A-400

It has three sections.

Naphtha Hydrotreating Unit (NHT)
Catalytic Platforming Unit (PLAT)
Continuous Catalyst Regeneration Unit (CCR)

NAPHTHA
HYDROTREATING
UNIT
Prepared & presented by:
Muhammad Irfan Shahzad

Naphtha Hydrotreating

The feedstock or charge to Catalytic Reformer is

naphtha that has been processed in a feed preparation
unit to remove contaminants such as sulfur, nitrogen,
arsenic & lead. These contaminants are temporary or
permanent poisons to the catalyst & must be
eliminated for satisfactory catalyst performance.
The feed preparation unit itself is a catalytic unit using
Co-Mo or Ni-Mo catalyst. H2 is included with feed to
feed preparation unit. These feed preparation units are
called hydrodesulfurization (HDS) units or
Hydrotreaters.

Hydrotreating

Catalytic hydrotreating is a hydrogenation process used to remove about

90% of contaminants such as nitrogen, sulfur, oxygen, and metals from
liquid petroleum fractions.

If these contaminants are not removed from the petroleum fractions

they can have detrimental effects on equipment, catalysts, and the quality
of the finished product.

Typically, hydrotreating is done prior to processes such as catalytic

reforming so that the catalyst is not contaminated by untreated
feedstock. Hydrotreating is also used prior to catalytic cracking to
reduce sulfur and improve product yields, and to upgrade middledistillate petroleum fractions into finished kerosene, diesel fuel, and
heating fuel oils.

In addition, hydrotreating converts olefins and aromatics to saturated

compounds.

Octane Number
Octane rating has been used to measure antiknock
performance of gasoline. The higher the octane
#, the less the tendency for a gasoline to
produce a knocking sound in an automobile
engine. Straight chain paraffin n-heptane was
assigned zero octane # & branched chain
paraffin, iso-octane(2,2,4-trimethyle pentane)
was assigned 100 octane #.
Octane # = (RON+MON)/2

Catalyst
A catalyst accelerates a chemical reaction. It does so by
forming
chemical
bond
with
reacting
molecules(ie.adsorption),such that they can react to a
particular product which detaches itself from the
catalyst(ie.desorption) & leaves catalyst unaltered so that
it is ready to interact with next set of molecules.
Catalytic reaction is a cyclic event in which catalyst
participates & is recovered in its original form at the end
of cycle. It creates a favorable reaction pathway. Almost
80% of all chemicals produced in world have been in
contact with one or more catalysts.

PROCESS DESCRIPTION

Processing capability of NHT unit is 25,400

BPD (168.26 m3/hr).
NHT is composed of the following process
sections:
1. Reactor section.
2. Stripping section.
3. Splitter section.
Make-up hydrogen is supplied from Platforming
process unit via Dieselmax process unit.

Sulfiding

Catalysts are sulfided to form sulfur metal complex

which activates the cobalt-moly,nickel-moly & Pt
catalysts. In addition, sulfiding enhances superactive
catalyst sites which would otherwise promote
hydrocracking & shorten cycle life. Sulfiding is carried
out by passing hydrogen & a sulfiding agent over the
catalyst at a temperature no higher than 450F until
hydrogen sulfide breaks through.
After start up, most of the sulfur will be stripped out
from the catalyst as H2S & removed from system in
product separator, stabilizer and stripper O/H gas.
The superactive sites then will have been rendered
inactive by coke or other feed contaminants.

Sulfiding:

 Catalyst

Life

Cycle life is period b/w catalyst regenerations.

Ultimate

Life

It is period b/w start up with new catalyst & discarding

of it for metal recovery. Life is expressed in time or
barrels charged per pound of catalyst.

PLATFORMING CATALYST
POISONS

Arsenic and lead compounds, are permanent

poisons to platinum containing catalyst.
Sulfur is a temporary poison.
Organic nitrogen is also a temporary poison.
Oxygen compounds are harmful to the
operation of a Platformer.

Metal Removal

Arsenic, Lead, Sodium, Ca, Mg contact of feed

with salt water or additives.
Metal removal is complete above temperature
of 315C & max 2-3 wt% of the total catalyst.

Desulfurization begins at 230C & increases with temp.

Olefin saturation & Decomposition of low
contaminant of Cl require same temp. as
desulfurization
Decomposition of O & N require a somewhat high
temp. than desulfurization.
Demtalization require at least 315C.
Recommended min. inlet temp. of first reactor is
315C, while design temp.of reactor is 399C.

For SRN of moderate S content,(40~75 nm3/hr)

For cracked naphtha (up to 500 nm3/hr)
More than 500nm3/hr does not contribute to reaction
Design H2/HC ratio = 110 nm3/m3

Approximate range of LHSV for SRN=4~12

For cracked naphtha = 2~8
NHT design = 5.13, min = 2.56, Catalyst vol.= 32.8m3

To avoid build up of carbon on catalyst, maintain H2/HC &

catalyst temp. properly.
The primary causes of catalyst deactivation are:
Accumulation of coke on active sties of catalyst
Gradual accumulation of inorganic species picked up from
charge stock, i.e. Arsenic, lead, Ca, Sodium, Silicon &
phosphorus.
5wt% of carbon on catalyst does not reduce desulfurization,
though N removal reaction may be decreased.

Catalyst deactivation caused by accumulation of

deposits may be remedied by Skimming, screening &
reloading catalyst.
2~3 wt% of metals do not cause deactivation of
catalyst.
When metal on catalyst is 0.5%, content of metal in
product should be checked to prevent breakthrough
to Plat catalyst.
When metal on catalyst is 1~2 wt%, replacement of
catalyst should be considered.
To avoid plugging of reactors caused by
polymerization due to dissolved O2 in feed, blanket
the stabilized naphtha tank with N2 properly.

Reactor Section

Conversion of organic sulfur compounds to hydrogen

sulfide.
Conversion of organic nitrogen compounds to
ammonia.
Conversion of organic oxygen compounds to water.
Saturation of olefins.
Conversion of organic halides to hydrogen halides.
Removal of organo-metallic compounds.

Stripping Section

Removes hydrogen sulfide.

Removes water.
Removes light hydrocarbons.
Removes Dissolved hydrogen.

Splitter Section

HTN is fractionated in a Naphtha Splitter.

Split C5 and C6.
Light naphtha (C5) is sent to gasoline blending.
Heavy naphtha (C6+) becomes Platformer feed.

PROCESS FLOW

Control Flow Plan of Naphtha Feed Section

PROCESS FLOW

Control Flow Plan of Reactor Section with Recycle Gas.

PROCESS FLOW

Control Flow Plan of Stripping Section

PROCESS FLOW

Control Flow Plan of Splitter Section

MAJOR EQUIPMENTS

Reactor No.1 (200-R1) and Reactor No.2 (200R2)

Stripper column (200-V2)
Splitter column (200-V3)
Feed surge drum (200-V1)
Separetor (200-V6)
Recycle compressor suction drum (200-V7)

Stripper receiver (200-V4)

Splitter receiver (200-V5)
Charge heater (200-H1)
Combined feed exchanger (200-E1A to F)
Products Condenser (200-EA1)
Charge pumps (200-P1A/B)
Recycle compressor (200-C1A/B)

PRODUCT SPECIFICATIONS
Heavy Naphtha:
Total Sulfur, wt-ppm
Total Nitrogen, wt-ppm
Chlorides, wt-ppm
Water, wt-ppm
IBP C
EP, C
Lead, wt-ppb
Arsenic, wt-ppb
Iron + Chloride, wt-ppm
Copper + Heavy Metals, wt-ppb

<0.5
<0.5
<0.5
2.0max
As per target
204.4max.
<20max.
1max.
1max.
<25max.

Troubleshooting
Examine Feedstock
Higher boiling point fractions generally contain Sulfur &
Nitrogen compounds that are difficult to remove. The
net effect is that operating severity usually must
increase if boiling range increases to the desired
product specification. A high % age of cracked stock
also contain more Sulfur & Nitrogen.
Presulfiding
Proper presulfiding is necessary to achieve max.activity,
incomplete or improper sulfiding can significantly
reduce catalyst activity & cycle life.

Prolonged exposure to H2 at elevated temp.can result

reduction of metal oxides to inert base metals. In excessive
cases catalyst activity loss could be complete because metals
can then not be converted to sulfides without being first
returned to oxide state (ie.regenerated).
Poor flow distribution through the catalyst bed during presulfiding. This can be indicated by non uniform bed
thermocouple reading or by pre-mature H2S break through.
Poor flow is generally due to improper or non-uniform
loading of catalyst into reactor or improper installed flow
distributor. It can also be due to flow rates being outside of
recommended range during presulfiding. Any of these
conditions can result in incomplete sulfiding & reduced
catalyst activity.

Reactor Temperature Response

The first & easiest way is to check product quality response to a

change in reactor temperature. If product sulfur specification
can not be achieved even in spite of increase in reactor
temperature, a recombination reaction may be occurring. If
little or no improvement in product quality is observed, two
likely problems are either H2 starvation or feed by-passing the
catalyst.

H2 Starvation

Sulfur removal = 19~20 Nm3/m3

Nitrogen removal = 61 Nm3/m3
Olefin saturation = 2 Nm3/m3
Polyaromatic saturation = 5 Nm3/m3

Feed by-passing the Catalyst

A frequent cause of a portion of feed by-passing the catalyst is

leaking heat exchanger. Heat exchanger leaks can be detected
by:
1- Dye test
2- Radioactive tracers
Bed Channeling
If feed fail to fully contact with catalyst bed, it is called
channeling. Reactor bed temp. profile can indicate presence of
channeling. Increased pressure drop from start of run may
provide evidence of particulate deposition on top or inside of
catalyst bed which may cause channeling problem. Channeling
problem may be due to non uniform catalyst loading or
misalignment of feed distributor. If channeling is suspected
increase feed rate & recycle gas rate upto 25%.

If product quality improves with higher feed rate, it is suggestive

of channeling problem. Solution to channeling requires that
reactor be opened for correction of distributor or scale
problems or as a maximum catalyst be reloaded for correction
of loading problem.

Permanent Catalyst Poisons

Sodium(0.2 wt%), silicon(3~5 wt%), lead, arsenic(breakthrough
at 0.5~1.0 wt%), nickel , vanadium(5 wt ppm), phosphorous
& sulphate(5~10 wt%).These contaminants are absorbed on
catalyst from feed. Regeneration will not remove these
contaminants.

A Decision Tree