-

REPORT
( INITIAL LINE UP & PROCESS DESCRIPTION )

BY: M. SALEEM CHOHAN (Trainee Engineer)

NRL# 11542
 NAPHTHA HYDROBON ( 102 UNIT )
INTRODUCTION :

Naphtha hydrotreatment is practiced to prepare feedstock for catalytic reforming. All reforming
catalysts are gradually poisoned by sulfur compounds in the feed that strongly adsorb on and
coordinate with the metal sites. High sulfur levels in the feedstock lead to excessive coking
and rapid deactivation. Therefore, in commercial operation, it is required that sulfur content
in the feed be extremely low. Basic nitrogen compounds adsorb on acid sites. They inhibit
principally the acid function, but to some extent they can alter the metallic properties of the
platinum. In the presence of water, they can also result in leaching of chloride. Hence, nitrogen
compounds should also be removed from the reformer feedstock.. For bimetallic Pt-Re catalysts
the accepted guideline for optimal catalyst performance is that the sulfur in the feed should be
below 0.25–1 ppm to prevent the reversible sulfur from poisoning the hydrogen transfer
capability. As a platinum catalyst is easily poisoned by the presence of sulfur,oxygen, nitrogen,
and metallic components, it is essential to pretreat naphtha before reforming. The cost of
removing sulfur from the reformer feedstock is easily justified by the extended life of the
reforming catalyst.

PROCESS DESCRIPTION:

The feed heavy straight run Naphtha (Lean, 85°C–200°C fraction,) of Arabian light crude is
obtained from 101 CDU unit that has run down in 182 S-61 and S-511 storage tanks. The feed
tank S-62( Rich Naphtha processed from local crude) may be utilized through 182 -FCV 302 for
meeting desired product quality. The HTN (hydrotreated Naphtha) from storage tank 182 S-512
is used during the start up procedure.

102 HP SYSTEM:

The feed (HSRN) is pumped by 102 P1 A/B up to 40 bar .The flow is controlled by 102 FCV-026
.It is then combined with the hydrogen-rich gas (70-80%) through 102 PCV 65 A .The H2/HC
ratio b/w 250-400 SCFB is normally required.The mixed feed then enters the shell side of the
combine feed heat exchangers 102 E1 A-H where it is preheated by the reactor (102-R1)
effluent up to 510 ºF .At this temperature the Naphtha is completely vaporized, it is further
heated in a furnace (102-F1) to get final reaction temperature up to 610 ºF. The preheated
feed now enters the reactor 102 R-1 (skirt supported ) which is down-flow fixed bed reactor
containing S-7 and S-120 catalyst (Cobalt / Nickel- molybdenum sulfides alumina supported )
.Inert ceramic balls are placed above the catalyst bed to distribute the feed evenly and to
support the catalyst bed as well.In the presence of the metal-oxide catalyst, the hydrogen
reacts with the HSRN to produce hydrogen sulfide, ammonia, saturated hydrocarbons, and free
metals .

HSRN is processed at 4-12 LHSV .The main hydrotreating reaction desulfurization starts at about
450°F and dematellaization occur at 600°F. All reactions (gas-phase) are exothermic and,
depending on the specific conditions, a temperature rise through the reactor of 5 to 20°F (3 to
11°C) is usually observed.

The reactor effluent is cooled by passing in the tube side of 102 E1 A-H at around 195 °F. It is
further cooled to 135°F in 102- E2 (condenser) and upto 100°F in 103-E3 A/B (shell side) by
cooling water (tube side ). A wash water (condensate) injection (3 Vol% of feed rate ) from 102
P-2 is supplied at reactor effluent line to product condenser. The cooled reactor effluent with
injected water now moves to 102 V-2 , a three-phase separator provided with a mesh blanket
coalescer. The gases (mainly 87.1 % H2 ) separated from the top are passed to a fuel gas vessel
177 V4 through 102 PCV 039 .The injected water is drained out from the boot. The oil
(Naphtha) with lighter ends is passed to 102 C-4 (stripper ) through 102 LCV 40 to carry out the
stripping of lighter ends at low temperature and pressure.

Wash water injection at hydrotreater unit is required to eliminate ammonia in the gas
recycle.The presence of ammonia in the gas recycle although in very small amounts (usually
around 200-400 ppm depending on the type of bait) would greatly disrupt the catalytic activity.

NH3 + H2O ----> NH4OH

Preventing fouling due to the formation of ammonia salts like NH4Cl (especially on the fin fan
cooler reactor effluent, upstream high pressure separator for the low temperature salt
compound easily precipitate).

NH3+H2S----->NH4HS

NH4HS formation is the result of the reaction of inorganic ammonia (NH3) with inorganic sulfur
compounds (H2S). The function of dissolving NH4HS in wash water is not to be deposited on the
inside of the fin fan cooler that will cause plugging.

102 LP SYSTEM:
Hydrotreated Naphtha ,still containing light hydrocarbons, is passed to the stripper (102-C4)
through preheater 102-E4 shell side ( with C-4 bottom in Tube side). The H2S, H2O & NH3 are
stripped out from liquid naphtha due to high bottom temperature 428 ºF (maintain by reboiler
102-F2) and low pressure 6.8 Barg of the stripper. The overhead product passes through a fan
condenser 102 E-5 as well as further cooled in 102 E6 (double pipe Heat exchanger) and is
collected in the overhead accumulator 102 V5.A small quantity as reflux (~ 0.25) is pumped
back to top of C-4 by 102 P-4A/B through 102 FCV 73.The gases separated from the top of 102
V-5 are passed to a fuel gas vessel 177 V4 through 102 PCV 071. The stripper bottom product
(HTN) sent directly to Platformer after heat recovery (102 E-12A) while partially to make up
intermediate HTN storage tank 182 S-512 through 102 LCV 054.

Overhead system of the stripper is protected from H2S attack, by injecting corrosion inhibitor
(from 102 P-6) which forms a protecting film on the metallic surface.UOP recommends 5ppm
dosage rate of the (2% Vol) Corrosion Inhibitor.

The stripped naphtha must have total sulphur and nitrogen below 0.5 wt-ppm as well as iron
and chlorides 1 wt-ppm max.

PROCESS VARIABLES:

The principal operating variables are temperature, hydrogen partial pressure, and space
velocity. Increasing temperature and hydrogen partial pressure increases sulfur and nitrogen
removal and hydrogen consumption. Increasing pressure also increases hydrogen saturation
and reduces coke formation.

Hydrogen consumption is an important consideration because :

o many of the components present in the feedstock are more valuable as unsaturates,
especially aromatics,
o hydrocracking is to be minimized since it results in the production of light gases
effecting H2 purity, and
o hydrogen is expensive

Increasing space velocity reduces conversion, hydrogen consumption, and coke formation.
Although increasing temperature improves sulfur and nitrogen removal, excessive
temperatures must be avoided because of the increased coke formation. Factors which
determine minimum RIT (600 °F) are

o Combined feed to charge heater(102-F1) is all vapors.

o Demetalization reaction must complete to protect platformer catalyst from poison.
The process variables are reactor pressure (300-500psig), reactor temperature (min. 600°F) ,
space velocity (4-12 LHSV), hydrogen/ hydrocarbon(H2/HC) molar ratio (250-400 SCFB), charge
stock properties (P.O.N.A), & catalyst activity.

In BTX production, the objective is to transform paraffins and naphthenes into benzene,
toluene, and xylenes with minimal cracking to light gases.

HYDROTREATING CATALYSTS

Cobalt–Moly Catalysts

By and large, CoMo catalysts have been designed primarily for desulfurization, but some
denitrogenation and demetallation is also achieved. These catalysts can treat feedstocks of
widely varying properties. CoMo catalysts have the lowest hydrogenation activity, therefore
they have the lowest hydrogen consumption for a given removal. They also have the lowest
sensitivity of H 2 consumption to changes in operating pressure. In general, CoMo catalysts
have the highest desulfurization performanceat the lower operating pressures (<600 psig, or <
∼ 40 barg). These catalysts also have the lowest denitrogenation performance due to low
hydrogenation activity. Because CoMo catalysts exhibit the highest sulfur removal per unit of
hydrogen consumed, they are best suited for desulfurization at lower pressures and when
hydrogen is in short supply.

Nickel–Moly catalysts

NiMo catalysts have been designed for desulfurization, but particularly for hydrogenation and
denitrogenation. Metal removal can also be achieved. These catalysts can treat feedstocks of
widely varying properties. NiMo catalysts have higher denitrogenation activities than CoMo and
are therefore used for cracked stocks or other applications where denitrogenation and/or
saturation is as important as desulfurization. The higher hydrogenation power of NiMo catalysts
allows them to be used as a topping layer to saturate olefins and other gum precursors to
mitigate catalyst bed fouling leading to pressure drop accumulation and poor liquid flow
distribution through the catalyst bed. The performance of NiMo catalysts is very good at high
pressures. NiMo catalysts show a greater response in denitrogenation and desulfurization
performance to changes in H2 partial pressure than CoMo.
 PLATFORMING UNIT ( 103 UNIT )
INTRODUCTION :

The Platforming process is a UOP-developed and engineered catalytic reforming process in

widespread use today throughout the petroleum and petrochemical industries.

In the Platforming process, HTN is contacted with a platinum-containing catalyst at elevated

temperatures and hydrogen pressures. The primary purpose is to produce high octane gasoline
or aromatics (BTX).Chemical-grade hydrogen, light gas, and liquefied petroleum gas (LPG) are
also produced as reaction by-products.

PROCESS DESCRIPTION:

The Platforming naphtha charge typically contains four major hydrocarbon groups: paraffins,
ole-fins, naphthenes, and aromatics (PONA). Desulfurised naphtha (90°C–140°C) is catalytically
converted to high octane gasoline by the reaction of a platinum (now platinum–rhenium)
catalyst in a reactor in a hydrogen environment.The primary purpose of the Platforming process
is to produce aromatics from the paraffins and naphthenes. The paraffins and naphthenes
undergo two types of reactions in being converted to higher octane components: cyclization
and isomerization.

103 HP SYSTEM:

Hydrotreated Naphtha feed from 102 unit pumped by 103 P7A/B to the Plat-forming unit is
mixed with recycled hydrogen gas through 103 FCV-50. This mixture is preheated by a vertical
exchanger (103-E6 taxes tower tube side) up to 825ºF. further heated to reaction
temperature 935 ºF by a fired heater 103 F-3 , & then charged to the reactor section. It is
worth mentioning that a chemical (Perc) & condensate from 103 P-6 is injected at the 103 E-6
tube inlet and outlet respectively . The primary purpose of chloride (Perc) injection is to
maintain acidic reaction sites which are responsible for the desired (Dehydrocyclization and
Isomerization) and undesired (Hydrocracking) reactions. The function of water injection is to
redistribute the chloride through the whole catalyst bed. Hence an adequate water /chloride
balance is required.

Most of the reactions that occur in the Platforming process are endothermic, the reactor
section is separated into several stages, or reactors (103 R-6,R-7,R-8) which are ring girder
supported. Temperature drops In the first reactor (103-R6) by 85 to 100ºF ,in the second
reactor (103 R-7) , by 35ºF to 45 ºF and 10ºF to 18 ºF in 103 R-8. Fired heaters (103 F-4 & F-5)
are installed between these reactors to reheat the process stream up to the correct
temperature for the next stage.One of the effluent stream from 103 R-8 is passed to tube side
of 103 E-13 (reboiler of 103 C-10) The other effluent stream is cooled ( up to 230 ºF )by
exchanging heat with the feed (103 E-6 shell side).The temperature of both streams is
controlled by 103 TCV 114 for maximum heat recovery. Additional cooling to near-ambient
temperature is provided by air cooler (103 E-8) & water cooling (103 E-9 A-D). The effluent is
then charged to the separation section, where the liquid and gas products are separated. A
portion of the gas from the separator 103 V-9 is compressed by 103 K1 A-D and recycled to the
103 reactor section through 103 PCV 53 as well as to 102 unit through 102 65-A.The remaining
portion of the gases is sent to 177 V-4 by 103 PCV 65-B.The liquid (Plateformate) is passed to
103 E-10 A-C shell side through 103 LCV 63.It is worth mentioning that a chemical (Perc) &
condensate from 103 P-6 is injected at the 103 E-6 tube inlet and outlet respectively . The
primary purpose of chloride (Perc) injection is to maintain acidic reaction sites which are
responsible for the desired (Dehydrocyclization and Isomerization) and undesired
(Hydrocracking) reactions. The function of water injection is to redistribute the chloride through
the whole catalyst bed.

103 LP SYSTEM:

The separator liquid is preheated up to 300 ºF in 103 E-10 (shell side) and sent to the product
stabilizer (103-C 10 debutanizer), where the more-volatile light hydrocarbons are fractionated
from the high-octane liquid product. Stabilizer Bottom Re-boiler 103 F-6 provides necessary
heat for vaporization by maintaining the temperature of the bottom material(440ºF) and at a
pressure of 17 Barg, under automatic pressure Control system. Light hydrocarbons up-to
Butane(C4) and H2 removed from Platformate at top temperature of 135ºF and collected in
overhead reflux vessel (103V11) after being condensed in air cooler (103 E14).Stabilized
Reformat from bottom is sent to storage tanks S-16/17/18/19 after being first cooled in feed
preheater 103 E 10 tube side, then in 103 E-11 (air cooling) and further cooled in 103 E-12
A/B/C (water cooling).From the reflux stream of stabilizer being pumped by 103 P8, LPG can be
withdrawn and sent to 120 PRU unit through 103 LCV 137. Typically, Platforming coverts the
naptha feed into 85% liquid reformate, 10% hydrogen and 5% LPG
PROCESS VARIABLES:

The yield of aromatics is increased by:

1. High temperature (increases reaction rate but adversely affects chemical equilibrium)

2. Low pressure (shifts chemical equilibrium ‘‘to the right’’)

3. Low space velocity (promotes approach to equilibrium)

4. Low hydrogen-to-hydrocarbon mole ratios (shifts chemical equilibrium ‘‘to the right,’’
however, a sufficient hydrogen partial pressure must be maintained to avoid excessive
coke formation)
It is clear, therefore, that optimum process conditions are determined by the desired
quality of the product distribution.

CHEMICAL REACTIONS IN 102 & 103 UNIT

HYDROTREATING REACTIONS:

The main hydrotreating reaction is that of desulfurization but many others take place to a
degree proportional to the severity of the operation. Sulfur removal difficulty increases in the
following order: paraffins < naphthenes < aromatics The type of sulfur compounds can be
classified as mercaptans, sulfides, disulfides, thiophenes, benzothiophenes, dibenzothiophenes,
and substituted dibenzothiophenes. The ease of removal of these sulfur compounds is in the
same order, the mercaptans being the easiest to remove and dibenzothiophenes the most
difficult. Olefin saturation is very rapid and highly exothermic

Typical reactions are:

There are fundamental differences in the removal of various impurities, largely because of the
structure of the different molecules. HDS and olefin saturation are the most rapid reactions,
and HDN and HDA are the most difficult. In contrast to HDS, for HDN the aromatic must first be
saturated, and then the nitrogen is removed. Most of the reactions are irreversible with the
exception of HDA, which is equilibrium limited at high temperatures, since at these conditions
the reverse reaction of naphthene dehydrogenation becomes favored. All the hydrotreating
reactions are exothermic, causing an increase in the reactor temperature as the feed passes
through the catalyst bed. As the number of moles of hydrogen required to remove each
organo-compound increases, the amount of heat released also increases.
In general, the ‘main messages’ concerning hydrotreating reaction rates, heats of reaction and
hydrogen consumption are:

 Desulfurization and olefin saturation are the most rapid reactions

 Olefin saturation liberates the most heat per unit of hydrogen consumed
 Denitrogenation and aromatic saturation are the most difficult reactions
 Hydrogen consumption and heat of reaction are related

PLATEFORMING REACTIONS:
Naphtha reforming involves different types of reactions which are thermodynamically and
kinetically favored at different reaction conditions. For example, dehydrogenations are favored
thermodynamically and kinetically at high temperature and low pressure while isomerization is
kinetically favored at high temperature and pressure.

Desirable reactions in a catalytic reformer all lead to the formation of aromatics and
isoparaffins as follows:

1. Paraffins are isomerized and to some extent converted to naphthenes. The naphthenes
are subsequently converted to aromatics.

2. Olefins are saturated to form paraffins which then react as in (1).

3. Naphthenes are converted to aromatics.

4. Aromatics are left essentially unchanged.

Reactions leading to the formation of undesirable products include:

1. Dealkylation of side chains on naphthenes and aromatics to form butane and lighter
paraffins

2. Cracking of paraffins and naphthenes to form butane and lighter paraffins

The overall process generates H2, part of which is recycled to keep coke formation to a
minimum.

DESCRIPTION:

Dehydrogenation of Naphthenes.
The dehydrogenation reactions are highly endothermic and cause a decrease in temperature as
the reaction progresses. In addition, the dehydrogenation reactions have the highest reaction
rates of the reforming reactions which necessitates the use of the interheaters between
catalyst beds to keep the mixture at sufficiently high temperatures for the reactions to proceed
at practical rates.

The major dehydrogenation reactions are:

1. Dehydrogenation of alkylcyclohexanes to aromatics:

2. Dehydroisomerization of alkylcyclopentanes to aromatics:

3. Dehydrocyclization of paraffins to aromatics:

The dehydrogenation of cyclohexane derivatives is a much faster reaction than either the
dehydroisomerization of alkylcyclopentanes or the dehydrocycli- zation of paraffins, however,
all three reactions take place simultaneously with different extent and are necessary to obtain
the aromatic concentration needed in the reformate product to give the octane improvement
needed.
Aromatics have a higher liquid density than paraffins or naphthenes with the same number of
carbon atoms, so 1 volume of paraffins produces only 0.77 volumes of aromatics, and 1 volume
of naphthenes about 0.87 volume. In addition, conversion to aromatics increases the gasoline
end point

Isomerization Reactions

Isomerization of paraffins and cyclopentanes usually results in a lower octaneproduct than does
conversion to aromatics. However, there is a substantial increase over that of the un-
isomerized materials. These are fairly rapid reactions with small heat effects.

1. Isomerization of normal paraffins to isoparaffins:

2. Isomerization of alkylcyclopentanes to cyclohexanes, plus conversion to benzene

Isomerization yield is increased by:

 High temperature (which increases reaction rate)

 Low space velocity
 Low pressure

Hydrocracking and Dealkylation.

The hydrocracking reactions are exothermic and result in the production of lighter liquid and
gas products. They are relatively slow reactions and therefore most of the hydrocracking occurs
in the last section of the reactor. The major hydrocracking reactions involve the cracking and
saturation of paraffins.
The concentration of paraffins in the charge stock determines the extent of the hydrocracking
reaction, but the relative fraction of isomers produced in any molecular weight group is
independent of the charge stock.

Hydrocracking yields are increased by:

 High temperature
 High pressure
 Low space velocity

In order to obtain high product quality and yields, it is necessary to carefully control the
hydrocracking and aromatization reactions. Reactor temperatures are carefully monitored to
observe the extent of each of these reactions.

REFORMING CATALYSTS

Reforming catalysts involve dual functions; acidity and dehydrogenation function. The acidic
center of the catalyst promotes the structural changes involved in isomerization reactions. The
dehydrogenation reactions are catalyzed by metal site of the catalyst. Reforming catalyst
usually contains Pt as the metal component and modified γ-Al2O3 as the source of acidity. The
acidity of the Al2O3 is further enhanced by incorporation of chloride ions into its structure.
Addition of small amount of Re along with pretreatment with H2S improves the life of the
catalyst. Resulfide breaks up the Pt metal surface into smaller entities and decreases the
probability of coke formation.

Catalyst Deactivation & Regeneration

Catalysts are mainly deactivated by coke deposition. Coke deposition can be minimized by
increasing H2 pressure. The catalysts can be regenerated by controlled burning of coke. Other
poisons such as sulfur compounds, water and traces of aromatics can also be removed during
coke burn off. The adsorbed sulfur and water on the catalyst can also be removed by
decreasing their partial pressures in the stream, when they are reversibly adsorbed

Poisoning and fouling by coke and sintering of the noble metal are the primary modes
of catalyst deactivation in catalytic reforming of hydrocarbons. Other poisons, such as
amines and extraneous sulfur compounds, are usually desorbed or combusted when the coke
is burned off.

Regeneration ( ACTIVATION )

The regeneration is conducted in fixed beds by carefully adding small amounts of 0 2 in N2 at

about 450°C and monitoring the exotherm to limit temperatures to no higher than about
550"C, to avoid excessive sintering of the Pt. The first reactor usually contains about 2-3%
coke and less than 1% after regeneration. The catalyst in the last reactor, however,
which processes the most kinetically unfavorable reactions, can accumulate as much as 15%
coke prior to regeneration. Because of the high process temperatures, some sintering of the
metal invariably occurs, leading to Pt agglomerates and a loss in Pt area. However, in
contrast to most other catalytic processes, the Pt can be redispersed by adding additional
amounts of CI, in the form of an organochloride compound, and about 5% 0 2 at 500-550°C for
2-3 h. This effectively breaks up the metal agglomerates into molecular Pt complexes, which
adsorb strongly and uniformly across the A1203 surface and are reduced to small metal
clusters in H2 at about 450°C.

Irreversible, permanent poisoning by traces of arsenic and lead in the crude requires
that a tight specification of the feed be maintained. Arsenic can not exceed 1 ppb and lead
must be less than 20 ppb.It is also necessary to maintain sulfur, nitrogen, chlorides and
fluorides below 1 ppm in the feed. Water or oxygenated hydrocarbons should be kept below 4
ppm
Table 1.1 Equipment Functions w.r.t. Tag Equipment tag name Function
Names for LPG 6
C-1 Deethanizer column
C-37 Chloride trap
C-2 Deethanizer overhead accumulator
C-3 Propane/Butane splitter
C-15 Feed surge drum
C-9 Compressor knock out pot