CATALYTIC REFORMING

UNIT (CRU/CCRU)
12TH Jun’20

by K Subash
 Background
• CRU units started as early as 1949 – First commercialized by Universal Oil Products (UOP)
• Objective – To convert low Research Octane number (RON) Naphtha to high RON reformate (MS/Gasoline
blending component)
• Position of CRU in Refinery Configuration:
 CRU is the primary unit for production of Motor Spirit/Gasoline/Petrol from a Refinery
 CRU unit is designed to treat Straight Run Naphtha (SRN) ex Atmospheric unit (mother unit)
 Normal cut range of SRN varies between C5 boiling point to 150 °C (FBP) (RON of ~ 60)
 This SRN is split into two components namely light Naphtha (C5-90 °C) and Heavy Naphtha (90-150 °C)
 Heavy Naphtha containing (Naphthenes + 2*Aromatics) > 55 forms a good feed to CRU unit after
hydrotreatment to remove impurities
 CRU converts the Paraffins, Olefins and Naphthenes in this hydrotreated heavy Naphtha to Aromatics thereby
increasing its RON to ~ 98-100.
 This product Reformate is the primary blending component of MS (gasoline) pool. CRU units can also produce
aromatic concentrates like Benzene, Toluene & Xylene based on feed and operating conditions.
 The by-products from the CRU unit are LPG and Hydrogen.
 General Refinery Configuration FUEL GAS
LPG

MOTOR SPIRIT
NHDT/CRU
SRN

SKO
HGU
AVU
CRUDE
DHDT
HSD
ISOM

LRU
COKER
FUEL OIL
OHCU PET COKE

BITUROX
ARU/SRU SULPHUR
RFCC
LPG MEROX
GASOLINE MEROX
BITUMEN
 RON
What is RON? RON MON
Cyclohexane 83 77.2
 It is a parameter used to qualify gasoline (Petrol) based on the knock
characteristics it exhibits in the IC engine. Methylcyclohexane 74.8 71.1
1,3 di-methylcyclohexane 71.7 71.
 RON is defined as “the ratio of Iso-octane in a mixture of Iso-octane and n-
Benzene 114.8 > 100
Heptane”.
Toluene 120 103.5
 Iso-octane (2,2,4-trimethyl pentane) – RON number of 100; n-Heptane – m-Xylene 117.5 115.
RON number of 0
 Higher the RON lower is the knocking in the IC engine and better is the  Branched Paraffins also have high
engine efficiency. Octane and the RON increase with
 Knocking is the sudden vibration/knock that is experienced by the engine branching
due to premature ignition of un-burnt hydrocarbons. Knocking may damage  Therefore RON of Naphtha can be
the IC engine. improved by Reforming the
Hydrocarbon molecule (molecular re-
 Gasoline of RON 95.0 means the gasoline sample matches with the knock arrangement)
characteristics of a blend of 95% Iso-octane and 5% n-Heptane.  Such re-arrangement takes place in
Reforming reactors in the presence of
For same carbon number compounds the order of Octane number is as below: Platinum catalyst through numerous
Paraffins < Olefins < Iso-paraffins < Iso-olefins < Naphthenes < Aromatics complex reactions
 Octane Number – Types of Measurement
• Types of Octane number measurement:
 Research Octane Number (RON) – determined at 600 rpm IC engine with variable compression ratio
 Motor Octane Number (MON) – determined at 900 rpm IC engine with pre-heated fuel mixture and
variable ignition timing. MON<RON (8-10 nos.)
 Anti-Knock Index (AKI) – Average of RON and MON i.e. ((RON+MON)/2)
 Road Octane Number (RdON) – simulated to real road conditions. RdON<MON<RON
 Octane index - calculated octane quality in contradistinction to the (measured) research or motor
octane numbers
 CRU – Licensors
Following are the various kinds of CRU units designed by Licensors since 1940:
 Rheniforming: Developed by Chevron Oil Company.
 CCR Platforming: A Platforming version, designed for continuous catalyst regeneration, by UOP.
 Powerforming: Developed by Esso Oil Company, currently known as ExxonMobil.
 Magnaforming: Developed by Engelhard and Atlantic Richfield Oil Company.
 Ultraforming: Developed by Standard Oil of Indiana, now a part of the British Petroleum Company.
 Houdriforming: Developed by the Houdry Process Corporation.
 Octanizing: A catalytic reforming version developed by Axens, a subsidiary of Institut francais du
petrole (IFP), designed for continuous catalyst regeneration.

Of the above, Platforming technology by M/s UOP and Octanizing technology by M/s Axens are the most
common.
 CRU – Types
Following are the types of CRU units based on design:
• Fixed bed – Earliest types of CRU with fixed catalyst bed. Catalyst to be dumped and replaced once activity
is lost. Higher downtime.
• Semi-regenerative (SR) – The reformer processes feedstock for a time and then shuts down for regeneration.
Better catalyst with increased life cycle due to regenerative capability. Lower downtime than fixed bed types
due to capability of regenerating catalyst in-situ inside the reactor for burning coke on catalyst.
• Cyclic Reformer – Improvised design over semi-regenerative design where catalyst in one reactor can be
regenerated while the other reactors are in service. Process of isolating and lining-up reactors cumbersome.
• Continuous regeneration (CCR) – Successful and latest design with catalyst circulating continuously
between the reactors and a dedicated regenerator. Catalyst is moved continuously through the reactors,
withdrawn from the last reactor, regenerated in regeneration section and returned to the first reactor as fresh
catalyst. Highest plant availability factor and safe design.
Majority of the existing functioning units comprise of either the semi-regenerative (SR) (older units) and the
continuous catalytic regeneration unit (CCRU)
 Block Flow of CRU Block
CRU BLOCK RSU Legend
NSU NHTU CCRU
NSU
Naphtha
C5 – 90 °C H2 Rich Gas Splitter Unit
Light Naphtha (LN)
H2S, NH3 Lt. Reformate NHTU
LPG Naptha
Hydrotreating
Unit
SRN Naphtha Naphtha CRU
Separator Reformate
C5 – 150 Splitter Hydro Separator Reactors Stabilizer
Splitter
CCRU
°C treater & Stripper and Continuous
Reactor Furnace
Catalytic
Reforming
Reformate Unit
Hy. Reformate
Heavy Naphtha (HN) RSU
90 - 150 °C Hydrogen
Reformate
Splitter Unit
 TYPICAL UNIT FLOW DIAGRAM OF CCRU BLOCK
NSU HDT REFORMING SECTION
NAPHTHA SPLITTER UNIT (NSU)
 Naphtha Splitting Unit (NSU)
FEED: SRN ex AVU, cut C5-150 deg C
Splits the SRN into Light Naphtha (C5 – 90 deg C) and Heavy naphtha (90 – 150 deg C)
• NSU can process both a mix of cold naphtha ex tank farm and SRN ex AVU
• Top temperature of NSU column is maintained based on crude source of feed Naphtha so as to
skim the benzene precursors to light naphtha and avoid benzene slip in to Hy. Naphtha in order to
produce low benzene reformate.
• It is also to be ensured that while avoiding benzene slip to the bottom Hy. Naphtha stream, loss of
C7 components to the top light Naphtha stream is to be avoided (minimized)
• Bottom material, Heavy naphtha (90 - 150 °C), is feed to Naphtha Hydro Treating Unit
• Top material, Light naphtha (C5 – 90 °C), is routed to Hydrogen Generation Unit (HGU) as feed.
• Proper operation of NSU is key to proper feed preparation for NHTU and CCRU
NAPHTHA HYDROTREATER UNIT
(NHTU)
 NHTU - SIMPLIFIED FLOW DIAGRAM NH3, H2S
MAIN HYDROTREATER RECYCLE GAS
REACTOR COMPRESSOR

FEED SURGE SHU

DRUM REACTOR REFLUX
DRUM

SEPARATOR

STRIPPER
CHARGE FEED TO REBOILER
HEATER F/E EXCH. FURNACE
RECYCLE H2 REFOMER

S R NAP. MAKE UP H2
 Naphtha Hydro Treating Unit (NHTU)
FEED: HN ex NSU bottom (Hot or Cold); Mix of low sulfur and high sulfur feeds
• The unit aims to protect the highly sensitive reformer catalyst from impurities like S, N2, H2O, Di-Olefins,
Arsenic and other metals
• Hydrotreatment of the feed takes place in the presence of Nickel-Molybdenum catalyst to convert these
impurities into easily removable products like, Sulfur to Hydrogen sulfide, Nitrogen to ammonia etc.
Arsenic and other metal impurities are absorbed on the catalyst.
• The unit is designed to handle a wide range of feed naphtha w.r.t Sulphur from very low sulfur (as in
indigenous neat Bombay high crude) to a sulfur content of 1500 PPM (as in Arab mix) so as to give treated
product of sulfur less than 0.5 PPM.
• Nitrogen is also reduced to less than 0.5 PPM and water content is reduced to less than 4 PPM.
• NHTU unit comprises of two reactors namely Selective Hydrogenation reactor (SHU) and main
Hydrogenator reactor. Hydrogenation of di-olefins and conversion of mercaptans take place in the fixed bed
axial SHU reactor.
• The hydrogenation of olefins, hydro de-sulfurisation and hydro-de-nitrification reactions take place in the
main fixed bed axial Hydrogenator reactor
• The liquid product from the reaction section is then stripped in the Stripper column to remove H 2S, water
and light hydrocarbon impurities.
 Naphtha Hydro Treating Unit (NHTU)
PROCESS VARIABLE – TEMPERATURE:
SHU Reactor:
• The Hydrogenation reaction rate is increased at higher temperature. Hydrogenation selectivity however is
favored by lower temperature. For catalyst stability the operation must take place at a lower temperature to
prevent polymerization of gum precursor compounds.
• Lower operating temperature keeps the reactants in the liquid phase by minimizing vaporization.
• The reactor exotherm is a function of the di-olefins content of the fresh feed and make-up hydrogen rate.
Main Hydrogenator Reactor:
• The hydrotreating reactions are favored by an increase of temp.
• But at the same time this increase of temperature increases the coke deposit on the catalyst.
• The optimum reactor inlet temperature is typically between 280 (new catalyst) to 340 C (At the end of the
cycle) for the designed feed cut.
• In case of lower sulphur content, the values can be reduced.
 Naphtha Hydro Treating Unit (NHTU)
PROCESS VARIABLE - SPACE VELOCITY:
LHSV = (Hourly feed flow rate in m3/hr at 15 deg C) / Volume of catalyst in m3
• It is the inverse of the residence time
• A low liquid hourly space velocity favors hydrogenation reactions in Hydrogenator reactor and decreases di-
olefin conversion in SHU reactor

PROCESS VARIABLE - HYDROGEN PARTIAL PRESSURE & H2/HC RATIO:

• An increase in hydrogen partial pr. favors the hydrogenation reactions and reduces polymerization reactions
and coke deposits
H2/HC ratio = H2 in recycle gas (m3/hr.) / Total naphtha feed (m3/hr at 15 C)
• The important criterion for a liquid phase hydrogenation is the content of dissolved hydrogen.
 Naphtha Hydro Treating Unit (NHTU)
PROCESS VARIABLE – OPERATING PRESSURE:
Higher operating pressure gives the following benefits:
• Improves di-olefin Hydrogenation in SHU reactor
• Reduces the polymerization reactions/coke deposits and increases catalyst cycle length in Hydrogenator
reactor
• Increases hydrogen dissolved in the liquid phase
• Improves liquid distribution in the reactor and reduces pressure drop due to vaporization
FEED QULAITY:
• High impurity content – higher RIT required
• Higher olefin content – Higher exothermicity across the main Hydrogenator reactor
• Feed stored over longer duration – Polymerization can take place
STRIPPER BOTTOM TEMPERATURE:
• Lower tray and bottom temperature – poorer stripping
• Poorer stripping leads to H2S and H2O slippage in CRU feed
 Naphtha Hydro Treating Unit (NHTU)
REACTIONS IN SHU REACTOR:
• Selective Hydrogenation of di-olefins
• Isomerization of Olefins
• Olefin Hydrogenation
• Conversion of Light Mercaptans to Heavier Sulfides
• Conversion of Light Mercaptans to Heavy Mercaptans
• Conversion of H2S to Mercaptans
REACTIONS IN MAIN HYDROGENATOR:
 Hydro-Refining reactions:
• Hydro de-sulphurisation
• Hydro de-nitrogenation
• Hydro de-oxygenation
 Hydrogenation reactions:
• Olefins Hydrogenation
• Aromatics Hydrogenation
 Naphtha Hydro Treating Unit (NHTU)
SHU REACTOR REACTIONS - HYDROGENATION OF DI-OLEFINS:
Di-olefins are hydrogenated into corresponding olefins with some hydrogenation to paraffins
Cyclohexadiene + H2  cyclohexene
1,2 – hepta di-ene + H2  1-heptene + 2 -heptene
ISODIOLEFINS
Isodiolefins hydrogenation produces also various isomers. Moreover, double bond migration can also occur
within
the newly generated isomer.
CH2=CH-CH2-CH2-CH2-CH3  CH3-CH=CH-CH2-CH2-CH3
1- Hexene 2 - Hexene
Sulphur reaction:
• Conversion of light mercaptans to heavy sulfides
• Conversion of light mercaptans to heavy mercaptans
• Conversion of sulfides to heavy mercaptans
• Conversion of H2S to mercaptans
 Naphtha Hydro Treating Unit (NHTU)
SHU REACTOR REACTIONS
Conversion of light mercaptans to heavier sulfides
RSH + (R’-C5 TO C7 OLEFIN  RSR’
Conversion of Light mercaptans to heavier mercaptans
Step 1
RSH + H2  RH + H2S
Step 2
H2S + (R’- C5 TO C7 OLEFIN)  R’SH
Conversion of sulfides to heavier mercaptans
C2H5-S-CH3 + 2H2  CH4 + C2H6 + H2S
H2S + (R’-C5 TO C7 OLEFIN)  R’SH
Conversion of H2S to Heavier mercaptans
H2S + (R’ C5 to C7 olefin  R’SH
 Naphtha Hydro Treating Unit (NHTU)
HYDRO REFINING REACTIONS - DESULPHURISATION
Mercaptides, sulphides and disulfides easily react leading to the corresponding saturated or aromatic compounds:

R-SH + H2  RH + H2S
R-S-R' + 2H2  RH + R'H + H2S
R-S-S-R' + 3H2  RH + R'H + 2H2S

Sulfur combined into cycles of aromatic structure, like thiophene, is more difficult to eliminate

+ 4 H2 C4 H10 + H2S
S
Thiophene n-Butane Hydrogen Sulfide
 Naphtha Hydro Treating Unit (NHTU)
HYDRO REFINING REACTIONS - DENITRIFICATION:
Nitrogen compounds inhibit considerably the acidic function of the reforming catalyst. They are eliminated
by production of ammonia. The nitrogen compounds of SR naphtha are methylpyrol and quinoline

HC CH

+4H2 C5H12 + NH3

HC C-CH3
N
Methyl Pyrrol n-Pentane Ammonia

HC CH CH
HC C CH
HC CH
+ 5H2 + NH3
HC CH
N HC CH
HC CH
CH
Quinoline Benzene
 Naphtha Hydro Treating Unit (NHTU)
HYDRO REFINING REACTIONS - HYDRO-DEOXYGENATION:
Oxygen or oxygen compounds modify the acidic function of the reforming catalyst. They are eliminated by
production of water. The oxygen compounds of straight-run are peroxides and phenols.
Oxygen is almost completely transformed into water.

HC CH
HC OH HC CH

+ H2 + H2 O
HC CH HC CH
HC CH
Phenol Benzene
 Naphtha Hydro Treating Unit (NHTU)
HYDRO REFINING REACTIONS - HYDROGENATION:
Olefinic hydrocarbons at high temperature provoke coke deposit on the reformer catalyst as well as in the
furnace coils. If present in small quantities, they are eliminated by transformation to paraffins. The reaction is
highly exothermic. Olefinic compounds are normally absent in straight run products.

Olefins and Di-olefins are converted into saturated compounds;

Cn H2n Cn H2n+2 (highly exothermic)
Aromatic hydrogenation occurs as a consequence of temperature and hydrogen partial pressure. But combined
with the H2S partial pr., the use of selected catalyst allows the limitation of these hydrogenation reactions. Less
than 1% wt. of aromatics of the feed are hydrogenated in the hydrotreater.

ELIMINATION OF ARSENIC AND METALS

Arsenic, lead, mercury, sodium and to lesser degree Cu, Ni, Fe damage permanently the reforming catalyst.
These compounds are absorbed on the catalyst.
 Naphtha Hydro Treating Unit (NHTU)
OPERATING PARAMETERS OF REACTORS:
SHU REACTOR:
• Inlet temperature (SOR/EOR) : 160 / 195 Deg C (SOR/EOR)
• Outlet pressure : 25 Kg/Cm2(g)

MAIN HYDROGENATOR REACTOR:

• Outlet temperature : 280 / 340 Deg C (SOR/EOR)
• Outlet pressure : 20.5 Kg/cm2(g)

SOR – Start of Run (or) Start of catalyst life cycle

EOR – End of Run (or) End of catalyst life cycle
CATALYTIC REFORMING UNIT (CRU)
 Catalytic Reforming Unit (CRU)
Hydrocarbon conversion in Platformer depends on the type of feeds;
“Lean” Naphtha (high paraffin, low Naphthene content) and
“Rich” Naphtha (lower paraffin, higher Naphthene content).
 For the richer feed, less paraffin conversion will be necessary, making the operation much easier and more
efficient.
CCRU - SIMPLIFIED FLOW DIAGRAM – DESIGN I
CCRU - SIMPLIFIED FLOW DIAGRAM – DESIGN
II
TYPICAL UNIT FLOW DIAGRAM OF CCRU BLOCK
Catalytic Reforming Unit (CRU)
 Catalytic Reforming Unit (CRU)
Typical products and their yields:

S. Attributes Unit Typical range

No
SR CRU CCRU
1 Reformate RON - 95-98 98-105
2 Reformate yield Wt% 89-91 91-94
3 Gas yield + loss Wt% 8-10 5-8
4 Purity of CRU H2 rich gas Wt% 91-93 95-96
 CRU – SECTION DESCRIPTION
REACTOR:
 The feed is pre-heated in the reactor combined feed/effluent exchanger (CFE) before being heated to reaction
temperature in the Charge Heater and flows to First Reactor. The reforming reactions that take place in the
reactors which is endothermic.
 Inter-heaters are required to reheat the reactor effluent from first, second and third reactor. The Convection
Section is used to generate HP Steam/preheat feed.
 Last Reactor effluent is heat exchanged with incoming feed in the CFE and Condensed products are separated
into recycle gas and reformate.
 The recycle gas from the Separator is compressed and enters with the feed to reactor.
 The reactors have a catalyst collector at the bottom of each stack. Catalyst is purged of hydrocarbons in
preparation for transfer to either other Reactor or to the CCR Regenerator Section

RE-CONTACTING & RECOVERY SECTION:

 Re-contacting of the Net gas with low temperature naphtha from separator is performed for maximizing the
recovery of the LPG components.
 The remainder gas being chloride treated with Net gas Chloride treater.
 After chloride treating, the hydrogen rich gas flows to the Poly bed PSA Unit for H2 recovery & purification .
Catalytic Reforming Unit (CRU)
 CRU – SECTION DESCRIPTION

Fractionation Section
 Debutanizer is used for the separation of the LPG components and stabilize the naphtha received from
recovery section.
 Overhead vapors re-contacted for the LPG recovery and bottom product is Reformate (stabilized).

Regeneration (for Catalyst)

Regeneration of catalyst involves the following major steps:
 Coke Combustion – for removal of coke on spent Catalyst
 Oxy-chlorination & Calcination - to readjust the chlorine level on catalyst
 Reduction – to bring the catalyst back to the active state
 Catalytic Reforming Unit (CRU)
EFFECT OF PROCESS VARIABLES – PRESSURE:
 Hydrogen Partial pressure is the basic variable due to its effect on reaction rates.
 De-hydrogenation, de-hydro cyclization are enhanced by low pressure.
 Lower the pressure higher the yields of both Reformate and Hydrogen for Octane number..
 However, lower pressure increases coke make which is undesirable.
 Operating pressure increase requires increasing the design pressure rating of process equipments.

EFFECT OF PROCESS VARIABLES – TEMPERATURE:

Catalyst activity is directly related to reactor temperature. Temperature adjustment is required for the following;
 To change the Reformate Octane
 To process a different feed quality
 To balance a temporary loss of activity due to temporary catalyst poisoning
 To balance catalyst ageing which occurs slowly over several years
 Catalytic Reforming Unit (CRU)
EFFECT OF PROCESS VARIABLES – SPACE VELOCITY:
 Weight hourly space velocity, WHSV = Wt. of feed / Wt. of catalyst
 Liquid hourly space velocity, LHSV = Vol. of feed per hour / Vol. of catalyst

EFFECT OF PROCESS VARIABLES – H2/HC RATIO:

 H2/HC = Pure H2 (Mole/Hour) in recycle gas/ Naphtha Flow rate (mole/hour)
 A lower H2/HC ratio decreases the Hydrogen partial pressure and increases the coke formation

EFFECT OF PROCESS VARIABLES – FEED QUALITY:

 N + 2A (or) 0.85N +A is more representative

 The higher this index, the lower the severity of operation to meet the same product specification.
 The lower this index (i.e. higher Parffins) higher the severity of operation that would be required to
meet the same product specification as the de-hydrocyclization of paraffins becomes important.
 Catalytic Reforming Unit (CRU)
EFFECT OF PROCESS VARIABLES – FEED QUALITY Contd…

 Light Naphtha have poor naphthenic aromatic content and consequently a high C6 Paraffin content
 Cyclization of C6 Paraffins to Aromatics is more difficult than cyclization of C7 or C8 Paraffins.
 Heavier naphtha fractions have higher Naphthenic and Aromatic hydrocarboin content thus need low
severity to obtain good yields.
 The higher fractions also contains poly-cyclic compounds which produce high coke deposits on the
catalyst.
 Catalytic Reforming Unit (CRU)
EFFECT OF PROCESS VARIABLES

PROCESS VARIABLES

 Pressure
 Temperature
 Space Velocity
 Hydrogen Partial
Pressure
 Feed Quality
 Catalytic Reforming Unit (CRU) - Catalyst
 Reforming catalyst is either mono-metallic (in case of older units) or bi-metallic, with metals impregnated
on Alumina base.
 The catalysts can be in the form of extrudates (as normally found in SR CRU units) or Spehrical beads (as in
the case of CCRU units)
 Most commonly used Reformer catalysts contain Platinum and Tin impregnated on Alumina base, where Tin
is the promoter for the main metal Platinum.
 The main features of these catalysts are :
o High purity alumina support - high mechanical resistance
o Platinum associated with Rhenium - high stability & selectivity
o Platinum associated with Tin - high selectivity & High regenerability
A Reforming catalyst must possess the following properties;
• Activity
• Selectivity
• Stability
• Regenerability
• Cost Effectiveness
 Catalytic Reforming Unit (CRU)
ACTIVITY:
• For motor fuel reforming, activity is generally represented by the temperature required to produce a given
Octane number Reformate. The lower the temperature required, the more active is the catalyst.
• The higher the space velocity, the more active is the catalyst.

SELECTIVITY:
• In catalytic Reforming, Selectivity of the catalyst means the percent of desired product yield obtained from
the feed stock.
• In motor fuel reforming, a high yield of Reformate of the desired Octance number means good catalyst
selectivity.
• In Benzene, Toluene, Xylene mode of operation, a high yield of BTX aromatics is good selectivity.
• A catalyst can have good activity but poor selectivity. The platinum/Tin bi-metallic catalyst has good activity
and selectivity.
 Catalytic Reforming Unit (CRU)
STABILITY:
• Stability is generally measured by the amount of feed treated per unit weight of catalyst (m3 of feed per kg of
catalyst)
• It is chiefly the coke deposit which affects the stability through its inhibition of the catalyst activity and decrease in
metal contact area.
CATALYST CHARACTERSETICS:
• The Octanizing catalyst is generally a multi metallic catalyst containing Platinum plus metal promoters like Tin on
an Alumina support.
• High purity alumina support has strong resistance to attrition.
• High selectivity due to presence of Platinum and Tin
• High regenerability ideally suited for CCR
• High Reformate yield
• High Hydrogen yield
• High on-stream factor
• Low catalyst inventory
 Catalytic Reforming Unit (CRU)
TEMPORARY POISONS: PERMANENT POISONS:

 Which can be removed and the proper Activity and  Which induce a loss of activity which can not be
Selectivity of catalyst is restored. restored.
 The most common temporary poisons (inhibitors )  Main permanent poisons are
are:
o Arsenic
o Sulphur
o Organic nitrogen o Lead
o Water o Copper
o Oxygenated organics o Iron
o Halogens o Nickel
o Chromium
o Mercury
o Sodium
o Potassium
 Catalytic Reforming Unit (CRU)
REACTIONS INVOLVED:
Following are the most prevalent reactions in the CCRU reactors;
 De-hydrogenation of Naphthenes to Aromatics - Desirable
 Isomerization of Paraffins and Naphthenes - Desirable
 De-hydrocyclisation of Paraffins to Aromatics - Desirable
 Hydrocracking of Paraffins to lower molecular weight compounds - Un-desirable
 Hydrogenolysis, Hydrodealkylation, alkylation, trans-alkylation, Coking - Un-desirable
Reaction Promoted By
Catalyst Temperature Pressure
Naphthene Dehydrogenation Metal High Low
Naphthene Isomerization Acid Low* ---
Paraffin Isomerization Acid Low* ---
Paraffin De-hydrocyclization Metal/Acid High Low
Hydrocracking Acid High High
De-methylation Metal High High
Aromatic De-alkylation Metal/Acid High High
 Catalytic Reforming Unit (CRU)
HEAT OF REACTIONS/RELATIVE HEAT OF REACTIONS IN CRU REACTORS (P<10 bar):

REACTIONS HEAT OF REACTION

K CAL / MOLE RELATIVE RATE

NAPHTHENES DEHYDROGENATION -50 100

PARAFFINS DEHYDROCYCIZATION -60 1 (BASE)
ISOMERIZATION
PARAFFINS +2 +10
NAPHTHENE +3 +10
HYDROCRACKING +10 +3

HEAT OF REACTION < 0 = ENDOTHERMIC REACTION

 Catalytic Reforming Unit (CRU)
A.DEHYDROGENATION OF NAPTHHENES TO AROMATICS
Principal reaction producing Aromatics from Naphthenes
NAPHTHENE (RON = 83) ----> AROMATIC (RON =>100) + 3H2
(CYCLOHEXANE)

 Naphthenic compounds dehydrogenated into aromatics with

production of 3 moles of H2 per mole of Naphthene CH CH
2
 Highly endothermic CH HC
HC CH
 Promoted by the metallic function of the catalyst 2 2
+ 3H
 Thermodynamically favored by high temperature, low HC CH HC CH
2
2 2
pressure and high number of carbons
CH CH
 Kinetically favored by high temperature, high number of 2
Cyclohe xane Benzene
carbon; not affected by the hydrogen partial pressure
 At the selected operating conditions, reaction is very fast
and almost total
 Catalytic Reforming Unit (CRU)
B. ISOMERISATION OF PARAFFINS & NAPHTHENES
 In case of Paraffins, molecular re-arrangement takes place with
no change in molecular weight but with substantial change in C H
7 16 C H
7 16
Octane number.
 Equilibrium is readily attained between Paraffins and Iso- Carbon atom C4 C5 C6 C7 C8
paraffins and mainly depends upon temperature. Pressure has %Isoparaffin at
no effect. 44 58 72 80 88
500°C
 Desirable reaction because of the subsequent dehydrogenation
of the alkylcyclohexane into an aromatic
 Difficulty of ring rearrangement and high risk of ring opening
(paraffin formation)
 Isomerization rate is favoured by increase in temperature.
Pressure has no effect.
 Isomerization reactions are reversible and are mildly RON MON
exothermic in case of Paraffins and slightly endothermic in Ethylcyclopentane 67.2 61.2
case of Naphthenes.
Methylcyclohexane 74.8 71.1
 Reactions are promoted by the acidic part of the Catalyst
Toluene 120 103.5
 Catalytic Reforming Unit (CRU)
C. DE-HYDROCYCLISATION OF PARAFFINS:
 Multiple step reaction
 Most desirable but most difficult reaction CH
2
CH
2
CH
2 CH CH
2
CH
2
+H
 This is a multistep reaction, which converts normal or CH
3
CH
2
CH
2
CH
3
CH
3 CH CH
2
CH
3
2

iso-paraffin to aromatics and gives a noticeable increase C H

C H
in Octane number. 7 16 7 14

 Promoted by both acidic and metallic functions CH

2
CH
2
 Kinetically favored by high temperature, and low CH CH
2
CH
2
H C
CH
CH
2 3
pressure CH
3
CH CH
2
CH
3 CH CH
2 2
 Dehydrogenation step becomes easier as paraffin
Methylcyclohexane
molecular weight increases, but is competed by hydro
cracking. CH
2 CH
2 CH CH

 Minimum six carbon chain is needed to cyclize to form H C CH CH

3 HC
C
CH + 3H
2 3 2
aromatics.
CH CH CH CH
2
 At the selected operating conditions, much lower rate 2
Toluene
than that of dehydrogenation
 Catalytic Reforming Unit (CRU)
(m)
HYDRO CRACKING: +H
2
 Hydrocracking affects either Paraffins or olefins C H
7 16
C H
7 14

 Promoted by both acidic and metallic functions (a)

+
+H
 Favored by high temperature and high pressure C H
7 14
2
C H C H
4 8 3 8
 Exothermic (risk of runaway reactions)
 At the selected operating conditions, hydro cracking
+H
(m)

reaction could be complete, but is limited by kinetics 2

 Decrease of Paraffins and increase of aromatics C H

4 8
C H
4 10
proportion (i.e. increase in octane) in the reformate and a
loss of reformate yield
 Decrease in hydrogen production (cracking reactions
consume hydrogen)
 Increase of light ends production and low molecular
weight Paraffins
 Catalytic Reforming Unit (CRU)
HYDROGENOLYSIS:
+H CH +
 Promoted by metallic function CH
2
4
CH
7 16 6 14
 Favored by high temperature and high pressure or
 Exothermic (risk of runaway reactions)
+H CH +
2 6
CH 2
7 16 CH
5 12

HYDRO DEALKYLATION:
 Breakage of the branched radical of an aromatic ring +H + CH
4
2
 Promoted by metallic function
 Favored by high temperature and high pressure Xylene Toluene

 Consumes hydrogen and produces methane

 But at the selected operating conditions, and with the +H
2
+ CH
4

selected catalyst, this reaction is not significant

Toluene Benzene
 Catalytic Reforming Unit (CRU)
ALKYLATION:
 Addition of an olefin molecule on an CH
aromatic ring 3
 Promoted by metallic function + CH2= CH – CH3 HC
 leads to heavier molecules which may
increase the end point of the product CH
 High tendency to form coke; must be 3
Benzene Propylene Isopropylbenzene
avoided

TRANSALKYLATION (ALKYL
DISPROPORTIONATION):
 Dismutation of 2 toluene rings to
produce benzene and xylene
 Promoted by metallic function +
+
 Favored by very severe conditions
of temperature and pressure
 At the selected operating conditions,
and with the selected catalyst, this Toluene Toluene Benzene Xylene
reaction is negligible
 Catalytic Reforming Unit (CRU)
COKING:
 Results from a complex group of reactions. Detailed mechanism not fully known yet
 Linked to heavy unsaturated products (polynuclear aromatics) and heavy olefins traces or di-olefins
present in the feed or in CCR reactions
 Coke deposit reduces active contact area and reduces catalyst activity
 Favored by low pressure

In CCR operating conditions, necessity arises for a continuous regeneration

to maintain a low level of coke
 Catalytic Reforming Unit (CRU)
REACTOR-WISE REACTIONS
1ST REACTOR 2ND REACTOR 3RD REACTOR
Dehydrogenation Dehydrogenation Cracking
Isomerization Isomerization -
- Cracking -
- De-hydrocyclization De-hydrocyclization

PARAFFIN AND NAPHTHENE CONVERSION PER REACTOR

Reactor No. 1 2 3 4 Total Conversion
   Conversion of feed, percent
Cyclohexanes 95 3 0* 1* 99
Cyclopentanes 39 35 9 4 87
Paraffins 7 7 13 12 39
CATALYST REGENERATION SECTION
OF CCRU
Catalytic Reforming Unit (CRU)
 Catalytic Reforming Unit (CRU)
CATALYST REGENERATION STEPS:
1.COMBUSTION IN TWO BEDS:
Elimination of coke by burning
C + O2 CO2

2.OXYCHLORINATION/CALCINATION:
 Catalytic Reforming Unit (CRU)
3.REDUCTION:

Catalyst (oxide)  Catalyst (reduced)

 Catalytic Reforming Unit (CRU)
TROUBLE SHOOTING:
The main issues that require trouble shooting are as below:
 Unexpected decrease in Octane number of product
 Loss in yield of liquid Reformate product
 Unexpected reduction in delta T across the first reactor.
 High hydrocracking and risk of run-away temperature
 High pressure drop across the reactor/Regenerator

UNEXPECTED DECREASE IN OCTANE NUMBER:

 Presence of Nitrogen in feed – temporary poison
 Presence of Sulfur in feed – temporary poison
 Low chloride content in catalyst resulting in poor hydro de-cyclization of Paraffins
 Channeling of feed through the reactor - lower delta P due to lower catalyst contact
 Catalytic Reforming Unit (CRU)
LOSS OF REFORMATE YIELD:
 Presence of Sulfur in feed resulting in lower activity of catalyst
 Presence of metal in feed leading to permanent poisoning of catalyst
 Too high chloride content on catalyst leading to hydrocracking
UNEXPECTED DECREASE IN DELTA T OF 1ST REACTOR:
Lower Naphthene content in feed – poorer conversion
Higher H2/HC ratio – will not affect product quality in spite of lower delta T
Presence of S and N2 poisons in feed
Channeling of catalyst bed
HIGH HYDROCRACKING:
 Catalyst very fresh or excessively active acid function of catalyst
 Too high severity
 Very high chloride content on catalyst
HIGH PRESSURE DROP IN REACTOR/REGENERATOR:
 Excessive catalyst attrition in lift pipe resulting in fines plugging grid
 Due to broken catalyst fines and dust due to improper ellutriation
Thank You..