PARCO-Mid Country Refinery Page 1 of 9

PROCESS DEPARTMENT Platforming Unit

Chloride Management in Platforming Unit U-300

Chloride Management in Platforming Unit

Anas Nadeem / Musa Kaleem

Prepared By: ……………………………
A-400
Irfan Qadir
Checked By: Group Head A-400 ……………………………

Nasir Zia Ahmed

Reviewed By: Chief Engineer (Zone-II) ……………………………
D
a Riaz A.K Butt t
Approved By: ……………………………
e Manager Process :
May 4, 2020
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

1.0 OBJECTIVE:
The objective of this report is to highlight the impact of chloride injection in the platforming
circuit, its downstream units and to analyzes the different technologies and practices
available to mitigate high chlorides in the platforming circuit.

2.0 INTRODUCTION:
Some of the Platforming reactions are acid-catalyzed, while others are promoted by a metallic
catalyst function. Therefore, it is necessary that a Platforming catalyst have a proper balance
between the metal and the acid functions. For this purpose, catalysts are dosed with organic
chloride, which promotes acidic catalyzed reaction. However, it also leads to formation
chloride compounds in the product streams at low ppm levels. If untreated, these
chlorides, containing hydrogen chloride (HCl) and various organic chlorides, cause
operational upsets. These problems include formation and deposition of ammonium
chloride, chloride related corrosion, green oil formation, poisoning of downstream
catalysts which affect product quality.

The tracking of chlorides and use of proper analysis techniques for the measurement of
HCl and organic chlorides in reformer product streams is critical for effective chloride
management in a running reformer unit to prevent associated operational issues. HCl is
comparatively easy to measure and detect more reliably. As a result, chloride guard
product developments have focused on improving the capacity of HCl removal.

3.0 IMPACT OF CHLORIDES ON DOWNSTREAM

The chlorides cause various problem in the circuit and downstream units if it breaks
through adsorber. Details of these problems are mentioned below with equipment wise
description

3.1 Deposition of salts in preheat exchangers and charge heater

Deposits of white salt in exchangers when opened often indicate a chloride problem.
This is seen, if there is any entrained water in the hydro processing unit feed or
chloride salts above saturation are present, there will be fouling of the feed preheat
exchangers and charge heater tubes.

3.2 Reactor Fouling

Chloride containing salts that reach the reactors will decompose or hydrolyze at
reaction conditions, releasing HCl and leaving metals fouling the catalyst. If,
somehow, sodium chloride is present in the feed, it will deposit directly in the catalyst
bed without decomposing, forming a hard layer and causing high pressure drop.

3.3 Reactor effluent fouling and corrosion

Heat exchanger tube and shell thinning or pitting, especially in reactor effluent
exchangers, is often seen. The most common corrosion location of concern is the
reactor effluent side of the feed/effluent exchangers where ammonium chloride salts
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

(NH4Cl) deposit in the exchangers, especially when wash water practices are
inadequate. If austenitic stainless steel is present, chloride stress corrosion cracking
presents an additional metallurgical challenge.

3.4 Stripper Fractionator Feed Pre-heat:

Some of the most difficult exchanger conditions are presented when fractionator or
stripper feed is preheated by high pressure reactor effluent. The fractionator feed has
a small amount of residual free water that is carried into the fractionator preheat
exchangers. This water contains dissolved ammonium chloride. As the stream is
heated, the water eventually evaporates, leaving ammonium chloride salt deposits on
the tubes where it evaporates.

3.5 Stripper and Fractionator:

Corrosion of the upper trays in a hydroprocessing unit stripper or fractionator may
indicate a problem. Deposits of iron sulphide will be observed in product rundown
coolers and tanks when chloride is active in a system.

3.6 Compressor Issues:

Make-up hydrogen compressors and recycle gas compressors will experience
chloride salt deposition on machine surfaces. In reciprocating compressors, valve
deposits form, resulting in high valve failure rates. Centrifugal compressors will
experience loss in efficiency.

3.7 Amine treating system:

Several hydrotreating units have high pressure amine scrubbers to remove H2S from
recycle gas. These scrubbers also effectively remove chloride from the gas. While the
hydrotreater may not have problems, the amine regenerator tower and overhead
system may suffer accelerated corrosion.

3.8 Fuel gas system:

Chlorides build up in fuel gas due to hydrogen and other off gases added in this
system. These are believed to be active in promoting corrosion of the fuel gas piping.

4.0CHLORIDE ABSORBERS:
In past, Absorbents were developed to effectively remove HCl. Even so, performance of
the ad- or ab-sorbent products has proven to be variable between one catalytic reformer
duty and another.

More recently, a growing concern for many refinery operators has become the removal of
organic chloride species. These compounds are less easy to detect and measure and
also are less readily ad- or ab-sorbed. The effectiveness of the available chloride guard
products is limited although improvements are being made to the formulations.

At the operating conditions in the reformer, the organic chloride used for dosing the
catalyst breaks down to HCl that is believed to be the active chloriding species. The
chloride, however, is not irreversibly bonded to the catalyst surface. Hence, the need for
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

continuous dosing, and chloride is inevitably found in the product streams leaving the
catalytic reforming reactors at low ppm levels.

Refineries have installed dedicated chloride guard beds to remove the chloride at various
locations in the downstream sections of the catalytic reformer. The nature and severity of
the problems experienced also influence the number and location of these guard beds.

A prevalent view was that the chloride was predominantly HCl or that the problems
experienced were dominated by the HCl component of the chlorides but studies have
showed that there has been a marked increase in concern for detection and removal of
the organic chloride species.

Chloride guards of all types, particularly in gas phase duties, do not give the expected
performance in certain conditions. After some analysis, the contributing factors seem to
be formation of green oil in the chloride guard bed and a higher level of olefins, aromatics,
and complex heavy hydrocarbons. A higher level of olefins, aromatics, and complex
heavy hydrocarbons adsorbs onto the guard material and fouls the material by blocking
access to the reactive sites.

Types of Adsorbent guard beds for Chloride removal are as below;

Physical Adsorption
The commonly available chloride guards for Chloride removal in gaseous phase are
based on simple activated alumina. The removal mechanism is physical adsorption
and the high alumina surface area is required to boost the capacity for HCl removal.
the activated aluminas have generally demonstrated a capacity of around 5–10 wt%
chloride when spent.

Chemical Adsorption
Chemical adsorbents are composed of Na, Zn and Al oxides. The performance of
the absorbent is based not only on the chemical composition but also on the
dispersion of the active agents and pore structure of the particles. The chemical
adsorbents demonstrated a capacity of approximately 40 wt% chloride.

Hybrid Adsorption
Promoted alumina are hydrid adsorbents in which a high alumina surface area has
been doped with a quantity of basic metal oxide or similar salts, often of sodium or
calcium. The alumina component removes HCl. The promoter (usually Sodium
Oxide), however, chemically reacts with the HCI giving an additional chloride removal
mechanism referred to as chemical absorption. The promoted aluminas have
generally demonstrated a capacity of approximately 24 wt% chloride.

4.1 Comparison of available adsorption types:

Physical Adsorption Chemical Adsorption Hybrid Adsorption

 It is active alumina  Rely on chemical  Promoted alumina is

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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

based and primary used reaction between HCl obtained by doping an

for gas phase to remove and the reactive phases alumina surface with a
HCl. in the formulation basic metal oxide, often
sodium or calcium. The
 It is a reversible process  This chemical reaction alumina component
so highly depends on is irreversible, and the removes HCl through an
surface area, bed reaction rate is favored adsorption process while
temperature, partial by relatively high the promoter chemically
pressure of HCl and temperatures. This reacts with HCl giving
H2O. means that higher chemical adsorption
temperatures of
operation can be used  Its dual nature enables it to
where a physical work on high temperature
adsorbent will have little than physical adsorption
effect (Debutanizer feed and can be installed on
or bottom). liquid entraining gases.

 It has high cost but  Liquid side reaction

 It has low cost but
unlikely physical (Chemical adsorption)
disadvantages cannot
adsorption can and can significantly suppress the
be ignored such as side
be used on liquid phase physical adsorption by
reaction (green oil
without any significance making a liquid film on
formation), ineffective
impact on rate of active sites.
on liquid streams.
adsorption.

4.2 Guard Beds Location:

In order to prevent downstream problems caused by chlorides, guard beds can be
installed at a variety of locations in a catalytic reformer unit. The nature and severity
of the issues experienced influence the number and location of the guard beds.

For a new unit, it is licensor experience that generally governs the location and
arrangement of chloride guard beds. Location also depends upon the refiner’s
preferences when options are available. Possible locations of chloride guard beds in
a reformer unit are;

4.2.1 Recycle Gas Stream:

The chloride guard bed is installed in the recycle gas as the basis of a preferred
design for reduction in chloride levels across the entire system. It is important to
limit recycle gas chlorides within 2-3 ppmv to minimize corrosion in the system.
With high levels of chlorides at the inlet of the net gas compressor, sticky oil
formation is occasionally experienced in the compressor’s high pressure stages.
Recycle or net gas chloride becomes spiked due to mixing of chloride moisture
rich reduction effluent (after catalyst reduction with hydrogen) with recycle gas by
design.
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

4.2.2 Reduction Gas Outlet:

A Chloride guard bed can also be installed on Reduction Gas outlet as product of
Reduction of Platforming catalyst is moisture which leaches out chloride from the
catalyst. These gases are than routed towards separator or Net Gas Compressor
suction drum; it keeps on concentrating HCL in Recycle Gas circuit and also
become the reason of Green Oil Formation Net Gas Compressor. A chloride
treater may be required for the reduction effluent before it is mixed with recycle
gas.

4.2.3 Net Gas Outlet:

Another most common location for installation of a chloride guard bed is on net
gas before its supply to consumers.

5.0 ORGANO-CHLORIDE CHEMISTRY:

Organic chlorides are formed due to the presence of olefins in reformer product streams.
These olefins react with HCl in the presence of an acid catalyzed bed (for example,
AlCl3) to form organic chlorides.

5.1Factors affecting Organic Chlorides Production:

The major factors that affect their production are:

1. Olefins breakthrough from upstream units

2. Loss in catalyst Surface Area.
3. Catalyst age.
4. Weighted Inlet Temperature (WAIT).
5. Platinum dispersion in catalyst.
6. Chloride addition in Regenerator.

The olefins breakthrough in Naphtha Stream from upstream crude distillation unit,
hydrocracking unit or inability of NHT catalyst to process these olefins can cause
formation of organic chloride.

The lower catalyst surface area hinders maintenance of critically important

platinum dispersion. Loss of platinum dispersion increases olefin production which,
along with higher HCl content, can increase organic chloride formation as the
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

catalyst ages. Higher organic chloride formation further accelerates reduction of

the chloride adsorbent’s lifetime.

The leakage rate of chlorides from the reformer increases as the catalyst
incrementally loses surface area with each regeneration. A lower surface area
catalyst requires a lower H2O/HCl ratio in order to maintain constant catalyst
chloride content. Chloride addition to the catalyst must be increased in the
regenerator to obtain the required lower H2O/HCl ratio since the H2O
concentration remains relatively constant. This increased addition of chloride to the
catalyst results in shortening the lifetime of the chloride adsorbent.

The impact of organic chlorides becomes more severe with aging of the reformer
catalyst. With aging, the olefins in the reformer product streams increase and more
HCl dosing is required to maintain the chloride on the catalyst. Partitioning of
olefins happens in the gas phase as well as the liquid phase. Typically, 800-1000
ppmv olefins in net gas and 0.7 - 0.9 wt% olefins have been observed in reformate.
However, this strongly depends upon weighted average inlet temperature (WAIT),
loss in catalyst surface area, and platinum dispersion in the catalyst.

5.2 Reason of Organic Chlorides Breakthrough:

Organic chlorides are less polar than HCl and less readily adsorbed in the guard
bed. They may break through months before HCl breakthrough and remain
invisible in the absence of testing, leading to operational problems in downstream
sections.

It is worth mentioning that if testing has indicated that HCl is not detectable in the
product streams but downstream corrosion is still occurring it may be that chlorides
are present but in the form of organic chlorides.
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

Hence, the best adsorbent selection & its replacement must be based on organic
chlorides breakthrough to avoid upsets in downstream units. Following are the
qualities to ensure a good quality adsorbent activity:

1. Minimize the acid strength of the chlorinated adsorbent.

2. Maximize the organic chloride pickup capacity of the adsorbent.
3. HCl and organic chloride lifetimes should closely match each other
4. Inhibit polymerization reactions.
5. Handle Liquid Entrainment
6.0 CHLORIDE ADSORBENTS REPLACEMENT
There are various methods for available for finding chloride guarding capabilities of the
Bed. A brief comparison of those methods that can be adopted are compared below .

Time Based HCL Based Replacement Organic Chloride

Replacement Based Replacement
Adsorbent changed Adsorbent changed after HCl Adsorbent changed after
based on expected breakthrough organic chloride
lifetime breakthrough
Most lifetime estimates
are based on HCl
breakthroughs. Organic chloride often
Adsorbent lifetimes will breaks through months Ensures chloride free
decrease when before HCl. Measuring only operation of downstream
reformer catalyst gets HCl will lead to months long units and equipment
older and leaks more undetected leakage period
and more chlorides to
the product stream

7.0 CONCLUSION:
Chlorides can enter refinery process units via several routes, mainly from Reforming
units. They will adversely affect unit’s reliability. The primary keys to controlling the
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PROCESS DEPARTMENT Platforming Unit
Chloride Management in Platforming Unit U-300

adverse effects is the elimination of the incoming chlorides, intercepting the chlorides that
do enter, and controlling the effects of the remaining chlorides.

8.0 RECOMMENDATIONS:
1. To determine the chloride content of most hydrocarbon streams down to less than 3
ppm X-rays, Wet chemical methods based on potentiometric titration with methanol
and ion chromatography or any other suitable method can be used.

2. Crude analysis for inorganic and organic chlorides in the crude before and after the
de-salters. Monitoring Chloride contents of any slops or recovered oil streams
reprocessed. If the chloride problem is in a specific boiling range, Chlorides to be
checked in that boiling range of the crude.

3. The use of proper technique for measuring the organic or total chlorides instead of
relying only on HCl measurement deciding factor for the absorber bed replacement
rather than time based calculation and to avoid organic chloride breakthrough
(UOP779 for organic chlorides and ASTMD7536 for total chlorides).

4. A detailed study is required to choose and replace the adsorbents which produce less
organic chlorides and can capture more organic chlorides instead of HCL.

5. Chloride saturation of the bed to be calculated to avoid undetectable slippage of

chlorides as well as the side reaction chemistry of polymerization / green oil formation
due to over-saturation of the guard bed.

6. Regular monitoring of temperature and pressure chloride treater. Any sudden

temperature rises and drop in pressure will greatly affect its performance.