API Manual:

Catalytic Reforming:

 Hydrocarbon: a molecule made up of hydrogen and carbon atoms. Crude oil is composed of
a variety of hydrocarbons that have bonded together in different sizes and shapes.
 Hydrocarbon Series: hydrocarbon are normally grouped into four major series or
classes.These include paraffins, olefins, naphthenes, and aromatics.The hydrocarbons within
each class are structured alike and have many of the same characteristics.
 Catalyst: A substance that facilitates or causes a chemical reaction but is not itself changed by
the reaction. Reforming catalysts are usually made of platinum or of platinum-rhenium on an
alumni base.
 Catalytic Reforming Feed: Feed to a reformer is usually a straight run naphtha that has been
produced by distillation of crude oil. Naphtha’s from other processes such as thermal
cracking, coking, and hydrocracking can also be used as feedstocks. The Naphtha feed
generally contains a high concentration of paraffins and naphthene which have a low octane
rating.
 Catalytic Reforming: A process which uses heat, pressure, and a catalyst to convert a low
octane naphtha into a high octane product called reformate. Chemical reactions that take place
in the catalytic refroming process rearrange the structure of hydrocarbon molecules, the most
important reactions convert paraffins and naphthenes into aromatic compounds.
 Refromate: The main catalytic reforming product. The reformate is primarily composed of
aromatic hydrocarbons like benzene, toluene, and xylene that have a high octane rating.
Reformate is normally used as a gasoline blending component or as a feedstock for
petrochemical operations.
 Octane Number: A measure of the antiknock quality of a gasoline. Knocking occurs in an
engine when gasoline in a cylinder ignites at the wrong time. This is usually an indication that
the gasoline octane rating is too low. Different types of engines have different octane
Requirements. Powerful engines with high compression ratios require high octane fuels.
Gasoline is blended in the refinery to meet specific octane requirement from different grades
of fuel.

 Hydrocarbon can be represented either in structural formula or chemical formula.

 The Hydrocarbons in crude oil are arranged in a variety of different shapes and sizes, This
chart shows the chemical formulas for some of these hydrocarbons,
 Propane , the smallest or lightest hydrocarbon listed, has the highest vapor pressure.
 Heptane, the heaviest hydrocarbon on the list, has the highest boiling point.
 So, the characteristics of a particular hydrocarbon are affected by its size.
 The shape or structure of a hydrocarbon also affect its characteristics.

 The characteristics of hydrocarbons are affected by both the size and shape of the molecules.
 The hydrocarbons in each class have a similar structure.
 They also have many of the same characteristics. Paraffins, for example, are all marked by
low octane numbers.
 Naphthene are cyclic hydrocarbon.
 Olefins do not occur naturally in crude oil. They are man-made compounds formed by various
cracking processes.
 Aromatics are chemically active. As a groupd , they also have high octane numbers.
 For use as petrochemical feedstocks and for gasoline blending, the reformate are the most
desirable class of hydrocarbons.
 Catalytic reforming is a process that rearranges the structure/Shape of hydrocarbons.
 This is accomplished by a series of reactions which use heat , pressure, and a catalyst to
reshape the molecules.
 The feed to the catalytic reformer is a naphtha that contains a high concentration of paraffins
and naphthenes.
 During the reforming process, paraffins and naphthenes are converted into aromatics.

MAJOR REACTIONS:

 Dehydrogenation: where naphthenes are converted into aromatics.

 Dehydrogenationis the most important and frequent reforming reaction. It converts a

naphthene into an aromatics.
 Another product of this reaction is hydrogen.
 Dehydrogenation is considered a favorable reaction because the aromatic produced has a
higher octane number than naphthene.
 The hydrogen is also a valuable and important product because it can be recycled or used in
other refinery processes.
 Dehydrogenation is an endothermic reaction. This means that It absorbs heat.
 Because energy is absorbed by the reaction, more heat must be added to the reformer to keep
subsequent reactions going.
 Some chemical reactions release heat. These are called exothermic.
 An exothermic reaction produces heat.
 Dehydrogenation is a heat user, so it is classified as an endothermic reaction.
 Here is another reaction that occurs during reforming.

 This reaction is called dehydrocyclization.

 Dehydrocyclization converts a paraffin into a naphthene.
 This is considered a good reaction because the naphthene produced will undergo
dehydrogenation and be converted into an aromatic.
 Dehydrocyclization also produces hydrogen.
 The reaction absorbs heat which means it is endothermic.
 Here is another reforming reaction.
 This one is called isomerization.
 Isomerization converts a paraffin into an isoparaffins.
 Isomerization is a good reaction because the isoparaffins have higher octane numbers than
normal paraffins.
 The reaction is slightly exothermic which makes isomerization a heat producer.
 Here is the fourth main reaction that occurs during reforming.
 This reaction is called Hydrocracking.
 One type of hydrocracking reaction breaks naphthenes into paraffins.
 Another type of reaction cracks paraffins into smaller paraffins.
 Hydrocracking reactions are not considered favorable because we would prefer to make
aromatics rather than paraffins.
 In addition, Hydrocracking is a hydrogen user.
 Hydrocracking releases a great deal of heat so it is classified as a very exothermic reaction.
 The net effect, however, of the four primary reforming reactions is endothermic.
 So, heat must be added to the process to keep it operating at a Steady, or proper temperature.
 The most desirable reforming reactions convert paraffins and naphthenes into isoparaffins and
aromatics.
 These reactions reform the naphtha feed into higher octane product.
 This high octane product is called reformate.
 Other product produced by the reforming reactions include light hydrocarbons and hydrogen.
The Reforming Catalyst

 The base of the catalytic reforming catalyt is made out of alumina which is a type of
aluminum oxide.
 As shown below.

 Dispersed across the alumina base are both metal and acid sites.
 The metal sites are usually composed of platinum or a combination of platinum and rhenium.
 Platinum and rhenium promote the dehydrogenation and dehydrocyclization reactions that
occur during reforming.
 The acid sites are normally provided by chlorides.
 These chlorides catalyze isomerization reactions.
 So, the major reforming reactions are promoted by two different types of sites dispersed
across an alumina-base catalyst.
 The metal sites are composed of platinum, or rhenium, while chlorides make up the acid sites.

Review
 The characteristics of a particular hydrocarbon are determined by its size and shape.
 Hydrocarbons are normally grouped into four major series or classes. These are paraffins,
naphthenes, olefins, and aromatics.
 The hydrocarbons with the highest octane ratings are aromatics.
 The feed to a catalytic reformer is usually a naphtha.
 During reforming the feed is heated, pressurized, and put in contact with a catalyst.
 The catalyst promotes several chemical reactions which rearrange, reform ,or change the
structure of the hydrocarbon molecules.
 Dehydrogenation and dehydrocyclization convert paraffins and naphthene’s into
aromatics.
 Isomerization converts paraffins into iso-paraffins.
 Hydrocracking breaks paraffins and naphthene’s into smaller paraffins.
 The main product produced by these four reactions is called reformate.
 Reformate has a high octane rating because it contains iso-paraffins and aromatics.
 Other products produced by catalytic reforming include hydrogen and light hydrocarbons.
 The major effect of the reforming reactions is endothermic.

Catalytic Reforming:

 Desulfurization or hydrotreating: A process that removes sulfur, lead, arsenic, nitrogen, and
other contaminants from naphtha. The feed to a catalytic reformer is usually hydrotreated to
remove impurities that could damage the reforming catalyst.
 Semi- Regenerative reformer: With this type of reformer, the reactors are run continuously
for long periods of time. When the catalyst becomes deactivated, the entire unit is shut down
so that all of the catalyst can be regenerated at the same time.
 Cyclic Reformer: a cyclic reformer utilizes an extra reactor so that catalyst through out the
system can be regenerated in cycles. Three reactors are always in operation while the catalyst
in the fourth or swing reactor is being regenerated. With this method of reforming, the catalyst
can be regenerated with out shutting down the unit.
 Continuous Reformer: In a continuous reformer, a portion of the catalyst is continuously sent
to separate regenerator where it is cleaned and conditioned prior to being returned to the
system.
 Catalytic reforming is a process that converts a low octane number into a high octane product
called reformate.
 This is accomplished by rearranging the shape or structure of the hydrocarbon molecules.
 The naphtha feed often contains impurities such as sulfur, nitrogen, arsenic, and lead.
 These impurities can poison or deactivate the reforming catalyst.
 So, before the naphtha is reformed, the impurities must be treated (removed).
 Normally, this is done by pretreating the feed in a desulfurize or hydrotreater.

Refromer equipment

 Exhibit 2 is a diagram of a typical catalytic reformer. The reformer equipment includes three
reactors and furnaces.
 Other major pieces of equipment include a separator, a stabilizer, and recycle compressor.
 Lets work through the process. The first step in reforming is to mix the feed with a hydrogen
rich gas.
 Then, the feed passes through a furnace, where it is heated to around 900-950 F and
vaporized.
 From the furnace, the feed-hydrogen mixture is charged to the first reactor.
 Basically, there are two different types of reformer reactors. This is a down flow reactor.

 When the feed enters the reactor, it contacts a deflector plate.

 The deflector plate distributes the vapors across the top of the catalyst bed.
 The vapors then pass through a layer of catalyst whose purpose is to keep the catalyst in
place.
 As the naphtha passes through the catalyst bed, several chemical reactions occur. These
reactions change the shape or structure of the hydrocarbon molecules.
 At the bottom of the reactor,the feed passes through another layer of alumina balls and a
screen.
 The screen prevents the catalyst or the alumina balls from exiting or leaving the reactor with
naphtha.
 Here is the second type of reactor that is used for reforming.

 Its called a radial reactor.

 In a radial reactor, the feed enters the catalyst bed from the sides instead of the top.
 Both downflow and radial reactors have certain advantages and disadvantages. The type of
reactor that is used in your particular unit is a design consideration.
 After leaving the first reactor, the feed is reheated and sent through two other reactors.
 The same basic process repeats itself in the remaining two reactors.
 When the feed contacts the catalyst, chemical reactions occur which reform/change/rearrange
the shape of the hydrocarbons.
 The Fastest Reforming reactions are dehydrogenation and dehydrocyclization.
 So, the majority of these reactions take place in the first reactor.
 Isomerization and hydrocracking are slower reactions.
 They show their effects in the second and third reactors.
 The product leaving reactor 3 is still in the vapor state. This Stream contains hydrogen, light
hydrocarbon gases, and the reformed feed or naphtha.
 The next step in processing is to send these vapors through a heat exchanger.
 The heat exchanger cools and condenses the majority of the vapors back to liquids.
 The hydrogen and light hydrocarbon gases do not condense because they have a very low low
boiling point. These components remain in Vapor state.
 From the heat exchanger, the vapor-liquid mixture is channeled to the separator, where the
uncondensed gases are removed overhead.
 Some of the hydrogen-rich gas is sent to the refinery gas plant for additional processing. This
stream is an important source of hydrogen for other refinery processe.
 The rest of the hydrogen is moved out of the separator by a recycle compressor and then
mixed with fresh reactor feed.
 Some of this hydrogen will eventually react with carbon atoms inside the reactors and form
hydrocarbon.
 These reactions are important because they reduce the amount of carbon that can be deposited
on the catalyst.
 Lets return to the separator. Liquid is pumped from the bottom of this vessel into a stabilizer.
 The stabilizer is a distillation column that separates out any light hydrocarbons that still
remain in the liquid.
 The product drawn from the bottom of the tower is stabilized reformate.
 The reformate is a primary source for benzene, toluene, and xylenes.
 These are aromatic hydrocarbons.

Catalyst Regeneration
 During the reforming process, carbon is gradually deposited on the catalyst as coke.
 These deposits deactivate the catalyst, making it more difficult to reform the feed.
 So, periodically the catalyst must be regenerated.
 This is accomplished by burning the coke off the catalyst with combustion air.

 Reforming operations are often classified by the way in which they regenerate the catalyst.
There are three different ways to do this.
 The Exhibit 3 is an example of a semiregenerative reformer.
 With a semiregenerative reformer, the reactors are run continuously until the catalyst requires
regeneration.
 At this point, the entire unit is shutdown so that all of the catalyst can be regenerated at the
same time.
 Before the coke can be burned off the catalyst , the reactors must be isolated from the source
of any hydrocabons.
 So, a metal blind is placed across the feed inlet line.
 All hydrocarbons inside the reactors must also be removed.
 This is accomplished by purging the reactors with nitrogen.
 When the reactors are free of all hydrocarbons, a blind is placed in the product outlet lines.
 This prevents hydrocarbons in other parts of the system from backing up into the reactors.
 After the reactors are purged and blinded, the coke is burned off the catalyst by adding
combustion air to the reactors.

 Exhibit 4 shows a cyclic reformer.

 This type of system utilizes a swing reactor.
 Three reactors are always in operation while catalyst in the fourth is being regenerated.
 Cyclic reforming allows us to regenerate the catalyst without a unit shutdown.
 Each regeneration stage or cycle cleans one quarter of the catalyst in the system.
 Before the catalyst in any of the reactors is cleaned, all hydrocarbon must be removed from
that vessel.
 And, the product inlet and feed outlet lines must be blinded.
 Exhibit 5 is a diagram of a continuous reformer.
 In this type of operation, the reactors are usually stacked or placed on top of one another.
 Catalyst from the bottom of reactor 3 is sent to a separate regenerating vessel.
 After cleaning, the catalyst is returned to the top of reactor 1.
 During the reforming operation, the fresh catalyst gradually flows down through the other
reactors.
 When it reaches the bottom of the reactor, the catalyst is again sent out for regeneration.
 This method of reforming allows us to regenerate the catalyst in a continuous cycle.
 And, during the actual regeneration none of the reactors are shutdown.

Reactivating the catalyst

 Regardless of what method of reforming is used, catalyst regeneration involves several

different steps.
 You have already learned that the first regeneration step is to burn the coke off the catalyst
with combustion air or oxygen.
 The catalyst can be permanently damaged by overheating, so the temperature during
regeneration must be carefully controlled.
 The temperature of the catalyst is controlled by limiting the amount of air or oxygen that is
added to the regeneration vessel.
 During this stage of regeneration, some of the oxygen chemically combines with the platinum
in a reaction known as oxidation.
 When the platinum is oxidized, it contains oxygen.
 Despite the care taken to avoid excessive temperatures, the heat generated during the carbon
burn off will cause much of platinum to agglomerate or ball up.
 To restore the catalyst to its original active state, the platinum must be redispersed across the
base of the catalyst.
 Another essential conditioning step is to restore the chloride level on the catalyst.
 Chloride, as you recall, promote (isomerization/hydrocracking) reactions.
 Chlorides and platinum are redispersed by the next step in regeneration called chloridization.
 The catalyst is chloridized by adding water and chlorine to the system.

 This reaction partially dissolves the platinum into chloroplatinic acid.

 The chloroplatinic acid flows over the surface of the catalyst and in this manner redisperses
the platinum and chlorides.
 At this point, the platinum is still in an oxidized state making it inactive for reforming
reactions.
 Before the catalyst can be returned to serveice, oxygen must be removed from the platinum.
 This is accomplished by the next regeneration step called reduction.
 The platinum is reduced by adding hydrogen to the system.
 In the resulting reaction, hydrogen combines with oxygen to form water.
 Following reduction, the catalyst is in an extremely active state. If it is put back into operation
in this condition, too many reforming reactions may take place too quickly.
 This could coke up the catalyst and make another regeneration necessary.
 So, after reduction the catalyst is usually passed through one final step called sulfidizing.
 In this step,sulfides are applied to the catalyst to temporarily diminish its activity.
 When the catalyst is put back in operation, the sulfides are gradually washed off its surface
which maintains the desired catalyst activity.
 This chart summarizes the five main steps that occur during catalyst regeneration.

 The specific manner in which these regeneration steps are accomplished will vary from unit
to unit.
 So, it is essential that an operator follow the actual detailed instructions or specifications for
his units’ regeneration.
Catalytic Reforming:
 Operating variables: Process conditions such as a reactor temperature or the hydrogen recycle
rate, whose value can change . Operating variable must be kept within a desired range of values
for the unit to produce quality products and sufficient yields.
 Instrumentation: most operating variables for a catalytic reforming unit are sensed, measured,
and controlled by instruments. These instruments may work automatically or require manual
control. An operator is responsible for monitoring and adjusting the condition of process variables
to make sure they stay within the desired range of values.

Operating variables:

 The goal in catalytic reforming is to convert a naphtha feed into a high octane product called
reformate.
 Other product produced include light hydrocarbons and hydrogen.
 A primary reforming reaction is dehydrogenation.
 This reaction convert naphthenes to aromatics.
 Dehydrocyclization and isomerization also improve the octane rating of the naphtha.
 In order to realize the desired product yields and quality, certain operating conditions or variables
must be controlled.
 By keeping the unit operating variables within their allowable tolerances, we ensure the most
favorable reforming reactions will occur.

Product yield versus quality:

 Normally a reformer is operated to produce maximum amount of reformate that meets a given
octane specification.
 This chart shows a typical relationship that exists between reformate yields and octane number.

 You can see that as the octane number

goes up, the volume of reformate
produced decreases.
 So, if a unit is producing a product that is above octane specs, reformate yields are being wasted.
 And, when yields are wasted, money is needlessly lost. Therefore, a reformer should be operated
to just meet octane specifiactions.
 Product yields and octane number are controlled by adjusting the unit operating variables.

Reactor Temperature:

 Because the net effect of the reforming reactions is endothermic, a constant supply of heat must
be added to the reactors.
 This makes the temperature in the reactors a key operating variable.
 Reactor temperature are maintained by passing the feed through a furnace prior to each reactor.
 When the reactor temperature are increased, more reforming occurs.
 If the reactor temperature are raised by 3 to 5 F, the octane number of the reformate will usually
increase by 1.
 Octane number adjustments are usually made by changing the reactor temperature.
 To increase the octane number, you raise or increase the reactor temperature.
 In most operations, the reactor temperatures are kept at a set value on a day by day basis. But,
catalyst deactivation or feed quality changes may cause the reformate octane rating to gradually
fall off.
 If this happens, you may need to raise the reactor temperature to meet octane specs.
 If the catalyst starts to coke up, however, less reforming will take place.
 So, less heat is consumed and the temperature drop across the reactor becomes smaller.
 A reduction in the temperature drop across a reactor may indicate that the catalyst is covered with
coke.
 Contaminants in the feed, like sulfur, may suddenly change the temperature drop across a reactor.
Sudden temperature changes usually indicate more serious problems.
 One way for an operator to determine if his unit is operating efficiently is to monitor the reactor
inlet and outlet temperatures.

Pressure:

 Another important operating variable is the reformer pressure.

 Pressure is controlled by regulating the flow of hydrogen out of the separator.
 Basically, reforming is a high pressure operation.The system pressure may range from 200 to 500
PSI. Pressure in the system is created by both hydrogen and hydrocarbon gases.
 Hydrogen is a product of several of the reforming reactions.
 And, Hydrogen is also mixed with the feed to protect the catalyst from excessive coke deposits.
 Hydrocarbon gases are formed because the feed is vaporized or heated as it passes through the
furnace.
 The system pressure is a design feature and is not normally adjusted to change product quality or
yield.
 If the system pressure is allowed to increase, more hydrocracking occurs in the reactors in return
for less dehydrogenation.
 This increases the yield of hydrocarbon gases, but decreases the production of hydrogen and
reformate.
 A drop in the system pressure increases hydrogen and reformate yields.
 But, at lower pressure more coke is deposited on the catalyst.
 So, the system pressure should always be maintained at a specified constant level.
 A pressure difference or drop occurs across each of the reactors.
 This is because the vapor encounter resistance as they flow through the catalyst.
 If the catalyst starts to plug up, this resistance will increase.
 And, the differential pressure across the reactors will also increase.
 An operator can check the condition of the catalyst by monitoring the differential pressure across
each of the reactors.

Feed Rate:

 A specified amount of feed is charged to a reformer each day.

 The feed is moved into the unit by pump.
 The feed rate is usually kept at a constant value to maintain a balance throughout the system. But
feed availability problems or mechanical difficulties may force a feed rate reduction.
 If feed rate changes, other operating variables will be affected.
 With a lower feed rate, the desired yields and octane can be obtained at lower reactor
temperatures.
 So, it may be necessary to reduce or adjust the reactor temperatures to keep the system in balance.
 Under normal operating conditions, however, the feed rate is kept at a constant value.

Feed Composition:

 Naphthenes are easier to reform and produce a higher-octane reformate than paraffins.
 Therefore, the most desirable reformer feed will contain a high concentration of naphthenes.
 The composition of the feed can be determined by a PONA analysis. This test tells us what
concentration of paraffins, olefins, naphthenes, and aromatics are present in the feed.
 The PONA content of the feed will affect how a reformer is operated and what types of products
It produce.
 The feed is also checked for heavy, high boiling point hydrocarbons.
 This is because heavy material in the feed may coke up the catalyst.
 Contaminants, such as water or sulfur, are sometimes present in the feed.
 These contaminants will interfere with the smooth operation of a reformer unit.
 It is important to identify contaminants in the feed so that these components can be removed prior
to reforming.

Hydrogen Recycle Ratio:

 To protect the catalyst from excessive coke deposits, Hydrogen is recycled and mixed with the
feed.
 The hydrogen recycle is expressed as a ratio.

 This ratio compares the amount of hydrogen in the recycle gas to the amount of hydrocarbon or
feed being charged to the unit.
 When the catalyst becomes inactive, it must be cleaned or regenerated.
 Another condition that affects the catalyst activity is the level of chlorides on the catalyst surface.
 Chlorides promote isomerization reactions.
 Chlorides can be injected into the feed or the recycle gas streams.
 These injection rates are normally set by the Supervisory staff.
 An operator’s job is to test and monitor the chlorides level.
 A small amount of water is sometimes injected into the feed or recycle gas streams to spread or
disperse the chlorides across the surface of the catalyst.
 To ensure the proper water of chlorides across the catalyst, chlorides injection rates must be
carefully controlled.

Vapor pressure:
 Vapor pressure is a measure of a liquid’s tendency to vaporize at given temperatures.

  You can see from this chart that light hydrocarbons, like propane and butane, have high vapor
pressures and boil at low temperatures.
 These characteristics cause propane and butane to vaporize or boil at normal temperatures and
pressures.
 We want the reformate to have a low vapor pressure so that it will stay in the vapor state under
average climatic conditions.
 Prior to stabilization, the reformate vapor pressure is usually higher than 100 PSIA.

 Stabilization removes light hydrocarbons from the reformate reducing its vapor pressure to
between 4 – 6 PSIA.
 The reformate vapor pressure is controlled by adjusting temperatures inside the stabilizer.
 Higher temperatures boil away more light material which reduces the vapor pressure of the
reformate.
 If the reformate does not meet vapor pressure specifications, It may be necessary to adjust the
Temperature inside the stabilizer.
