Combating green oil formation in a

CCR reformer
The addition of a chloride adsorber guard bed solved a refiners issues with
contamination affecting a CCR reformers rich gas compressor
Osman Kubilay Karan, Mehmet Asim Ay and Koray Kahraman Tpras Kirikkale Refinery
Arnaud Selmen Axens Technology &Technical Services

CR reformer units need chloride injection

during regeneration to promote platinum
dispersion and to restore catalyst acidity.
This leads to hydrogen chloride formation, and a
highly viscous green oil may also be formed at
some locations in the unit. This is one of the
main reasons why the operation of a CCR
reformers rich gas compressors can affect unit
reliability. This article looks at a real-world
example of green oil formation, and shows how
the main cause was identified and then
overcome.
When looking for a high rate of unit utilisation
in a refinery, the availability and reliability of all
equipment is of utmost importance to prevent
loss of production and negative effects on profitability. So a refiner should either perform proper
maintenance or find a way to deal with any kind
of problem that threatens unit reliability.

Catalyst deactivation
It has been known for many years that acid
gases are present in the petroleum industries in
liquid or gas streams. These gases include hydrogen halides such as HCl, HF, HBr, HI and
mixtures thereof. From an acid gas point of
view, one of the key processes of the petroleum
industry are reforming reactions such as those in
CCR reformer units. In the catalytic reforming
process, sweet heavy naphtha is processed in
contact with a platinium-based catalyst to
produce a high-octane product. Hydrogen is a
byproduct of the catalytic reforming process and
some of this product is recycled to the reaction
section to maintain catalyst stability. This
reforming catalyst is promoted with chloride in

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the presence of water, resulting in the production of hydrogen chloride. Thus, the gas that is
not recycled but sent to downstream catalytic
processes and known as net gas contains hydrogen chloride. As a result, this chloride-containing
gas can deactivate downstream catalysis because
it can poison catalysts and cause undesired
reactions.
Even the presence of a small amount of HCl in
the net hydrogen gas can seriously interfere with
the operation of downstream processes that use
hydrogen. It can also cause corrosion problems
in equipment such as pipes, valves and compressors. In addition, the formation of polymerised
long-chain hydrocarbons, generally called green
oils, is a common problem in CCR reformer
units.
Green oils are actually the end products of
undesirable polymerisation reactions taking place
over the catalyst surface area, in which the reaction of HCl with hydrocarbons leads to
chlorinated hydrocarbons. The presence of HCl
will promote olefin polymerisation reactions with
green oil downstream of the reaction section.
These reactions are mainly chemical combinations of relatively small molecules with huge
chain-like or network-structured molecules.
Polymerised molecules formed in this fashion
have complex multi-chain chemistries and high
boiling points, and are typically waxy in nature.
These molecules are green or red in colour and
contain mainly C6-C18 hydrocarbons, with a potential tail above C40, and are believed to be
oligomers of light olefinic hydrocarbons, with
some aromatic nuclei included in the structures.
HCl in gas or liquid hydrocarbon streams must be

PTQ Q3 2013 1

Regenerator

Reactors and
heaters

Booster
compressor
Separator

H2-rich
gas

Recontacting
drum
Chilling
system

Feed

Recycle
compressor

Unstabilised
reformate

Figure 1 Flow scheme for Tpras Kirikkale refinerys CCR reformer unit

removed, since it may cause undesired catalytic

reactions and poison the catalyst systems of the
downstream units. Moreover, HCl is considered a
hazardous material, so the release of this
substance to the environment must be avoided.

Chlorine source
For the time being, the exact mechanism of
green oil formation is unknown, but it is believed
that it is formed by the catalytic reaction of HCl
with hydrocarbons, which leads to chlorinated
hydrocarbons. Classically, a chlorination agent is
injected during catalyst regeneration in the
oxychlorination part of the regenerator to restore
the optimal metallic phase dispersion of the
platinum-based catalyst and to restore a normal
chlorine content of 0.9-1.1 wt% on the catalyst.
This leads typically to a recycle gas chlorine
content of 1 ppmwt with a water content of less
than 30 ppm. The HCl content of the recycle gas
is kept under control, but hydrogen gas from the

2 PTQ Q3 2013

reduction section is also a chlorine source and

both streams enter the net gas booster compressor section. The main chlorine contributor in the
net gas comes from the reduction gas, which
leads to exacerbated issues of green oil
formation.
Tpras Kirikkale refinerys CCR reformer unit
is licensed by Axens and was put into operation
in 2008. The basic flow scheme is shown in
Figure 1. Shortly after unit startup, the CCR
reformers H2-rich gas compressor was encountering frequent emergency shutdowns. These
shutdowns were initiated by serious vibrations
threatening the operation and reliability of the
compressor. When it was dismantled for investigation, some deposits were found (see Figures
2a-e).
The findings of this investigation included:
Dark green oil was adhering to the bottom of
the first suction snubber
Liquid oil was found in the third-stage cylinder,

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Figure 2a First-stage No.1 suction snubber

Figure 2b First-stage No.2 suction snubber

and the valve plate was covered with coked

hydrocarbon. Part of the valve ring was damaged
When draining the suction line of the third
stage, a small amount of green and yellow oil
was found. This oil was very sticky and gum-like.
For analysis purposes, the sticky oil samples
were sent to an accredited laboratory.
Inductively coupled analysis (ICP) was carried
out because there was not enough sample available for X-ray fluorescence (XRF) analysis. The
dominant metal in the fouling material is iron at
8 wt% content. This suggests that the residue of
the particulate analysis is mainly iron oxides.
The iron can be present in the sample as metal
particles or as Fe2O3. During analysis, metallic
iron is oxidised so a distinction cannot be made.
The laboratory reported that the sample from
the CCR reformer compressor contains 73 wt %
C and 10 wt % H. No sulphur or nitrogen is

detected. Next to that, several metals were

detected, with iron being the most dominant at
8 wt%. The molar H/C ratio is 1.64, indicating
very likely an olefin structure together with an
aromatic nucleus. There are no signs of oxygen
present in the sample. Approximately 8 wt% of
the elemental contents cannot be explained, but
based on the process this is possibly organically
bonded chloride. However, this needs to be
confirmed with a different analysis, because the
current results are not conclusive. Further structural detailed information can be obtained by
means of GC-MS.
The same kind of liquid was found in a Korean
refinery complex designed by Axens, and the
problem was solved by the installation of a chloride adsorber at the outlet line of the reduction
chamber.
Discussions with Axens about this specific
issue were initiated and the H2-rich gas compressor was dismantled to discover the extent of the

Figure 2c Third-stage discharge valve cover

Figure 2d Third-stage discharge valve

Laboratory analysis

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PTQ Q3 2013 3

Figure 2e Rod packing carbon seal rings

deposit. Finally, an adsorber drum was recommended, and an action plan has been defined to
implement a chloride guard bed on the hydrogen
gas from the reduction chamber.
It is clear that green oil formation is highly
dependent on the chlorine content of the H2-rich
gas handled by the rich gas compressor. In addition, hydrogen gas used for catalyst reduction is
the main contributor of chloride. Besides good
chloride management, the strategy to tackle this
issue was to remove chloride from this process
stream by means of a specific adsorbent before
the suction section of the compressor.
Axens carried out the design of the hydrogen
chloride guard bed to be implemented at the
outlet line of the reduction chamber. A non-regenerative promoted alumina was selected for
the removal of HCl in the gas phase. A simple
flow sheet for the scheme is shown in Figure 3.
Alumina-based adsorbent is widely used in the
petroleum refining industry as a trapping material for various impurities. Some special
H2 from
reduction

H2 to
reduction

Reduction
chamber

Figure 3 PFD after adsorber drum

4 PTQ Q3 2013

Conclusion
Currently, the H2-rich gas compressors are
running smoothly without any problem. The
compressors were recently opened by the
mechanical maintenance group and no green oil
formation was found, although they ran for
almost one year without a major interruption,
indicating that the vibration problem was
correctly identified. This case shows that a good
licensor and refinery relationship is essential for
solving problems that require both technological
and operational experience.

Dedicated
chlorine trap

Recycle gas

Reaction
section
Catalyst stream
Process stream

formulations loaded in a fixed-bed vessel enable

the removal of small quantities of chloride in
liquid or gas streams. The adsorbent used for
this process is generally disposed of at the end of
its useful life; in other words, it is not regenerable. As the alumina-based adsorbents pick up
HCl, the sodium or calcium promotor, as well as
aluminium, reacts with HCl to form chloride
salts. Green oil may also be formed in adsorption beds, and when these green oils are formed
in fixed-bed adsorbents they cause fouling and
result in the premature failure of the sorbent,
which can be understood by a delta P increase
through the bed.
Drger tube chloride analyses are a simple way
to check on a weekly basis the adsorbents
performance and to check if there is any Cl
breakthrough to determine adsorbent replacement time, reported to be typically more than
one year.
This new arrangement to mitigate the problem
was put on stream in January 2012. Weekly
Drger tube measurements are taken at the
outlet stream of this adsorber and the results are
0 ppm HCl, whereas inlet concentration averages 30 ppm HCl.

To booster
compressor

Separator
drum

Osman
Kubilay
Karan
is
the
Hydroprocessing
Units
Process
Superintendent with Tpras Kirikkale
refinery. His 25 years of refinery experience
includes the operational and process sides
of crude, vacuum units, hydrocracker,
hydrogen production plants, CCR and
DHP units. He holds a degree in chemical
engineering from Middle East Technical
University, Turkey, and is a certified Energy
Supervisor for industrial plants.
Email: osman.karan@tupras.com.tr

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Mehmet Asim Ay is CCR/NHT/ISOM Units Process Superintendent

with Tpras Kirikkale refinery. He holds a degree in chemical
engineering from Middle East Technical University, Turkey.
Email: MehmetAsim.Ay@tupras.com.tr
Koray Kahraman is CCR/NHT/ISOM Units Process Chief Engineer
with Tpras Kirikkale refinery. His six years of refinery experience
includes the process side of hydrocracker and hydrogen
production plants, sulphur recovery, NHT, ISOM, CCR and DHP
units. He holds a degree in chemical engineering from Middle
East Technical University, Turkey.
Email: koray.kahraman@tupras.com.tr
Arnaud Selmen is Axens Technology Manager for Naphtha
Hydrotreatment and Reforming Technologies. He has worked
mainly with bottom-of the-barrel technologies, specialising
in heavy crude oil upgrading. He has also been involved in
the process design of aromatics complexes and NHT, as well

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as reforming units startup and troubleshooting. He holds an

engineering degree from the ENSGTI engineering school and a
DEA in refinery process modelling from IFP School.
Email: Arnaud.SELMEN@axens.net

LINKS
More articles from: Axens
More articles from the following categories:
Corrosion/Fouling Control
Rotating Equipment

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