Chemical cleaning and fouling
removal technologies
Chemical cleaning technologies for the removal of hazardous gases and problematic
fouling deposits are explained
Berthold Otzisk and Luis Del Castillo
Kurita
A
refinery or petrochemical plant shutdown can last
several weeks if storage tanks, vessels, distillation
equipment, and pipework have to be cleaned exten-
sively. The reduction of cleaning and shutdown times helps
minimise cleaning and maintenance costs. The safety of
the employees who have to enter the columns, vessels, and
tanks is always the top priority. Under no circumstances
should they come into contact with hazardous gases or
other dangerous substances. The use of chemical clean-
ing programmes is part of very well-developed safety
concepts. Chemical cleaning and degassing concepts have
proven very successful in recent years.
Cleaning and decontamination
A shutdown is a very labour-intensive time and requires
perfect organisation and scheduling. Often hundreds
of workers are on site for mechanical cleaning, repair, or
replacement of equipment, where every delay means high
production losses. Persons in charge try to minimise expo-
sure of workers to any situations where health risks or
pyrophorically induced fires could be initiated. The forma-
tion of iron sulphide (FeS) is very common in oil refineries
and ethylene production plants.
Iron sulphide deposits accumulate in distillation col-
umns, pipes, trays, structured packings, vessels, and heat
exchangers. During shutdowns, there is a high potential
for spontaneous ignition in the presence of oxygen due
Recirculation method
To flare
Figure 1 Chemical cleaning methods
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to the pyrophoric iron sulphide nature. Keeping such
deposits wet to avoid unwanted fire hazards is not a
good option. Pyrophoric materials must be eliminated and
removed safely.
Meanwhile, very efficient cleaning and degassing pro-
grammes have been established where chemical additives
can be used to clean the equipment quickly in a proper way.
Pyrophoric iron sulphide species are neutralised and elimi-
nated, reducing the risk of unwanted ignition in contact with
the ambient air. Distillation columns and heat exchangers
no longer need to be mechanically cleaned, and packings
can often remain in the columns during shutdowns if they
are clean and no longer contain pyrophoric iron sulphides.
Dangerous emissions, including benzene, H2S, NOx, CO2,
SOx, and VOCs, can be reduced to a minimum. This is becom-
ing increasingly important in today’s world. The high partial
pressure of light hydrocarbons makes it more difficult to
separate them from other volatile gases in the vapour phase.
To trap (scavenge) light hydrocarbons into the wash water,
the gas molecules need to be polarised. This polarisation can
be achieved by electric induction or by using chemical clean-
ing programmes. Downtimes can be shortened, resulting in
higher productivity, reliability, and operability.
Chemical cleaning methods
After distillation columns, vessels, heat exchangers, and
piping have been drained for cleaning, it is common to
Steaming method
To flare
Sewer Steam
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Steam
To scrubber
Oxidiser
Air
Steam
Mixing tank
Figure 2 Oxidiser cleaning circuit
rinse for some minutes with clean water to remove surface
impurities. Afterwards, chemical cleaning can then be car-
ried out. In practice, the recirculation method or the steam-
ing method are well-known technologies for cleaning and
decontamination procedures.
Using the recirculation method on a closed-loop basis,
20-30% aqueous washing solution of the total volume is
usually introduced at distillation columns and circulated
from the top towards the bottom for at least 8 to 12 hours.
Either warm condensate is used as wash water or the wash
water is heated to 60 to 80°C with steam. Between 0.5 and
2.0 wt% of the cleaning additive is completely dosed into
the wash water within 30 minutes, according to the amount
of wash water supplied.
As a rule of thumb, a warm 60-80°C chemical aqueous
dilution with high fluid velocity will give far better results
than a cold cleaning solution with poor agitation. The
chemical cleaning solution should disperse the sludge into
the aqueous diluent, providing maximum hydrocarbon
recovery, minimum solid waste for disposal, and accomplish
the job in the shortest possible time. To achieve excellent
results, good agitation plays a very important role. The
cleaning solution should be pumped at a high velocity so
that dissolved components are well mobilised, preventing
precipitation and fouling.
With the steaming method (see Figure 1), a correspond-
ingly smaller amount of the cleaning additive is continu-
ously fed into the steam over 8 to 14 hours. To avoid thermal
decomposition of active substances, the steam pressure
should be <10 bar. It is recommended to dilute the cleaning
additive with water, which is then dosed via the steam path
and can thus be distributed more quickly on the distillation
trays or packings.
Case study 1: Unifining unit - aromatics plant
A hydrofining unit, part of the aromatics plant, was shut
down for maintenance and inspection. Previously, the plant
had been flushed several times with water and treated for
days with hot steam to remove the aromatic components
such as the carcinogenic benzene as much as possible.
Past success had always been moderate because benzene
could not be removed completely from the oxidiser and,
therefore, the vessel could only be entered with increased
high safety efforts and an autonomous air respirator.
Previously, plant management decided not to take such
a risk and did not enter the oxidiser. Now the aim of the
chemical cleaning and decontamination was the removal of
sludge residues, complete removal of pyrophoric iron sul-
phide, and elimination of hazardous gases such as H2S and
benzene. If possible, no autonomous air respirator equip-
ment should be required.
For this purpose, the oxidiser was emptied according to
schedule, rinsed with water, and steam applied to remove
part of the benzene. After a mixing tank had been con-
nected to the points preceding it using flexible pipes, about
30 m3 of water was pumped in via the mixing tank to fill the
system and heated to 95°C with MP steam. After reaching
this temperature, 140 kg of Turbodispin D80 was dosed
and the circulation was maintained for seven hours.

Time H₂S NH₃ LEL VOCs CO Temp. (ºC) Additional

(ppm) (ppm) (%) (ppm) (ppm) cleaning solution information

03:00 10 12 2 238 3 78
05:00 14 10 5 320 2 90 Cleaning with
07:00 10 8 6 350 5 92 Turbodispin D80
09:00 12 4 8 380 2 94
12:00 Drainage to sour water tank
14:00 2 0 2 38 2 68
16:00 2 0 5 70 6 85
19:00 3 0 8 76 1 95
21:00 2 0 7 37 1 95 Cleaning with
23:00 0 0 3 22 0 96 Kurita CD-5201
01:00 0 0 0 5 0 95
03:00 0 0 0 8 0 94
05:00 0 0 0 4 0 96
07:00 Drainage to sour water tank

Table 1 Oxidiser analytical results cleaning

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 Time H₂S NH₃ LEL VOCs CO Temp. (ºC) Additional information
(ppm) (ppm) (%) (ppm) (ppm) Cleaning solution

13:00 0 0 0 60 0 26 Preperation of the cleaning solution

with circulation and heating
by means of steam
16:00 0 0 0 48 4 40
17:00 0 0 0 20 9 61 Reaching the recommended
minimum temperature
18:00 0 0 0 10 4 67
19:00 0 0 0 5 0 67
20:00 0 0 0 3 0 66
21:00 0 0 17 4 0 71
22:00 0 0 50 180 60 76
23:00 0 0 0 0 0 70
00:00 0 0 0 1 0 70 Finishing the chemical cleaning

Table 2 Analytical results absorber cleaning

Serving as a dispersant, the additive brought petro-
chemical impurities into a form suitable for blowdown so
that they can be easily removed. Starting at 10:00, some
contaminated cleaning solutions were drained, and the cir-
culation was refilled with 25 m3 of water. After these dirty
cleaning solutions were completely dried up, the system
was flushed with 5 m3 of water to remove the remaining
dissolved sludge. The system was then refilled with 30 m3
of water and brought to a temperature above 90°C.
At 15:45, 400 kg of Kurita CD-5201 was dosed and cir-
culated through all flexible hose routes. At 21:00, another
200 Kg of product was dosed. At 1:00, another 200 kg was
injected, and the cleaning solution was circulated until 6:00.
The cleaning was then completed. The dirty cleaning solu-
tion could be drained at 7:00 to flush the remaining resi-
dues with some water afterwards.
The subsequent control measurements showed no ben-
zene or VOCs were detectable after the last flushing with
water. This was the first time after 30 years of operation
that the oxidiser could be entered directly. No autonomous
air respirator equipment was required.
Case study 2: Merox unit cleaning
Mercaptans are undesirable components, impairing prod-
uct quality. Sulphur compounds are separated in the Merox
process and oxidised with excess air to form alkyl disul-
phide. During a planned shutdown, a Merox plant was
chemically cleaned, with a special scope on cleaning the
extractor column. It is filled with Raschig rings and still
contained high concentrations of VOCs after water wash-
ing or steaming. For chemical cleaning of this process unit,
three independently operating circulation circuits were
set up to clean the metal surfaces and remove pyrophoric
iron sulphide and hazardous gases such as H2S, mercap-
tans, benzene, and VOCs. Overall, total columns and ves-
sel volumes were not large, so small wash circuits were
used. The numbers in brackets describe the total volume
of the columns in each case and, based on one-third of the
total volume, a 2 wt% aqueous Kurita CD-5201 solution
was prepared. Adding medium pressure (MP) steam, the
cleaning circuits were operated in a temperature range of
60-80°C.
Circuit No. 1: Absorber (54 m3)
Circuit No. 2: Pre-washer (35 m3)
Extractor (47 m3)
and filter (28 m3)
Accumulator drum (35 m3)
Circuit No. 3: Oxidiser (7 m3)
All three cleaning cycles were started on the same day,
but since only one column of the cleaning solution was
applied to circuit No. 1 (absorber) and circuit No. 3 (oxi-
diser), these cleanings were completed after about 10
hours of treatment. The benzene and LEL concentrations
were 0% after drainage and flushing with clean water at
the end. VOC concentrations were brought down from
peak values of 140 and 180 ppm, respectively, to values
<1 ppm. H₂S and ammonia gases were not detected during
chemical cleaning due to standard pre-washing and steam-
ing of the systems.
Circuit No. 2 was more complex, with several columns and
pipelines. During the preliminary planning, it was decided
to flush the pre-washer and extractor together with the
cleaning solution over 8-10 hours. In practice, it turned out
that it was not technically possible to keep the level in the
mixing tank stable if both columns were flushed with clean-
ing solution at the same time. After 11 hours – due to the
interruption for exclusive treatment of this column – clean-
ing of the extractor was completed (see Table 2).
The unpolluted solution from the extractor was passed
on to the pre-washer, and this part was also flushed for
several hours. After about eight hours of circulation, the
cleaning solution was then transferred to the sand filter
system. After approximately 10 hours, this section was
also properly cleaned, and the cleaning solution was finally
passed to the accumulator drum and circulated for five
hours. After that, the used unpolluted solution was drained,
and the system was flushed with clean water. In total, due
to the interruption, the cleaning of the entire Merox system

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was carried out over 38 hours, after 36 hours were fore-
seen in the preliminary plans.
For later cleanings, it is recommended to install appropri-
ate manifolds and valves so two separate cleaning circuits
with a pre-washer plus extractor and sand filter system
plus accumulator drum can be operated simultaneously.
Compared to previous treatments, cleaning times have been
significantly reduced, and safe conditions for workers have
been achieved. The refiner was very pleased with the results
obtained. Previously, very strong odours had always been
reported, and it had been fraught with danger to remove
the Raschig rings, which were still dirty and highly contami-
nated. With the achieved work done now, the Raschig rings
were clean, no bad odours were noticeable, and further
treatment by the customer was easy to perform.
Case study 3: Amine unit cleaning
After draining an alkanolamine system, clean water was
recirculated to remove sludge and hydrocarbons. To ensure
that all important equipment parts in the amine plant could
be cleaned and decontaminated, two independently oper-
ating circulation circuits were set using flexible hoses and
mobile mixing tanks. In the first run, the flexible hoses were
installed so a closed circuit could be connected between the
absorber column, flash tank separator, two rich amine heat
exchangers, and the four air-fin coolers up to the filter sys-
tem. From there, the return flow was sent back. For better
contact of the cleaning solution with the vapour phase in the
flash tank separator, two valves were used to recirculate the
cleaning solution into the vessel. Low-pressure steam was
added to maintain 60-80°C of the cleaning solution. Excess
gas was routed to a scrubber to scavenge the volatile gases.
To improve the dissolution of the sludge in the bottom
area of the flash tank separator, three perforated diffusers
with a length of approximately 3-4 metres were inserted
through the open bottom valves via packing gland systems
at the bottom left, middle section, and bottom right. These
quills were connected to the circuit and ensured a good agi-
tation in the sludge phase. For the chemical cleaning, a 1
wt% chemical cleaning solution, based on about 20% total
volume, was prepared and distributed for 12 hours.
In the second circuit (see Figure 3), the amine regenerator
OVHD
Regenerator accumulator
Steam Reboiler
Steam
Mixing tank
Figure 3 Second cleaning circuit amine unit
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with an overhead system including air-fin coolers and the
overhead accumulator drum were connected via flexible
hoses to a mixing tank. Also, a 1 wt% cleaning solution
with about 20% of the total volume was distributed by two
pumps for 12 hours in the defined temperature range. The
overhead accumulator drum was also equipped with three
diffuser quills in the bottom area so the sludge could be
loosened and better transported away.
First, according to the usual cleaning procedures, the liq-
uids in the absorber, regenerator, and flash tank separa-
tor were drained, and clean water was circulated in both
installed circuits. To help dissolve the fouling deposits in
the columns and vessel, Turbodispin D80 was dosed into
the water and circulated for 10 hours. Subsequently, the
very contaminated cleaning solution was drained, and both
circulation systems were refilled with clean water. The flash
tank separator was filled to 20%, and the absorber, regen-
erator, and heat exchangers were filled with 30% wash
water, based on the total volume. Then the appropriate
amount of Kurita CD-5201 was added to use a 2% clean-
ing solution. Both circuits were rinsed for 18 hours. After
cleaning, the very dirty cleaning solutions of both circuits
were sent to the wastewater plant. No pyrophoric iron sul-
phide was detected and, as defined before, no VOCs or LEL
concentrations were analysed.
Conclusion
Chemical cleaning has now been proven in practice at many
refineries and petrochemical plants. Ensuring safe working
conditions is a very important factor that must be considered
during shutdown planning. Cleaning metal surfaces, remov-
ing pyrophoric iron sulphide, and eliminating H₂S, benzene,
and other harmful gases are very important measures. This
can significantly reduce downtime and increase productivity,
which helps to achieve the targets at the end of a fiscal year.
References
1 Otzisk B, Chemical cleaning and degassing refinery equipment, PTQ
Q1 2008.
2 Otzisk B, Urschey M, Chemical cleaning and decontamination of re-
finery and petrochemical distillation equipment, International confer-
ence on heat exchanger fouling and cleaning, June 2015, Ireland.
3 B Otzisk, L Uradnicek, Maximising heat exchanger cleaning, PTQ Q2
2018.
Berthold Otzisk is Senior Product Manager for process chemicals with
Kurita Europe, located in Germany.
Email: berthold.otzisk@kurita-water.com
Luis Del Castillo is Account Manager with Kurita Europe, located in
Spain, focusing on refinery and petrochemical applications.
Email: luis.delcastillo@kurita-water.com
LINKS
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Corrosion and Fouling Control
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