-Prevention of hydrogen sulfide poisoning: Best method for prevention of H2S poisoning is to stay out of areas known or suspected to contain it.Ch.Treatment of sub acute poisoning Keep patient in dark to reduce eyestrain. indigestion. atmosphere should be checked repeatedly for presence of H2S. dizziness. Where sub acute poisoning is suspected. and weakness. Edema of lungs may occur. .6 Hazard Assessment D-Sub acute hydrogen sulfide poisoning: Breathing air or gas containing H2S anywhere between 10 to 500 molppm for an hour or more may cause sub acute or chronic hydrogen sulfide poisoning. atmosphere in which people work should be checked from time to time for appreciable concentrations of H2S. Fresh air masks or gas masks suitable for use with hydrogen sulfide must be used in all work where exposure is likely to occur. F. E. have a physician treat inflamed eyes and throat. As mentioned above. Persons who must work on or in equipment containing appreciable concentrations of H2S. inflammation of eyes and throat. Watch for possible edema. Masks are checked frequently to make sure they are not exhausted. excessive saliva.Symptoms of sub acute poisoning: Symptoms of sub acute H2S poisoning are headache.

unconsciousness. Do not enter or even place your head into a vessel which has a high concentration of nitrogen. Breathing an atmosphere deficient in oxygen will rapidly result in dizziness. A. Examples include: Reactors Separators Fractionators Drums Receivers Pumps Fired Heaters Storage Tanks Neutralizing Basins Water Treatment Basins API Separators (1) General precautions: Vessel must be positively isolated. However in vessels or areas where there is a high nitrogen concentration. Safe Vessel Entry Precautions apply equally to entry into all forms of vessels. Refinery personnel who must enter a contaminated or inert atmosphere follow all prescribed standard safety precautions and regulations which apply for refinery. Safe access to vessel must be assured. . or death depending on length of exposure. no individual should go in to help him without first donning a fresh air mask. It is important to emphasize that if a person has entered a vessel and become unconscious. Personnel entering vessel must be provided with safety harnesses. Do not stand close to a valve where nitrogen is being vented from equipment at a high rate which may temporarily cause a deficiency in oxygen close to valve. including enclosed areas which may not normally be considered vessels. there is also a deficiency of oxygen for breathing. Man way and internals must be provided.CATALYTIC REFORMING [3] Precautions atmosphere: for entering contaminated or inert Nitrogen is non-toxic. Two persons must be available outside vessel to assist personnel inside.

Any hazards found during survey are isolated or removed. Minimum of one harness for each person entering vessel and at least one spare harness for persons watching at man way should be provided. permanent ladder and platform or scaffolding strong enough to support people and equipment who are involved in work to be performed. there should be minimum two people available outside vessel. Radio. (2) Positive isolation: Every line connecting to a nozzle on vessel to be entered must be blinded. Scaffolding is preferred when vessel is large enough to permit its use.6 Hazard Assessment Safety of atmosphere inside vessel must be confirmed by checks for toxic gases (eg H2S). one of whom is specifically assigned responsibility to observe activity of people inside vessel. Exterior access should be a solid. Access to interior must be strong and solid. (4) Safety harness: Any person entering a vessel should wear a safety harness with attached safety line. (3)Vessel access: Proper access is provided both to exterior and interior of vessel to be entered. A communication system must be provided for man way watch so that they can quickly call for help in event personnel inside vessel encounter difficulty. oxygen content. or public address system is necessary for that purpose. These people should not leave their post until those inside vessel have safely exited. A supply of fresh air must be available for people who will rescue personnel entering vessel in event they encounter difficulty. and explosive gases.Ch. (5)Man way watch: Before a person enters a vessel. A vessel entry permit must be obtained and registered with responsible persons. . Area around vessel man ways is surveyed for possible sources of dangerous gases which may enter vessel while person is inside. telephone.

fan. Oxygen content of atmosphere inside vessel is checked before every entry and vessel is blinded. Each mask must have backup air supply completely independent of main supply. . (8) Checkout prior to startup: Risk of exposure to hydrocarbons. Primary danger is nitrogen. and catalyst dust is low during new unit checkout. Permit is typically issued by safety engineer or shift supervisor. Each point of entry and any dead areas inside vessel. a check of supply header is made to ensure it is properly lined up and there are no connections where nitrogen can enter system (nitrogen improperly used as backup for instrument air by some refiners).CATALYTIC REFORMING (6) Fresh air: Vessel must be purged completely free of any noxious or poisonous gases and inventoried with fresh air before permitting anyone to enter. Fresh air can be circulated through vessel using an air mover. Fresh air purge should be continued as long as people are inside vessel. Auxiliary supply must have an alarm that alerts user he is on backup supply. and should be sufficiently large to give user five minute autonomy to escape from danger. It must also be independent of electrical power. a vessel entry permit must be obtained. or. Vessel entry procedure must be rigorously followed during checkout of new unit. Minimum one fresh air mask for each person entering vessel and at least one spare mask for manhole watcher should be provided at vessel entry. vessel can be purged using dry certified instrument air from a hose or hard piped connection. toxic or poisonous gases. should be checked. Safety department must test atmosphere within vessel for toxic gases. in cases where moisture is a concern. Vessel entry permit ensures that all responsible parties know that work is being conducted inside vessel and establishes safe preparation procedure to follow in order to prevent mistakes which can result in an accident. such as receiver boots or areas behind internal baffles where there is little air circulation. oxygen and explosive gases before entry. Independent blinds at each vessel nozzle are preferred. (7) Vessel entry permits: Before entering vessel. This must be repeated every 4 hours while there are people inside vessel. When instrument air is used.

wear appropriate respiratory protection such as selfcontained breathing apparatus. Another factor to be cautious of is heat stress especially if entering a vessel immediately after unit has been shut down. Wearing clothing that has been wet with benzene almost guarantees that person will inhale benzene vapors over a long period of time. Equipment which has been in service must be thoroughly purged before entry. If liquid hydrocarbon remains or if odors persist afterwards. possibility that vessels contain dangerous gases is much higher. Wash any skin areas exposed to benzene with soap and water. Vessel should have been steamed out (unless steam presents hazard to internals). it should be removed immediately. Do not wear clothing that has been wet with benzene until garment is decontaminated by washing or dry cleaning. or air mask with external supply. Special instruction: If clothing (including gloves. Take complete bath if body area is wetted with benzene. shoes) becomes contaminated with benzene. Benzene: Benzene is extremely toxic. B. Avoid draining benzene to concrete or into sewers where it can vaporize and create health hazard. then fresh air circulated through it until all traces of hydrocarbons are gone. every vessel nozzle must be blinded with no exceptions. Blinds must all be in place before vessel is purged. If you must enter an area of high benzene vapor concentration resulting from a spill. Do not use hot water or steam which aggravates vaporization of benzene. repeat purging procedure until vessel is clean. resulting in potential health hazards. In a turnaround inspection.Ch. . Aromatic Hydrocarbons: i.6 Hazard Assessment (9)Turnaround inspections: In turnaround inspections.

NIOSH/OSHA guidelines for toluene. . proper ventilation. and proper maintenance of operating and safety equipment. solvent-resistant gloves. skin contact (Especially eyes) and inhalation must be minimized. Avoid breathing aromatic vapors. Minimizing exposure to aromatics: Operating and laboratory personnel involved in obtaining samples wear chemical-type safety goggles or shield. protective apron or laboratory coat. bathe. substitute for safe working conditions. Toluene. In all sampling situations. Medical attention: U. All new or current employees should be alerted to early signs and symptoms resulting from exposure to aromatics.CATALYTIC REFORMING ii.S. and approved respiratory protective equipment where ambient concentrations exceed allowable limits. iv. xylene and ethylbenzene set forth recommendations for medical monitoring of personnel working in environments where exposure to these materials can occur. etc) becomes wet with such aromatics. iii. In all cases. remove clothing. and put on fresh clothing. and any workers experiencing such symptoms must seek professional medical attention. These simple precautions greatly minimize exposure to hydrocarbon vapors. This protective equipment is not. Sampling liquid hydrocarbons requires some care to limit personal exposure and release to atmosphere. personnel are instructed to remain at arm's length from sample container and to situate themselves upwind of container if possible. good personal practices. shoes. If clothing (including gloves. To minimize vaporization. however. xylenes and heavier aromatics: These compounds are moderately toxic and are believed not to have destructive effects on blood forming organs as does benzene. hot hydrocarbon streams must be routed through a cooler before drawing a sample.

The OSHA 8hour time weighted average exposure limit to inorganic arsenic compounds is 10 micrograms per cubic meter of air. R-55. iron sulfide. and vanadium. hazardous dust. in lesser amounts. R-60. which is not currently listed by OSHA as a hazardous substance. and vapors may be inhaled. which might present hazards to human health and/or the environment if handled or disposed of improperly. iron pyrites. R50. R-16. ii. hydrocarbons. Arsenic: Arsenic is a recognized carcinogen and can cause acute and chronic toxicity. with nausea. and vapors during catalyst unloading operations. R-18. blood disturbances. Only following fresh catalysts (R-11. or contaminate the eyes and skin. fumes. It is the purpose of this safety section to provide information and recommendations which will allow safe handling and proper disposal of these catalysts. Spent Platforming catalysts may also contain additional hazardous chemicals.6 Hazard Assessment C.Ch. such as: arsenic. Major constituent of UOP Platforming catalyst is alumina. liver damage. R-14. These catalysts do contain other constituents. R-19. For the unprotected worker. Hydrogen sulfide: Hydrogen sulfide is both an irritant and an asphyxiant. Material Safety Data Sheets should be obtained from UOP at the time of catalyst supply and should be available to the operating personnel. kidney damage. R-51. Symptoms of acute toxicity are somewhat dependent upon route of contact and can include (for ingestion or inhalation): irritation of the stomach and intestines. R-12. Current OSHA permissible exposure limits are 20 ppm ceiling concentration and 50 ppm peak concentration for a maximum 10 minute exposure. vomiting and diarrhea. R-62) contain hydrogen sulfide. fumes. and allergic reactions. lead. ingested. Greatest potential for human exposure to catalyst materials comes from catalyst dust during reactor loading and from dust. . The toxic properties and exposure limit of the most hazardous of these chemicals follow: i. carbon. Safety Information for UOP Platforming Catalysts: It is during periods of opening and cleaning equipment or in sampling that bodily exposure to UOP Platforming catalyst can occur and caution must be exercised.

voice or signal line communication with standby personnel. Subpart 1. Section1910. CF). Personnel working in reactors should wear a supplied air respirator with a hood or helmet. Avoid cleaning methods which raise dust. product. personnel in the reactor should be equipped with safety harnesses and safety lines for rescue and a means for visual. which should then be labeled as to the contents and hazards. The OSHA regulations concerning use of respirators (29 CFR. In addition. use local mechanical exhaust ventilation Wear a NIOSH-approved toxic dust respirator with full face-piece. • Handling UOP Catalysts Safely: UOP believes that OSHA exposure limits to catalyst chemicals will not be exceeded if proper handling procedures and worker protective clothing/safety devices are used. . During loading operations. Return material to supplier for metal recovery. protective clothing. or in a continuous flow mode (NIOSH Respirator Code SAFE: PD.134) should be read and thoroughly understood before undertaking to place personnel in reactors during catalyst loading and unloading operations. During unloading. the hazards may include inert (nitrogen) atmosphere. toxic feedstock. or purge materials present with the catalyst. Dispose of all catalyst wastes properly in containers. operated in a pressure-demand or other positive-pressure mode. especially to personnel working in the reactor. Do not dispose of catalyst wastes in a public water system or in the normal solid waste. large quantities of catalyst dust may be generated. protective clothing. PP. In areas where natural ventilation is insufficient. who should be strategically located with suitable rescue equipment. and emergency supply of air. UOP recommends that the following minimum safety procedures be established and adhered to: Handle catalysts only in a well ventilated area. and gloves for normal catalyst handling operations Reactor loading and unloading operations present extraordinary health risks. or toxic forms of catalyst chemicals. and gloves. This respirator should have a primary.CATALYTIC REFORMING • Handling Catalyst spills and Deposited Catalyst Dust: Always wear NIOSH-approved self-contained breathing apparatus or combination of toxic dust respirator-rubber frame eye goggles. secondary.

Materials which on exposure cause irritation but only minor residual injury even if no treatment is given. or which are readily dispersed in air and which will burn readily.Ch. Worn-out. Liquid and solids that can be ignited under almost all ambient temperature conditions. broken or defective safety equipment and clothing should be removed from service and repaired or replaced. or smoke in areas where the catalyst is being handled or where exposure to catalyst dust is likely National Fire Protection Identification of Color Coding: Color Blue: Type of possible injury Association Materials which on very short exposure may cause death or major residual injury even though prompt medical treatment was given Materials which on short exposure may cause serious temporary or residual injury even though prompt medical treatment was given Materials which on intense or continued exposure may cause temporary incapacitation or possible residual injury unless prompt medical treatment is given. Materials that must be preheated before ignition can occur. Materials which on exposure under fire conditions offer no hazard beyond those of ordinary combustible materials. drink. . Materials that must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. Color Red: Susceptibility of material burning Materials which will rapidly or completely vaporize at atmospheric pressure and normal ambient temperature. Good personal hygiene after handling a catalyst or being exposed to catalyst dust is an essential part of a responsible catalyst safety program. Materials that will not burn.6 Hazard Assessment Protective clothing and all safety devices should be thoroughly decontaminated after each use. Do not eat.

but which may become unstable at elevated temperatures and pressures or which may react with water with some release of energy but not violently Materials which in themselves are normally stable.CATALYTIC REFORMING Color Yellow: Susceptibility of release of energy Materials which in themselves are readily capable of detonation or of explosive decomposition or reaction at normal temperature and pressure Materials which in themselves are capable of detonation or explosive reaction but require a strong initiating source or which must be heated under confinement before initiation or which react explosively with water Materials which in themselves. are normally unstable and readily undergo violent chemical change but do not detonate. (C1-C4) Hydrogen Hydrogen Sulfide Benzene Toluene Xylene Phosphate DMDS Caustic Soda UOP Platforming Catalyst . sweetened Hydrocarbons. even under fire exposure conditions and which are not reactive with water Hazardous materials: List of attached material safety data sheets: Naphtha Reformate LPG. Also materials which may react violently with water or which may form potentially explosive mixtures with water Materials which in themselves are normally stable.

Ch.7 Plant Design .

4. The turbines or engines used to generate electricity can be operated non condensing and supply exhaust steam for processing purposes. Markets for Finished products The large oil refiners are located along the seacoast or near large cities where a market exists for the finished products. the plants own source or principle supply if the demands for water are large. Power and fuel supply The fuel best plan is to locate near large coal field if coal is the primary fuel or to tie up by long contracts sufficient gas and /or oil to ensure the continuity of operation over a long term. Markets and transportation The existence of transportation facilities has given rise to many of the greatest trade centers of the world. Raw materials supply T h e lo catio n o f th e ra w m a terials o f a n in d u str y co n trib u tes m o re to w ard th e ch o ice o fp lan t site th an an y o th er fa cto r. W ater S u p ply Water for industrial purposes can be obtained from two general sources. Crude oil is easily pumped by pipelines or shipped from the oil well sin the interior. v 2. lakes. Cheap rates are thus secured for a crude low-priced commodity. Sources of power: Power for chemical industry is primarily from coal water and oil. It is more economical for the industry to supply its own water such a supply may be obtained from drilled will rivers. A location should be chosen. if possible which has several competition will help to maintain low rates and given better service. The exact type of economic study of plant location will vary with each company making a study. damned streams . Consumed in large quantities while the finished products are made in the center of the market in order to lower the distribution cost. 3. T h is is esp e cially n o ticeab le in th o se in d u stries in w h ich th e ra w m a te rial is in ex p en siv e an d b u lk y an d is m a d e m o re co m p a ct an d o b ta in s a h ig h b u lkalu e.CATALYTIC REFORMING PLANT LOCATION The final choice of the plant site usually involves a presentation of the economic factors for several equally attractive sites. 5. Factors Affecting Plant Location 1.

Sensible use of floor and elevation space. 6. 3. d iv ersity . f 8. E ssen tially a p ro cess m u st b e d esig n ed fo r p ro d u ctio n o f a co m m o d ity o r co m m o d ities u n d er th e m o st eco n o m ic co n d itio n s. many factors must be considered such as: 1. L abor B efo re lo catin g an in d u stry in an y p articu lar lo catio n a carefu l stu d y o f th e su p p ly o f av ailab le lab o r m u st b e m ad e. ef icien cy an d co sts. 2. in tellig en ce. K in d . 7. 8. Weather condition are they amenable to out door construction. Waste disposal problems. w ag e scale. Water natural quality is as diverse as the sites and regions from which it is. F acto rs to b e co n sid ered in lab o r stu d ies are su p p ly . reg u latio n s. Also the site information is essential in the selection of apian location.7 Plant Design before a company enters up on any project. Sanitary and fire demands both present and future. Of great importance is a nature of the subsoil the need of piling or other expensive foundations can materially affect construction costs. power and gas. The chemical industry is usually of minor importance. if o u t sid e p lan t clim ate d o es n o t fit in to th e p ictu re o f p ro d u ctio n . C o m m u n ity an d site characteristics In the selection of a definite plant site in a designated area there are many minor factors to which some attention should be given. 5. 6. Economic distribution of services-water process steam. 7. Safety consideration possible hazards of fire explosion and fumes. the relative price are of greatest economic importance in determining the value of water to the chemical industry. Building code requirements. th en p ro cess an d p ro cess equipm ent.Ch. . it must ensure it self of as insufficient supply of water for all industrial. Water temperature and chemical characteristics such as organic and inorganic contaminants. The relative importance of each of these depends upon the service for which the water is wanted. New sites development or addition previously development. PLANT LAYOUT For marketing. Future expansion. C lim ate C h em ical p lan ts as g en eral ru les are rath er d ifficu lt to in su late o r to p ro v id e w ith artificial h eat o r co n d itio n al air. 4.

Thus the delineation of the shape and extent of a unite area and of interrelation ships of each area in a master plot plan is one of the first take of layout planning. . Unite areas are often delineated by means of distant process phase and operational producers by reasons of contamination and by safety consideration requirement.CATALYTIC REFORMING The layout will bed one by the use of (unite areas) concept method which are particularly well adopted to large plant layout.

Ch.8 Design .

2 10 6 0 .11 lb/ft3 ∴ ∴ ∴ ∴ Mass flow rate of C5+ = 49.3 = 1357.11 * 1112.4%] [(C1 + C2) wt% = 2.92 = 54655.6 = 558.and 45° API: ∴ ρC5+ = 0.2046 330 24 60125 lb / hr Molar flow rate of naphtha = 60125 / 107.C3 wt% = 3%] [H2 wt% = 2.22 ft3/hr ∴ Volume flow rate of C5+ = 0.18 10 3 2 .4 = 44.2 * 106 ton/yr Sweet naphtha flow rate = 18 % of crude flow rate ∴ Naphtha flow rate = 1 . (6-4): 3) From fig.4 = 49. (6-3): 2) From fig.3 lb/ft3 ∴ Volume flow rate of Naphtha = 60125 / 44.03 * 60125 = 1803.8 + 32 = 104 f° ∴ ρNaphtha = 0.7.8%] From Kern by tmean = 40 * 1.028 * 60125 = 1683.92 ft3/hr At tmean = 104 f° . (6-6): [C5+ vol% =82%] [C4 vol% = 6.C.=98):1) From fig.78 lbmol /hr By using catalytic reforming yield correlations at (K =11.71 * 62.O.5 lb/hr Mass flow rate of (C1 + C2) = 0.N.0225 * 60125 = 1352.787 * 62.25%.22 = 1112.5 lb/hr .82 * 1357.81 lb/hr Mass flow rate of C3 = 0.75 lb/hr Mass flow rate of H2 = 0. (6-5): 4) From fig. R.CATALYTIC REFORMING Material balance Crude flow rate = 1.

79 75.75+1683.5 + 90.79 lb/hr ∴ Mass flow rate of total lb/hr H2 = 1683.44 54655.8 Design ∴ Mass flow rate of C4 = 60125 – (54655.44 lb/hr C5+ C3 C4 .Ch.16 lb/hr recycle H2 lb/hr C1-C2 1683.81 629.5+1352.00151 lb H2/lb Naphtha ∴ Mass flow rate of recycled H2 = 60125 * 0.44 lb/hr Assume recycle ratio of H2 = 8000 Scf /bbl = 0.29 Material balance on flash drum:- 90.79 = 1774.5) =629.65 lb/hr net H2 C1-C2 1352.5 lb/hr 1803.81+1803.5 lb/hr 1277.75 lb/hr 629.5 1774.75 lb/hr C1-C2 lb/hr C4 lb/hr C5+ lb/hr H2 lb/hr C3 54655.29 1803.00151 = 90.

75 lb/hr C3 1803.44 lb/hr C4 1803.5 lb/hr C5+ 54655.5 lb/hr C5+ .75 lb/hr C3 629.44 lb/hr C4 54655.CATALYTIC REFORMING Material balance on stabilizer:- 629.

8 Design .Ch.

so A. Types of heat exchangers: 1-parallel flow heat exchanger: In this type of heat exchanger the two fluids flow in the same direction .If we assume that specific heat capacity is constant . To vaporize a liquid stream. -A multiphase mixture. Role of heat exchanger in chemical processing: Heat or cool a stream flowing from item of equipment to another. . -A gas. The stream may be: -A liquid. To condense a vapor stream.they are used widely in refinery industry to cooled products or preheat feed.CATALYTIC REFORMING Shell and tube exchangers: Heat Exchanger: Heat exchangers are devices build for efficient heat transfer from one fluid to another .Counter flow heat exchanger: In counter-flow heat exchanger fluids flow in opposite direction.

3.the required surface area for this heat exchanger is calculated from tables it's between surface area for counter flow and parallel flow. Preparation of design heat exchanger: 1.8 Design So rate of heat transfer between two fluids will be dQ/dT= U*A*dTlm where: U : overall heat transfer coefficient. and latent heat (for phase changes).Cross flow heat exchanger: In it the direction of fluids are perpendicular to each other . A phase change involved in the system: A quick look at the boiling points compared with the entrance and exit temperatures. 2. .Ch. The physical properties of the streams involved: you should get the physical properties for each zone separately to ensure accuracy. B. Physical properties that you will want to collect for each phase of each stream will include: heat capacity. thermal conductivity. density. Operating pressures are particularly important for gases as their physical properties vary greatly with pressure. A : area of tubes dTlm = (dt1-dt2)/Ln (dt1/dt2). The flow rates and operating pressures: This information is critical in establishing the mass and energy balance around the exchanger. These are in addition to the boiling points of the streams at their respective pressures. viscosity. but in some cases it is acceptable to use an average value.

Typical pressure drops are (5-8 psi) on the tube side and (3-5 psi) on the shell side. The Area of the exchanger: These can be found in most textbooks dedicated to the subject. use the equation Q=U A dTlm to get your preliminary area estimate. so does viscosity and the fluids ability to transfer heat. Once you've estimated the overall heat transfer coefficient. 6. Some guidelines may be as follows: 3/4 in. As the pressure drops. while erosion and material limits are motivation to keep the velocity low.CATALYTIC REFORMING 4. the pressure drop and velocities must be limited. . 7. The velocity is directly proportional to the heat transfer coefficient which is motivation to keep it high. Therefore. and 1. If your pressure drop requirements are low. Typical liquid velocities are (3-10 ft/s). The allowable pressure drops and velocities in the exchanger: Pressure drops are very important in exchanger design (especially for gases). 5. The Heat duty of the system: This can be calculated by a simple energy balance from one of the streams.0 in. baffle and tube spacing. diameter tubes are the most popular and smaller sizes should only be used for exchangers needing less than 30 m2 of area. tube sheet layout. Prepare layout for my exchanger: selecting a shell diameter. then check your velocity and pressure drop requirements to see if they're being met. Typical gas velocities are (50-100 ft/s). avoid using four or more tube passes as this will drastically increase your pressure drop.

steam is usually employed for this purpose. .The principal parts are two sets of concentric pipes.heat transfer surface . 15 or 20ft effective length .Double pipe exchangers are usually assembled in 12 . although in oil refineries hot recalculated oil serves the same purpose.Hairpins are useful as inexpensive heat . . tees and a return head and a return bend. -The return bends which is usually exposed and does not provide effective .Ch. two connecting. Double pipe exchanger: Heaters are used primarily to heat process fluid. IPS 2 2 1 /2 3 4 Inner pipe . IP 1 1 /2 1 1/4 2 3 .8 Design Other Considerations:     Materials of Construction Ease of Maintenance Cost of Exchanger Overall Heat Integration The tubular element: The full filament of many industrial services requires the use of large number of double pipe hairpins (double pipe heat exchangers).transfer surface. Double pipe exchanger fittings: Outer pipe . .Water is the main cooling medium. -The inner pipe is supported within the outer pipe by packing glands.

and these are now fairly standard.In some industrial uses it is desirable to install tubes in a tube sheet so that they can be removed easily. copper. 70 – 30 copper .Heat exchanger tubes are available in a verity of metals which include steel. . . admiralty.They can best be obtained by means of shell and tube equipment. and the stainless steels. aluminum bronze. brass. Heat exchanger tubes: The outside diameter of heat exchanger or condenser tubes is the actual outside diameter in inches with in a very strict tolerance. .Shell and tube equipment involves expanding a tube into a tube sheet and forming a seal which does not leak under reasonable conditions. aluminum. I1 Tubes are laid out on cither square or triangular pattern . The most common diameters arc % and 1 inch O.They are obtainable in a number of different wall thickness defined by Birmingham wire gage. Tube pitch: Tube holes can not be drilled very close together.nickel. which is usually referred to as BWG or gage of the tube. the shortest distance between two adjacent tube holes is the' clearance or ligament.CATALYTIC REFORMING .D. . -The tubes actually packed in the tube sheet by means of ferrules using a soft metal packing ring. .The use of a large number of double pipe hairpins consumes I considerable ground area and also entail a large number of points at which leakage may occur.

transfer coefficients result when a liquid is maintained in a state of turbulence to include turbulence outside the tube it's customary to employ baffles which cause the liquid to how through the shell at right angles o the axes of the lubes.to . Baffles: It is apparent that higher heat .8 Design Shells: Shells are fabricated from steel pipe with nominal IPS diameters up to 12 in above 12 in the actual outside diameter and the nominal pipe diameter are the same. which is satisfactory for shell-side operating pressure up to 300 psi. .center distance between baffles is called balled pitch or baffle spacing. The standard wall thickness for shells with inside diameters from 12 to 24 inch inclusive is 3/8 inch . The center .Ch.

Assume 85% of hot vapor amount used to heat naphtha and 15% used to heat recycle H2 in separated heat exchanger So M1= 0. For hot vapors: 1.(5) CP= 0. Data given: Hot fluid: Vapor from 3rd reactor mvapor= 60290 lb/hr T1=550 ˚f T2=250 ˚f Cold fluid: Naphtha feed mnaphtha = 60125 lb/hr t1=100˚f Design Steps: Step (1): Heat duty of heat exchanger.85*60290 = 51246.5 lb/hr .(1) K= 0.8˚ 2.(14) μ= 0.3388 lb/hr.˚ f b.(6) Sp.From Fig.ft d.42=0.57 3. Tmean= (550+250)/2 = 400 ˚f & API= 61.082 Btu/hr.CATALYTIC REFORMING Heat exchanger design: Choosing heat exchanger which used to exchange heat between the hot vapor from third reactor and naphtha feed need to preheated before enter the furnace.gr= 0.From fig.ft.545 Btu/lb.From fig.From fig.14*2. from kern book find physical properties of hot fluid: a.˚f c.

Ch.5 ˚f .356= Cpc (t2-100) Assume t2 ˚f 300 350 330 335 Tmean ˚f 200 225 215 217.T2) = 51246.75=60125 Cpc (t2-100) 139.595 Y=139.593 0.4 ≈ y So t2correct=335˚f From Kern Book: and tmean= 217.602 0. Heat duty Q Btu/hr: Q = M1 CP (T1.356 116.586 0.5*0.39 139.5 Cpc Btu\lb.8 Design 4.˚ f 0. API=61.6 150.8˚  Cpc=0.595 Btu\lb.545*(550-250) = 8378802.5 136.75 Btu/hr Step (2): Outlet temperature of naphtha feed t2=? ˚f for cold fluid : mcold= 60125 lb/hr t1=100˚f t2= ? ˚f Q constant = mcold Cpc (t2-100) 8378802.˚ f .

D: Use counter-flow heat exchanger which fluids flow in opposite direction.gr= 0.M.hr  Sp.CATALYTIC REFORMING  Kc= 0.ft.087 Btu\hr.42=0.T.31*2.˚f  μc=0. So rate of heat transfer between two fluids will be Hot: T1=550˚f Cold: t1=100 ˚f ∆T1=215˚f T2=250˚f t2=335˚f ∆T2=150 ˚f LMTD =(215-150)/ln (215/150) =180.7502 lb\ft.653 Step (3): L.55˚f Correction factor for ∆Tlm: .

˚f.˚f.Ch.hr Assume U=57 Btu/ft2. (10-34)A [1shell pass and 2 or more tube passes] We found f=0.hr Step (5): Area calculation A= Q /U*∆Tlm .5 ˚f Step (4): Assuming overall heat transfer coefficient U Btu/ft2.hr From table (10-17) U Range= (40-75) Btu/ft2.The cold-side effectiveness: R = (550-250)/(355-100) = 1.˚f.52 B.8 Design A.Capacity rate ratio: P = (335-100)/(550-100) = 0.9 LMTD corrected = 0.9*180.55=162.1765 From fig.

594/ (16-0. Actual no of tubes Nt: From table (10-10)E Choosing 4 passes.5)*0.D . 1.6 ft2 Step (6): Heat exchanger layout Using floating head heat exchanger for expansion and [ 1"O. Ntubes = 242 tube.CATALYTIC REFORMING Acal = 8378802. Number of tubes required Ntubes: Ntubes=A/ (L-0.4*Ntubes/pass*0.2618 = 222.92 ≈ 223 tubes 2.gr*62.75 / (57*162.Ntubes/pass=242/4 = 60. ∆BWG14.5) = 904.5)*ai ai: area of tubes per ft of length ft2/ft Ntubes = 904.5 ≈ 61 tubes Step (7): Velocity inside tubes Choosing naphtha feed (cold fluid) inside tubes V= W (lb/hr) /3600*Sp. IDS=24 in .25" P .00379 . L=16 ft ] 1.

23 4.at = Ntubes/pass * cross section area of tubes(ft2) = 29*0. IDs=24 in Step (8): Tubes side film coefficient (hio): 1.0965/0.1099 = 547038.6=39 tubes V=2.653*62.7502 =50692.79 ft/sec ≈ 3.8 ft/sec Check: V in range (3-6) ft/sec ok Choose : Ntubes=228 tubes No of passes =8 Ntubes/pass = 29 tubes.Re =Gt*Di/µ c =547038.Gt = 60125/0. L/Di JH=160 6.11 ft2 2.5=29 tubes V= 3.L/Di=16/0.486 lb/ft2.069=230 5.4*61*0.79 ft/sec < 3 ft/sec (1) Increase no of passes to 6 passes From table Ntubes=232 tubes .Ntubes/pass =232/6=38.hi = JH*(K/Di)*(µ*Cp/K)1/3 .00379 = 0. Ntubes/pass= 228/8=28.8 Design = 60125/3600*0.1099≈ 0.00379 = 1.from fig(10-46) by Re.486*0.hr 3.81 ft/sec < 3 ft/sec (2) Increase no of passes to 8 passes From table at Ntubes=228 tubes.Ch.

hr Step (10): Fouling resistance Ro.CATALYTIC REFORMING = 160*(0.076 Btu/ft2.5/0.25 in = 24*0.hr Step (9): Shell side film coefficient (ho): 1.0015 from table (10-12) .06)*(0. (10-54) by Re.7502*0.Ri Ri =reformer charge = 0.Re = Gs*De/µ h = 64058.˚f.˚f. C=0. baffle cut Δ.087) 1/3 = 345.as = ID*C*B/144*P .Gs =51246.125*0.8 ft2 3.087/0.25% JH = 57 6. P=1.ho = JH*(K/De)*(µ h*Cp/K)1/3 = 57*(0.082) 1/3 = 102.˚f.834/1) =288.06/0.hr 4.8 = 64058.125 lb/ft2.From fig.3388 = 11337.hio = 345.082/0.4*(0.25 in.25*24/144*1.4 Btu/ft2.1 Btu/ft2.3388*0.0695)*(0.25 = 0.hr 7.72 5.595/0.545/0.assume baffle spacing B= 24 in its range(24"-2") 2.

2618 = 228*15.48 Btu/ft2.Areq)/ Areq]*100 = [(925.7)/838.2-838.5)*0.Ch.0015+0.2 ft2 C.0015 U = 61.75/ (61.3% ok in range (10-25%) Step (13): Pressure drop A-Pressure drop in Shell side: 1.0015 Step (11): Calculation of overall heat transfer coefficient U Btu\ft2.hr (1/u) = (1/hio)+(1/ho)+Ri+Ro =(1/288.618 = 925.7]*100 = 10.˚f.Area available: Aav=Nt*(L-0.5*0.7 ft2 B.48*162.1)+0.hr so ok Step (12): Area required and Area available A-Area required: Areq=Q/U*∆Tlm =8378802.076)+(1/102.φs is neglect .˚f.8 Design Ro =reformer effluent = 0.5) = 838.˚f.Check: Excess Area % = [(Aav.hr > U assume =57 Btu/ft2.

DS=ID=24 in .22*1010*0.Ns+1=L/B =16*12/24=8 3.486)2*16*8 ΔPt= 5.00017*(547038.Npasses=8 pass .1 psi < 5 psi ok B.57 = 0.09231≈0.CATALYTIC REFORMING 2.00017 0.from fig (10-138) at Re=50692.22*1010*0. (10-140) at Δ .Pressure drop in tubes side: ΔPtubes=ΔPt+ΔPr f *Gt2*L*N passes [1] ΔPt = 5. S=0.653 = 2.23 f=0.0695 ft.75 psi .22*1010*Di*S a.0695*0.7486 ≈ 2.06*12*0.06 ft 0.25% and Re=11337.00251*(64058.72 f=0.De=0.L=16 ft Di=0.125)2*24*8 5-ΔPs= 5.00251 4.653 b.from fig.

8 Design [2] End Return Losses(ΔPr ): a.8 = 7.75+4.ΔPr = Δpr (fig)* no of passes = 0.Ch. Sp. .k.8 ft/sec .8 psi ΔPtubes = ΔPt+ΔPr = 2.6 psi b.653 Δpr (fig) = 0.(10-139) by V=3.6*8 = 4.from fig.55 psi < 10 psi check is o.gr=0.

CATALYTIC REFORMING .

this heat is circulated around the tube of the furnace (in which the liquid exists) in heater.8 Design FURNACE DESIGN A fired heater is necessary for heating the feed to the desired temperature (Process temperature). and this increase furnace efficiency by allowing more heat to be used before it leaves through the stack .Lighting pilots: protection of pilots by wearing the safety clothes while working 4. In the study of furnace we will choose some items help in knowledge of its performance.Inspection: the pilots inspect the furnace before it starts so as to ensure its stable performance 2-purging the furnace 3.Furnace equipment First: furnace start up This is made by 5 steps 1.Furnace start up 2.Ch.Heat transfer: Heat is produced by the combustion of fuel in the burners. Heat transfer has two methods in furnace Radiation & Convection In radiation section: heat is transferred to the tubes (Radiant tubes) by radiation In convection section: flue gases carry heat to the tubes (convection tubes).Lighting furnace: slowly open the gas valve then start lighting procedure 5. This heating is made by burning the fuel and use the heat liberated from this operation to heat the feed to the wanted temperature. and these are as follow: 1.Normal operations Second: heat transfer and combustion .Heat transfer and combustion 3.

2.CATALYTIC REFORMING -Combustion: To make the combustion there must be three factors present in the same time fuel + air + ignition source fuel: it could be natural gas or fuel oil ( mazot ) or both .Gives a more amount of heat . but in industry we prefer natural gas as it has some advantage like .Less expensive .Fire box: it produces the flames to heat the fluid . Third: furnace equipment 1.More cleaner . As air help in complete combustion it helps in utilizing the maximum amount of heat in the fuel. incomplete combustion also leaves some fuel in furnace which accumulated causing bad furnace performance .Don't cause problems with environmental laws * Air: in furnace we use air with specified ration to fuel and it is as follow 20 % excess air in case of natural gas 25 % in case of mazot air is used to give the Oxygen necessary for complete combustion because incomplete combustion doesn't make the best benefit of fuel heat it also produces Co which cause conflicts with environmental laws .Radiant tubes: in which the fluid pass in the radiation section . Air also is used to keep the flame temperature in its range because if it increased it causes Nox production which causes cancer.

from the floor of the heater. . Types of vertical fired heaters:1-Vertical-cylindrical.5 to 20 million Btu/hr. and doesn't permit any air to enter the combustion zone 3. 2-low efficiency design.Damper: control the flow of hot gases out of the furnace 8.Burner: it mixes fuel with air in a manner to keep stable combustion and it differs according to the fuel type.Convection section 6. 4-typical duties are 0. whether the tubes are vertical or horizontal.it requires a minimum of plot area . 3.Draft: for the pass of flame gases organizing 7. Classification of furnce:The principal classification of fired heaters relates to the orientation of the heating coil in the radiant section. so they are termed as (shield).Chock bank: bank of tubes between convection section and radiation section.A covering material covers the floor and walls of the furnace this material: . These tubes rows are usually being subjected to the highest heat-transfer rates in the fired heater. or (shock) tubes 5. Firing is also vertical. Properties:1-heaters of this type represent a low-cost. all radiant: Here the tube coil is placed vertically along the walls of the combustion chamber.reflects heat back into the tubes 4.reduces heat losses .Ch.8 Design Note that: the flame doesn't touch the tube this is called flame impingement it destroys the tubes.

and firing is vertical from the floor. The radiant-section tube coil is disposed in a vertical arrangement along the walls of the combustion chamber. The distinguishing feature of this type is the use of added surface area on the upper reaches of each tube to promote convection heating. the vast number of existing units of this type warrants its mention in any review of fired heaters. also fired vertically from the floor.CATALYTIC REFORMING 2-Vertical-cylindrical. feature both radiant and convection sections. 3-requires a minimum of plot area. 2. So we will include vertical furnace design in our study. 4.5 to 20 million Btu/hr.Vertical-cylindrical. This surface area extends into the annular space formed between the convection coil and a central baffle sleeve. Medium . 4-one limitation on these units is that generally only one flow path is followed by the process fluid. with cross flow convection: These heaters. 5-heating duties run from 0.The convection section tube coil is arranged as a horizontal bank of tubes positioned above the combustion chamber. high-efficiency design that requires a minimum of plot area. 3-Vertical-cylindrical. Properties: 1-This design also represents low cost.Low efficiency. This design is likewise vertically fired from the floor. Typical duties are 10 to 200 million Btu/hr. helical coil: The coil is arranged helically along the walls of the combustion chamber. This configuration provides an economical. with its tube coil installed in a vertical arrangement along the walls. with integral convection: Although this design is rarely chosen for new installations.

or horizontal between the riser portions of the U-tubes. In addition. The typical duty range for each cell runs from about 20 to 125 million Btu/hr.Arbor or wicket: The radiant heating surface is provided by U-tubes connecting the inlet and outlet terminal manifolds. 5. and in various reheat services. Typical duties are 10 to 100 million Btu/hr.Ch. a cross flow convection section is normally installed to provide supplementary heating capacity for chores such as stream generation. Typical applications are found in petroleum refining.8 Design efficiency can be achieved with a minimum of plot area. where this design is often employed in the catalyticreformer charge heater. double fired: Vertical radiant tubes are arranged in a single row in each combustion cell (there are often two cells) and are fired from both sides of the row. . Another variation of these heaters uses multilevel side-wall fired. This type is especially suited for heating large flows of gas under conditions of low pressure drop. these represent the most-expensive fired heater configuration. which gives maximum control of the heat-flux profile along the length of the tubes. Single-cell models are available for smaller duties. As a group. Firing modes are usually vertical from the floor. Such an arrangement yields a highly uniform distribution of heat-transfer rates (heat flux) about the tube circumference. Multilevel side-wall fired unites are often employed in fired-reactor services and in critical reactor-feed heating services.Vertical-tube. 6. Typical duties for each arbor coil of this design are about 50 to 100 million Btu\hr.

CATALYTIC REFORMING

Types of horizontal fired heaters:1- Horizontal tube cabin: The radiant-section tube coils of these heaters are arranged horizontally so as to line the sidewalls of the combustion chamber and the sloping roof or "hip." .the convection-section tube coil is positioned as a horizontal bank of tubes above the combustion chamber. Normally the tubes are fired vertically from the floor, but they can also be horizontally fired by sidewall-mounted burners located below the tube coil. This economical, high-efficiency design currently represents the majority of new, horizontal-tube, fired-heater installations. Duties run 10 to 100 million Btu/hr. 2- Two-cell horizontal tube box: Here the radiant section tube coil is deployed in a horizontal arrangement along the sidewalls and roof of the two combustion chambers. The convection section tube coil is arranged as a horizontal bank of tubes positioned between the combustion chambers. Vertically fired from the floor, this is again an economical, high-efficiency design. Typical duties range from 100 to 250 million Btu/hr. for increased capacity, the basic concept can be expanded to include three or four radiant chambers. 3- horizontal tube-cabin with dividing bridge wall: The radiant-section tube coil is arranged horizontally along the sidewalls of the combustion chamber, and along the hip. The convection-section tube coil takes the form of a horizontal bank of tubes positioned above the combustion chamber. A dividing bridge wall between the cells allows for individual firing control over each cell in the combustion chamber. Available options permit horizontal firing with sidewall-mounted burners or

Ch.8 Design

vertical firing from the floor along both sides of the bridge wall. A typical duty range for this design is 20 to 100 million Btu/hr. 4- End-fired horizontal tube box: The radiant-section tube coil is disposed in a horizontal arrangement along the sidewalls and roof of the combustion chamber. The convection-section tube coil is arranged as a horizontal bank of tubes positioned above the combustion chamber. These furnaces are horizontally fired by burners mounted in the end walls. A typical duty range for this design is 5 to 50 million Btu/hr. 5- End-fired horizontal tube box with side-mounted convection section: Here the radiant section tube coil is disposed in a horizontal arrangement along the sidewalls and roof of the combustion chamber. The convection-section coil is arranged as a horizontal bank of tubes positioned along side the chamber. The unit is horizontally fired from burners mounted on the end wall. These furnaces are found in many older installations, and occasionally in new facilities that burn particularly poor grades of fuel oil containing a high ash concentration. This relatively expensive design provides duties ranging from 50 to 200 million Btu/hr. 6- horizontal-tube, double-fired: Horizontal radiant tubes arranged in a single row and are fired from both sides to achieve a uniform distribution of heattransfer rates around the tube circumference. Such heaters are normally fired vertically from the floor. They are often selected for critical reactor-feed heating services. For increased capacity, the concept can be expanded to provide for a dual combustion chamber. A typical duty range for each cell of this design is about 20 to 50 million Btu/hr.

CATALYTIC REFORMING

In industry we prefer the vertical furnace as it has some advantage than the horizontal. Which are: - Little space used - Easy maintenance - Less expensive - Better draft

Data given:Fluid:Heavy sweet naphtha, 61.8◦ API, Flow rate (Gnaphtha) = 60125 lb/hr, Boiling range (171-400 F◦ ) Recycle H2, Recycle (C1 –C2), lb/hr Flow rate (GH2) = 90.79 lb/hr Flow rate (G (C1-C2)) =75.16 [Total flow rate= 60290.95 lb/hr] Inlet temperature (t1) = 871 F◦ Outlet temperature (t2) =1010 F° Fuel gas, LHV=19700 Btu/lb

788% 4.Efficiency 1.33 Btu/lb 3. 10000 Btu/hr ft2 Design steps:Step 1:.Ch.FGT= 871 + 150 =1021 F◦ [>400 F°] O. 2.% heat extracted = (14733. (3) Berman: By excess air =15 %.Calculated efficiency = 74.2 .K.33 / 19700) * 100 =74.788 . 15% Average radiant rate.8 Design Design basis:Vertical –cylindrical heater with horizontal –tube convection section. and FGT = 1021 F° Ha. Excess air.From fig. FGT = 14733.

CATALYTIC REFORMING

F.G.T

T1

Radiation

T2

ξ =72.788% 5- At (tm= (871 + 1010) / 2 = 940.5 F°) of fluid and 61.8 API from Kern obtain its physical properties:Cp naphtha= 0.765 Btu/lb F° ,CpH2= 3.5 ,Cp(C1-C2) = 0.85 6- Q duty = [60125 * 0.765 + 90.79 * 3.5 + 75.16 * 0.85] * [1010 - 871] = 6446441.364 Btu/hr 7- Heat fired = 6446441.364 / 0.72788 = 8856461.73 Btu/hr 8- Fuel consumed = 8856461.73 / 19700 = 449.567 lb/hr 9- from fig. (2) Berman: By excess air =15%, L.H.V=1000 Btu/ft3 Flue gas / fuel ratio =19.0625 lb-flue/lb-fuel 10-flue- gas flow = 449.567 * 19.0625= 8569.863 lb/hr

Step 2:- Radiant /convection duty split
1-select tube coil having 3 passes of 4 in IPS Sched. 40 [4.5 in O.D. * 0.237 in avg. wall] 2- Fluid mass velocity= (60125 + 90.79 + 75.16) / (3600 * 3 * 0.0884) = 63.15 lb/s ft2 O.k. in the range [45-70 lb/s/ft2]

Ch.8 Design

3-fluid temperature at radiant inlet (tc)=

t c 871 1010 tc

5 12

tc = 911.88 F° Assume fluid temperature at radiant inlet = 915 F° 4-radiant section average fluid temperature:

tB

1010 915 962.5F 2

5- Radiant section average tube metal temperature: tm= 962.5 + 75 = 1037.5 F° 6- Bridge wall temperature (Bwt) From fig. (6a) Berman by tm= 1037.5 F° and aveg. Radiant rate (qr) =10000 Btu/ft2 hr Bwt =1658.76 F

1010F°

915F°

900F°

871F° Fluid

radiation tflame

shield

convection 1021F° 1448.76F° Flue gas

1658.76F°

7- from fig. (3) Berman: By excess air=15% and Bwt=1658.76 F° Ha,Bwt = 10790 Btu/lb QR =(10790 / 14733.33) * 6446441.364 = 4721071.361 Btu/hr Qc= 6446441.364 - 4721071.361 = 1725370 Btu/hr

Step 3:- Furnace layout
1- AR = (4721071.361 / 10000) = 472.11 ft2 2- Assume 24 radiant tubes on 8 in center 3- Tube circle diameter (TCD) =(24* 8) / (12*π) = 5.093 ft

CATALYTIC REFORMING

4- ETLshield bank = 5.093 – 1 = 4.093 ft ≃ 4.1 ft 5- With 6 tubes per row on 8 in center 6- Shield bank free area = 6* 4.1* ((8 - 4.5) / 12) = 7.175 ft2 7- gflue gas= 8569.863 / (3600 * 7.175) = 0.332 lb/s/ft2 8-surface area of one shield row = 6 * 4.1 * π * (4.5 / 12) = 28.981 ft2 9- Vertical tube radiant surface area= 472.11-28.981 = 443.129 ft2 10-vertical tube radiant length= (443.129 * 12) / (24* π* 4.5) vertical tube radiant length = 15.672 ft 11-check for L/D ratio = 15.672 / 5.093 = 3.08 O.k. in the range [2-4]

5.093 ft

4.093 ft

26 Ln( ) 541.76 + 1448.76)0.332)0.8 Design Step 4:.76 R° Flue gas 1658.0925 Btu ft 2 F hr 5-hrg = 0.1 * (5.14* (0.5 ∆Tmin=541.76) / 2) + 460 = 2013.4 5.3844) = 9.76 fluid 907.26 541.76 .26 751.53F 3-Tga = ((1658.0.5)0.28 (4.3844 Btu/ft2F°hr 6.5 F° 2- Tlm 751.h0 =1.5 907.3246 Btu/ft2F°hr .6 * (2013.0925 + 3.0025* (2013.460) .26 640.26 ∆Tmax=751.26 4- hc 2.5 = 3.Ch.76 1448.Shield bank 1.average fluid temperature in shield bank=(915 + 900) / 2 =907.

shield=11932.975 Btu/ft2F°hr 11.Ri= (4.782 hi hi 0 .000818 Rt= 0.185) = 0.= 907.943 * 640.000818 = 0.8 * ( 0 .0726 * 12) = 1174276.975 * 86.k.210) = 1448.754 Btu/lb F° Kmix= 0.981 = 86.86 ) 0.158) / 4721071.5 / 4.76 F° .07 = 0.CATALYTIC REFORMING 7-determine physical properties of fluid at tavg.03 = 0.42 * 0.237 = 1367 Btu/ft2F°hr 10.1072 + 0.Re = (63.026) * (1 / 1367) = 0.361] * 10790 = 11932.86 Pr= (0. ≃ (BWT .Qshield = 8.361 + 499814.943 ft2 12.5 9.shield= [(4721071.07 Btu/ft2F°hr Mmix= 2.00335 R0= 1 / 9.1114 = 8.027 * (1174276 .1114 Ushield= 1 / 0.333 * 333 .324 Btu/lb and excess air=15% From fig.026) * (1 / 333.158 Btu/hr 13.07 4 .782 ) 0.5 * 3600) / (0.324 Btu/lb By Ha.1072 Rw= (4.0726) / 0.53 = 499814.754 * 0.(3) Berman Tsh=1475 F° O.15 * 4.5 F° Cpmix= 0.Check of flue gas temperature above shield bank Ha.5 / 4.Ash= 3 * 28.hw= 324 / 0.00335 + 0.3246= 0.185 Btu ft 2 F hr 12 * 0 .0726 lb/ft hr 8.

863 / 6. 76 ln 150 307 . 44 F 3-try 3 fins/in with each 3/4in high *0.05 * 0 .037 Btu/ftF°hr 7-Re= (1276.76 + 1021) / 2= 1234.convection section 1-Q'c pure=1725370 .75 * 3 = 6 * 4 .33 ft2/ft) 1021 Flue gas 1448.8 Design Step 5:.05in thick (At=7.From fig.842 Btu/hr 2- T lm 548 .013 .76 4-fin bank free area 8 4 .499814. K= 0.76 fluid 871 900 ∆Tmin=150 ∆Tmax=548.7138 ft 2 5-Gflue gas= 8569.268 Btu/lb F°.=(1448. Cp= 0.1 lb/ft hr.Ch.1 * 12 12 6 .464 * 4.1) = 4786. 76 150 548 . (7) by Re= 4786.464 lb/ft2hr 6.Determine physical properties of flue gas at Tavg.74 J= 0.5 2 * 0 .7138=1276.158 = 1225555.5) / (12 * 0.88 F° M= 0.74 8.

268 * 1276 . 578 Btu ft F hr 2 10-From fig.2071 Ri = (7.CATALYTIC REFORMING 9- h0 0 .Aconv.005087 Rt = 0. 84 ( 7 . 037 2 3 5 .318 ft2 .5 12 ) ho(eff.Ro= (1 / 4. (8) by KT= 1.35 .829) = 0.291 307 .) = 4.33 = 180.ho(eff.23305) = 4.02087 + 0.842 = 4.75 in and h0= 5.0056 ft 2 14. 1225555 . 33 4 .2071 + 0.H= 0.578 Btu/ft2F°hr ξfin = 84% 11.33 / 1. 013 * 0 .33 / 1. 578 7 .Surface area per convection row = 6 * 4.1 * 7.) = 5 .054) * (1 / 1367) = 0.829 Btu ft 2 F hr 12.23305 Uconv.02087 Rw = (7.185) = 0.291 Btu ft 2 F hr 13. 464 0 . 268 0 . = (1 / 0.44 929 . 33 ( 0 .005087 = 0.054) * (1 / 333. 1 * 0 .5 12 ) 4 .

ρflue = 0.318) = 5. 176 ft Assume average gas temperature in stack = 1021 – 75 = 946 f° Assume stack-exit gas temperature = 871 f° Draft under arch = 0. ∴ ρflue =0.2 * 0.007 lb/ft3 Shield-bank loss = 3 * 0. =1234.464/3600) )2 * (1276.003 * (1.863 3600 0 . = 1553.76 f° in shield-bank of flue gas.88 f° in convection of flue gas.8 3 .332)2 * (0.25 * (1276. ρflue = 0.33 /0.8 Design 15.0088) ) = 0.2 * 0.0088 lb/ft3 Fin-bank loss = 6 * 1* 0.Stack design: Size stack for mass velocity of 0. = 946 f° in stack of flue gas.025 lb/ft3 .0147 in At ∴ tavg.8 flow Cross-sectional area = Lb at 125% of design gas sft 2 1 .05 in At tavg.007) ∴ Shield-bank loss = 0.Number of finned rows = (929. 72 ∴ Stack diameter (D) = 2 .003 * (1.14247 in At ∴ tavg.Ch.25 8569 .0056 / 180.15 Number of finned rows = 6 rows Step 6 :.72 ft 2 4 * 3 .464/(3600*0.

= 871 f° in stack exit of flue gas.8)2 * (0. 00196 in Net stack effect/ft = 0.3 14 .9 0. 69 1 540 1 1406 ( 0 .8/0.0512 + 0.00675) = 50.8/0.3398 in Stack draft gain/ft 0 .00871 – 0. ρflue = 0.69 1 540 1 1694 .05 Subtotal = 0.52 4.03 lb/ft3 Stack-exit loss = 1 * 0.14247 + 0.09216 in At tavg.04145 = 0.025) = 0.03072 in Damper loss = 1.8/0.8 ) 2 211000 0 .00196 = 0.38125 – 0. 176 0 .38125 in Convection-section draft gain= 0. 52 * 1 * * 14 .34 ft .03072 + 0. 00871 in Stack fractional loss 1406 2 .CATALYTIC REFORMING Stack-entrance loss = 0.025) = 0.3398 / 0.04145 in The required stack draft = 0.003 * (0.003 * (0.0512 in Subtotal = 0.8)2 * (0.003 * (0.5 * 0.03) = 0.0147 + 0.00675 in Stack height required = (0.09216 + 0.5 * 0.8)2 * (0.

026 / 12) = 385. 12 0.026 63.shield = 6 / 3 = 2 passes Nrow = 3 + 6 = 9 rows Le = 2 * 9 * (4. = 1.00365 8- P 0.662 = 8.Le.03 4.395 = 667.∆Pact.8 ft 3.17 ft 5.5 f° of fluid .Re 4.25 * 6.117 / (1050586.1 + 3* 30 * (4.026 / 12) + 8 *15. = 24 / 3 = 8 passes Le = (8 – 1) * 50 * (4.For ( Crossover ) :- Le = 2 * 4.1 + 1.00365 (63.0726 7.975 ft 2. sp.395 ft 4.25) = 0.364)0.33 psi .8 + 38. and µ= 0.Fluid pressure drop:1.026 ∆P = 6.By tavg = (871 + 1010) / 2 = 940.5) + (2 * 9 – 1) * 50 * (4.Ch.662 psi 9.15) 2 667.026 / 12) = 38.00517 0.4 0.03.0726 lb/ft hr 6.rad.For ( Convection + Shield ) :- Npasses.17 62.For ( Radiation ) :- Npasses.f = (0.8 Design Step 7:.672 = 242.gr = 0.975 + 242.15 3600 1050586364 .total = 385.

CATALYTIC REFORMING .

XA) A Where. (50 hr-1) . Derivation of the Plug-Flow Reactor Formula τp C Ao V F Ao 1 k CAo n -1 XA XA C Ao 0 dX A . The reactor is an ideal plug flow reactor. The reactor is a one-phase reactor and neglecting the presence of catalyst. The reactor is iso-thermal. 5. for its very small and negligible volume compared to the volume of voids.rA (1 0 XA) n dXA (1 . -rA = rate of disappearance of reactant A k = rate constant of dehydrogenation reaction.Ch. XA = conversion at the end of reactor. 4. CAo = concentration at XA=0 (mol/m3). V = volume of reactor without catalyst. 2. 3. Optimum conversion is as high as 60%. FAo = molar flow rate in (mol/hr).8 Design Reactor Design Assumptions to ease Design Procedure 1. Feed is pure ethyl cyclohexane with recycle hydrogen and is only subjected to the dehydrogenation reaction due to the high rate of this reaction and its high equilibrium state which lead to that the reaction nearly goes to equilibrium in the first reactor. as heat is constantly supplied.

105 ( 1 .CH3 1 . (*) V 0.XA ) 2 A XA ) 1 -1 2 ( 1 .CH3 + 3 H2 rA n 1 k C A1 Then Performing the integration.XA ) Setting: Conversion XA = 0.V XA 0 0 V XA CH2 .6 0 ( 1 XA ) A ( 1 ( 1 .105 ( 1 FAo A) CAo A ) ………………. and substituting with (n = 1) p 1 k CAo 0 1 k A 0. V XA ε = fractional volume change = CH2 .CATALYTIC REFORMING n = order of reaction.6 and Rate constant k = 50 hr-1 ( Calculated Analytically ) p CAo V FAo 0.

4 1000 x 273 .2 = 3402 mol H2/hr FAo = 3402 + 217717 = 221119 mol/hr ………………….nXA 0 0 nXA 874271 .186 x 18288.186 mol H2/kg naphtha = 60.(1) For basis of 1 hr. and isothermal reactor nXA=0 = 221119 mol nXA=1 = 3402 + 4 x 217717 = 874271 mol nXA A 1 .000 lb/hr = 18288.221119 221119 A = 2.95 ………………………………………………(2) * Volume at XA=0 (T=798 °K and P=30 atm) P 1 V1 T1 P 2 V2 T2 V2 x 30 798 221119 x 1 x 22.8 Design Data Given and Calculated Naphtha Feed Mw. Naphtha Density Hydrogen recycle = 112 (C8 H16) = 755 (56 °API) = 8000 scf H2/bbl naphtha = 0.2 kg/hr = 217717 mol/hr Naphtha Feed Design Procedure Recycle H2 = 0.Ch.

wt of 112 of naphtha feed that led to the high no.105 ( 1 + 2.9 m Notes The reactor volume seems to be very large for :  The massive flow rate of naphtha.CATALYTIC REFORMING Hence. If the presence of hydrogen in the feed is neglected. (3). CAo = (221119/482. the volume of the reactor would be 150 m3 and ( D = 4 m . L = 12 m ) . (2).61) = 458 mol/m3 ……………(3) From (1).95 ) ( 221119/458) = 200 m3 Using the assumption of L = 3D for the reactor 200 m3 = (3π/4) D3 D = 4.3 m L = 12. of moles in the gaseous phase which led to the high volume of feed.  The small assumed M. I n (*) V = 0. V = 482.61 m3 Hence.

8 Design .Ch.

96126 1.000 Xb 0.7872 1.04234 0.000 Xd 0.01770 0.0067 0. .910 C1 36.0000743 0.000 0.000 0.000 0.06578 0.02719 0. Bottom temperature = 243 oC.05807 0. Feed temperature =164 oC.000 1. Top temperature = 86 oC .0462 H2 16.108 C2 40.051817 0. Top pressure = 1 atm Bottom pressure = 2 atm .50 C6 summation 621.01518 0.36521 0.000 Flow rate of naphtha = 621.02269 0.CATALYTIC REFORMING Tower design: Design data: Component Flow rate lbmole/hr 0.060 n-C5 + 489.81 Xf 0.164 i-C4 6.15098 0.81 Kgmol / hr Feed API = 50 ~ 53˚ Yield = 83% by vol.650 n-C4 16.470 i-C5 11.000 0.32293 0.02648 0.01070 0.000867 0.0004125 0.904 C3 4.000 0.037179 0.02966 0.

425. Total Material Balance :F = D+B Individual Material Balance on the component :FXf = DXd + BxB .81 ( 0. 621.6 Composition C3 i-C4 n-C4 i-C5 n-C5 C6+ i 2.048 31.0513 1.16 244. Step(2): Light key is ( n-C4 ). (°F) -43.744 0.1282 .q=1 Feed properties : Boiling Pt.474 11.00117 Kgmol /hr B=509.0000743 ) = D ( 0.4 97. Feed enters at boiling point . Heavy key is (i-C5).1 292.56 385.5 365.667 1 0.564 2.8088 Kgmol / hr.81 Kgmol / hr.Ch.352 82.79 342.0004125) + 0 D= 112.1 357.8 Design Design steps : Step (1) F= 621.04 Pi° (psia) 1000 800 650 390 290 50 Heat of vaporization KJ / Kg.

) n i i xif i i 1-q = i=1 n xid - Rmin + 1 = i=1 Where :xif = The values for each component in the feed.1 Calculation of the minimum number (Nmin) of theoretical plates by the Fenske equation :XdLk XbHk log Xdhk Nmin = Lk XbLk log Hk Nmin = 17. xid = The values for each component in the distillate. Solution :=1. = the relative volatility of component (i) with respect to the heavy key component.32 . q = the feed thermal condition . = the underwood's constant.CATALYTIC REFORMING By using underwood's shortcut method to calculate the minimum reflux ( Rmin.2 Rmin .268 Rmin = 1.6 Rop =1. Rop = 1.

If take plate efficiency =50% Nact = Nthoer / = 19.4 * 259.2 plate .347484X4 Where: X=(Ropt-Rmin)/ Ropt = 0. of trays * H / 12 + 2*5 H = 24 in Z = 40 * 24/12 + 2 * 5 = 90 ft.8 Design To calculate theoretical number of plates : By using Gilliland correlation relating number of stages to reflux ratio : Y= 0.1 Ib / ft 3 v = 0.75X0. 2) Tower diameter (D) : P =latm .v ) / v)1/2 K = 0.608295-1.27= 40 trays Step (3) : To calculate the tower diameter and tower height : (1)Tower height (Z): Z = no.4 ft3 /lbmol VD = 398. Nact = Nthoer / = 18.16667 Y=(Nt-Nmin)/(Nt-1) = 0.84=103520 ft3 / hr.5 = 36 trays By Gilliland–Eduljee method : Y= 0.365/ 0.532489X3-0.75-0. L =RD V = D (R + 1 ) = 259.2/ 0.8 Ib / ft Vc.5663 = 0. TD=86oC.Ch. VD = 359 * ( 460+86 )/(460+32)* 1/1 VD = 398.16 from (Fig 2) . 3 L =48.1893X+0.365 plate .332227X2+0.84 ft3 /hr.4783 Ntheor =19.s =K ( ( 1 .5 =39.4935 If take plate efficiency =50% Ntheor =18.

274 (0. . VC.997 .45 Adc2 = 28.45) =12.7233 ft2 LW2 / D = 0. / 1.997*6*12=71.616 in .461 (6) *12=33.879 ft.S = 1. H = 24 in.274 ft2 Adc1 = 0. standard D= 6 ft Sieve Tray design : Given data : D = 6 ft.dW /D = 0.23 ft.192) = 5.097 Lwl = 42. A = V/v = 26. dwl= 6.S Design = VC.784 in dW =0.05 * 28. L = 1650 Gpm Advantages of sieve tray : (1)lower pressure drop than bubble cap tray (2)performance and design is more simple (3) stability condition is achieved on each tray [1] Down flow area : Adf / AT = 20% Adc / AT = 10% Adc1 / AT = 0.461 Lw2=0.CATALYTIC REFORMING VC.15 = 1. ./sec.2dw dw2 = 4* 12 – 2 (33.984 in Adc2 /AT =0.85 ft.59 dwl/D = 0.S Max./sec.48 in .07 ft.2 D = (4A / )½ = 5.274 = 1.4137 ft2 Lw1 / D = 0.05 AT = /4 D2 AT = 28.192 in dw2 = D . From (Fig 3) Type of flow is double pass.

304) dw3 '= 34 in dw3'/An' = 0.796 * 5) Adis = 890.45 dw' / Dm' = 0.796*2)) Aeff = 2162.64)-363.1 (3631.54 * 5)+2(67.796 in dw3' = dw' + 1/2 dw2' = 31.A4' -2 (Lw2' * x) Aeff = ((3631.Ch. y = 3in Dn' = D .348) = 5. x = 5in .fig (8-48) Adc3' /An'= 0.984 +5-2 dwl ' = 9.461 dw' = 0.0142 ft2 [3] Liquid distribution area : Adis = 2(Lw1 *5/12)+2(LW2*5/12) =2(3.348 in dw2' = Dn' – 2 (dw' ) = 68 .997 (68) = 67.9 ft2 Adcs' /An' = 0.168 in2 Aeff =An '-2Adcl' .2 =12*6-2(2) Dn' = 68 in An' = /4(Dn )2 =3631.68) =363.115(3631.5 A4 = An' * 2 ( Adc3' / An' .984/68 = 0.408 in2=15.64 in2 =2.Adc2' / An' ) A4 = 0.2(31.867% .5 from Ludwig .1469 From Ludwig Fig (5-4) Adcl' /An' = 11.183 ft2 Distribution area percent: 21.36 in2 = 6.8 Design [2] Effective area : assume : =2 in.304 in Lw2' = 0.68) =417.984 in dwl '/Dn ' = 9.68)-2 (417.168 -2 (67.348 + 1/2 (5.461 (68) =31.5% Adcl' = 0.68 in2 dwl' = dwl + y-a dwl '= 6.

CATALYTIC REFORMING [4] end westage area : Awest = AT – Adc – Aliq – Aeff = 28.5 do [7] Tray thickness (t) : t = 1/4 in2 [8] % of hole area ( ) : assume =12.c * H * 37.7 4) total wet pressure drop on tray (ht) : ht = hdt + he Then by using . 5-6) co = 0.2) / co2 ) = 5.655 * 24 * 37.274 – 0.476 * 10-3 fsmin2 3) effective head (he) : assume he = 1.152 sec > 5 sec [6] Hole size (do) and spacing ( c ): do = 3/16 in2 c =2.092((L/2)/lw2)2/3 how = 0.837 in.4)/L TR = (5.822 ft2 [5] Check on residence time (TR ): TR = (Ad.75 from (Fig.003 fs2 * ( w / l) ((1.183 -15.75 in so. 2) calculate dry pressure drop (hdt) : hdt = 0.Fig(5-7) Fs min = 16 .8 % ( very small diameter)From ludwig fig (5-5) [9] Height of weir(hw) : Assume hw = 1 in how = 0.4 ) / (1650/2) TR = 6.2 *28.01422 Awest = 2.274 -6. it’s good liquid distribution [10] Minimum hole velocity ( Fsmin) "weeping" : 1) do/t = 0.4867 > 1/4 in liq assume hLs = 1.

he = 1. liq [15] Pressure drop for tray (∆ p) : ∆ p = ( ht * L ) / (12*144) = 0.Ch. 2.189 psi < 0.5 [12] Design hole velocity .81/2 = 35.62 =108.476 * 10 fs ht = hdt + 1.8 Design [11] Max .031 in Hd = ht + 1.assume Fs max > 16 where Fs max at Hd =1/2 (H+hw )..(Fs design ):Fs design = ( F s min + F s max ) /2 F s design = 31.476*10-3 F2s max Fs max = 47 at Hd = 1/2 (24+1) = 12.8 3.2 -3 2 hdt = 5. Hole velocity ( Fs max ) " Flooding ": 1.5 in 4-hdt = 5.225 in2 [14] Total wet pressure drop (hi) :Fsdesign = 32 ..5 = 6.assume he = 1.81 in.2 psi .56 ((L/2) / 449 (Ad))2 hdu = 0.78 ft/sec [13] Number of holes available on the tray :V=N*(π/4)*(do2/144)*v0 N= 2360 holes From fig available no of holes =2860 holes Excess no of holes =2860-2360=500 hole Excess area =500/4.Hd = Ht+ h1s + hdu hhu = 0.5=32 Vo design = Fs / v 1/2 = 32/0.

CATALYTIC REFORMING .

P.M. : Head .3) : speed ratio .8 Design Pump Design: Here we will design the pump which pumping feed at the first of the catalytic reforming process. : Hoarse power required . : Flow ratio . Ft : specified speed . mec Data: mf = 60125 Lb/hr API = 61. r. G. : mechanical efficiency . in standard : Blade inlet width .25° : Blade outlet angle . < 90° : Blade inlet angle .p.45° ) : Absolute outlet angle .p. : Relative outlet velocity fl / sec : Residual portion of outlet tangential velocity ft / sec : inlet diameter. mano : manometric efficiency.15-0. 0. ( 20 .Ch. ( 10-30° ) over : over all efficiency . (0. : Blade outlet width .5 T = 40 C◦ = 104 ◦f Total dynamic head = 49 m = 161 ft . r.m : flow Rate . DEFINITION OF SYMBOLS USED IN DESIGN:Vf1 Vf2 U1 U2 Vr1 Vr2 VW2 D1 D2 B1 B2 H Ns N Q HP : inlet absolute velocity ft / sec : outlet absolute velocity ft / sec : inlet tangential velocity ft / sec : outlet tangential velocity ft / sec : Relative inlet velocity ft / sec. in standard : outlet diameter .m : impeller speed .

p.7 D1 -assume ( Ψ ) from range (0.5 / 75 * 100 = 86 % tep(3): alculation of inlet and outlet diameter of plate (D1.5 – 3) take it = 2.48 / 60 = 169.5 =0.75 = 834 r.15 . .1-0.3) take it =0.VF2 = Ψ * (2 * g * H) 0.p.1-0.4) take it = 0.CATALYTIC REFORMING Design steps:from kern charts by T = 104 ◦F .15 * (2 * 32.2 G.28 ft / sec .m .7 .D2) -assume (n) from range (0.5 =0.3 = 1357 ft3/hr = 1357 * 7.5 / (H)0.n= B1/D1 so B1=0.5 = 15.4 = 44.2)0.71 density = 0.5/ (161)0.m in the range of (1450-2950).2 * 161)0. Q = 169.28 ft / sec VF = VF1 = VF2 = 15.it should to be in the range (500-3000) .3 Lb / ft3 Q= mass flow rate / density = 60125 / 44.2 G.1 D1 .1 .assume N= 2900 r.P.M find overall = 64.1) by using NS = 834 r.75 = 2900* (169.90%) take it = 75 % .M find specific gravity Step(1) :calculation of specific speed(Ns) .p.Ns= N *(Q)0.so D2= 2. API = 61.Q = * B1 *D1 * VF1 .71 * 62.m (in the range so it is ok) Step(2): calculation of manometric efficiency ( man ) from chart(1.5% -assume mech from range (70% .man = overall / mech *100 = 64.assume (D2/D1) from range (1.P.

U2) .U1 = ( * D1 * N) / 60 = ( * 0.36 in D2 =2.756 * 2900 ) / 60 = 114.8 * 0.125 in .756 ft =9.28 D1 = 0.VW1 = zero .B1 = 0. VW2) .28 =0.Ch.28 =0.28 * 2900) / 60 = 42.2) / ( 114.5 ft /sec .336 in Step (5) : Calculation of inlet and outlet tangential velocity (U1.28 * 3600 ) = 0.Q = * B2 * D2 * VF2 B2 = 1357 / ( * 0.VW2 = (H * g) / (U2 * man ) = (161 * 32.B2) .8 ft / sec Step (6) : calculation of inlet and outlet wirl velocity (VW1.52 ft / sec .7 * 0.1 D1) * D1 * 15.756 * 15.01 ft = 0.28 ft = 3.U2 = ( * D2 * N) / 60 = ( * 0.86) =52.028 ft =0.1 * 0.027 in Step(4) : Calculation of inlet and outlet width of impeller (B1.8 Design 1357/3600 = * (0.

m ( < 2900 ) so it is ok .28 / 42.127 in range (0.52 ) = 19.95 – 1.2 * 161) =1.23 o ( < 20 o ) so it is ok .25 ) : .45 o ) nearly satisfy.8 o in range (20 o .95 . b) plate angle at outlet calculation ( ) : = Tan-1 (VF2 / (U2 – VW2)) = Tan-1(15.8 o (< 90 o ) so it is ok .CATALYTIC REFORMING Step (7): calculation of pump's angles a) absolute outlet angle calculation ( ) := tan-1 ( VF2 / VW2 ) = tan-1 (15. Step(9): calculation of horse power required(HP) HP = Q H / 75 overall *3600 = 5 HP (standardized) . c) plate angle at inlet calculation ( -1 ) :- = Tan VF1 / U1 = Tan-1 (15.= U2 / (2 g H) 1/2 =114.8 / (2 * 32.25) so it is ok . b) NMIN < NASSUMED : Nmin= 120 * man * VW2 * D2 3.5)) = 13. Step (8): check on design a)speed ratio( ) must be in range (0.28 / 52.28 / (114.p.1416*(D2²-D1²) = 2645 r.5) =16.1.8 – 52.

8 Design Compressor design .Ch.

2 psia .9)0.9 >> 5 So we must divide the compressor to multi stage.5 = 3.5) so it is ok) So there are two stages.7) + (5 /2) =57.7 = 13. Step (2): calculation of number of stage (n) Rci= (Rct) (1/n) = (13.72 (in range (3 . Data given: suction pressure (P1) = 14.72 * 14.CATALYTIC REFORMING Compressor design Here we will design the compressor which compresses air for regeneration. Step (3): Calculation of discharge pressure a)Discharge pressure for the first stage(P12) : P12 = (Rci * P1) + (ΔP / 2) = (3.7 psia final pressure (P2) = 205 psia suction temperature (T1)= 85 ˚F air flow rate mair = 5100 lb / hr pressure drop of inter cooler (ΔP)= 5 psia cooling water temperature (Tw) = 90˚F Design steps:Step (1): Calculation of compression ratio (RCt) RCt= P2/P1 = 205/14.

6 MMSCFD a) for first stage :Qa1 (at 14.2 psia RCI = P12 / P1 = 57.91 CHECK: is ok Rc2 = P2 / P22 = 205 / 52.2 – 5 = 52.92 Step (4): Calculation of outlet final temperature from table (12.96314 *10-3*QS* (Ti+460) = 1.4 = 804 ˚R = 344˚F (<350 ˚F) SO IT IS OK Step (5): Calculation of capacity at actual condition (Qa1.6 * (100+460) =1.96314 *10-3*1. Qa2) Qs = 5100 / 0.4-1)/1.2 =3.0766 = 66580 SCF/hr = 1.4 Psia.7 =3.9 (1.4 TF= T1 * RC (K-1)/K = (85+460) * 3.2 / 14.76 MMSCFD .96314 *10-3*1.4 Psia. T1=85˚F) = 1.1) find k for air kair = 1.Ch.6 (85+460) = 1.8 Design b) Inlet pressure for the second stage (P22): P22 = P12 – Δp/2 = 57. T =100˚F) = 1.71MMSCFD b) for second stage :Qa2 (at 14.

4 ) find BHP/MMCFD=88 a) For first stage:(BHP) 1 =Qa1 * BHP/MMCFD (@14. t = 100˚f) =1.5) = 1385 CFM from table (7 – 1) single stage horizontal type try to use cylinder of PD = 1410 CFM EV % = 100 – Rc – Vpc (Rc 1/k – 1) = 100 – 3.CATALYTIC REFORMING Step (6): calculation of Brake horse power from figure (7 -2 ) by known (Rc =3.5665 = 800 CFM .71 * 88 =150.0.5 = 173 BHP) 2st = BHP) 2 * BHP) st /BHP) t = 154.9 * 350 /305.9 – 24 (3.4 Psia.5 = 177 Step (7): Cylinder selection of size for each stage PDEV = HP * 104 / (BHP/MMCFD)(Pi – 0.4 Psia.5 *350 /305.5 HP b) For second stage:(BHP) 2 = Qa2 * BHP /MMCFD (@14.9 1/1.4 – 1) = 56.5 BHP standardized (BHP)total = 350 HP BHP) 1st = BHP) 1 * BHP) st /BHP) t = 150.5) a) for first stage:PDEV) 1= 173 *104 / 88(14.7 . K= 1.9 HP total Brake horse power = (BHP)1 +(BHP)2 = 305.9. T=85˚f) = 1.65 % PDEV) 1st = 1410 * 0.76 *88 = 154.

65% 410 72.5) from table(7 – 1) single stage horizontal type try to use cylinder of PD = 410 CFM EV% = 100 – 3.5 (3.D EV% R.3 % PDEV) 2st = 410 * 0.8 Design b) for second stage : PDEV) 2= 177 *104 / 88(52.3% 300 450 20 12 13 7 Second horizontal stage .P.9 – 14. No. of cycle horizontal 1 1 Cycle type P.Ch.4 – 1) = 72.M Dia Max PSI 35 20 S. of stage First stage No.723 = 297 CFM PDEV 297 CFM.5 . so we can use it.9 1/1.0.L 1410 56.

CATALYTIC REFORMING Tank Design .

228.4 / (3.13 * 24 * 30 = 825.4 = 84.228.56. T = 104 ˚F).228. find specific gravity of reformate = 0.783 * 62. .86 = 1146.364 m3 >> 1000 m3 ( so we wil design large tank) Step(1) : calculation of suitable dimensions of tank (D .8).94 T = 104 ˚F Design steps: from kern chart by known (API = 44.13 ft3 / hr assume production capacity = 30 day V = 1146. Data given: mp = 56000 lb / hr API = 44.calculate D/H)OPT:D/H)OPT = 4 C1 / (C2+C3 + C4 + C5) C4 = C5 = zero C1 = C3 = 2C2 D/H)OPT = 8 / 3 2).4 * 4) / ( * (8/3)2 )(1/3) =52.H) 1).4 ft3 = 825.86 lb / ft3 so Q = mass flow rate / density = 5600 / 84.Ch.87 ft standrized (H) by find the aproximately number which can divide into (6.281)3 = 23.calculate the hieght of tank(H):V=( * D2 * H ) / 4 H= ( 825.783 density = 0.8 Design Tank design Here we will design the tank which used to storage reformate.

42 -825.47 .42) *100 = 0.265.check ((Vact – Vgiven)/ Vact) < 10% := ((831.265.60 6 36 0.03 Tst(in) 0.CATALYTIC REFORMING Hst = 54 ft (which can divide into 6 and give 9) so the number of courses = 9 3).4) / ( * 54))0.calculation of actual volume(Vact) : Vact = ( * Dst2 * Hst ) / 4 = ( * 1402 * 54) / 4 = 831.73 % <<< 10% (SO IT'S OK) Step(2) : .0001456 * Dst * ( H – n ) (n from 1 to 9 ) n H (ft) 1 6 2 12 3 18 4 24 5 30 0.72 7 42 0.228.5 ft Dst= 140 ft 4).4) /831.35 0.228.25 0.96 9 54 1.265.42 ft3 5).25 0.84 8 48 0.calculate the diameter of tank(D) :D= ((4 * V ) / ( * H ))0.5 = 139.5 =((4 * 825.design of shell courses (tn) :tn = 0.

4 ft3 .8 Design ∑ tn = 0. Vroof) Calculation Vbottom = * Dst2 /(4 * 4 * 12 ) = * 1402 / (4 * 4 * 12 ) = 320.03 = 5.7 = 641.72 + 0..47 / 12 ) = 1202 .25 + 0.96 +1.25+ 0.7 ft3 Vroof = 2 * Vbottom ………….6 + 0.84 + 0.Ch.47 + 0. 47 in Step(3): volume of steel(Vsteel )calculation Vsteel = * Dst * 6 * ( ∑ tn /12) = * 140 * 6 * ( 5. (rough estimation) = 2 * 320.35 + 0.9 ft3 Step (4): Volume of Bottom & Roof (Vbot.

New York. Inc. 2003. Marcel Dekkar. French Institute of Petroleum. Mustafa Awad. Robert A.Inc. Antons.CATALYTIC REFORMING References Speight. and Jose' M.Catalytic Naphtha Reforming. Ludwig. Marcel Dekker. Applied Process Design for Chemical and Petrochemical Plants. Taylor & Francis Group. J. McGraw-Hill Handbooks. Fourth Edition.G. . New York. Meyers. University textbook. CRC Press.. Abdullah M. The Chemistry and Technology of Petroleum. Editions TECHNIP. Thermal and Catalytic Processes in Petroleum Refining. Third Edition. Aitani. Petroleum RefiningConversion Processes. Serge Raseev. New York. Parera. Handbook of Petroleum Refining Processes. 2007. George J. Pierre Leprince.

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