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Boilers and Steam Lines Chemical Cleaning

Article  in  International Journal of Engineering and Technical Research · March 2020

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Published by : International Journal of Engineering Research & Technology (IJERT)
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Vol. 9 Issue 03, March-2020

Boilers and Steam Lines Chemical Cleaning

Prem Baboo
DGM (Production & Process)

Abstract:- The aim of Chemical Cleaning is to is to safely (a) Steam pressure -46 kg/cm2
remove all deposits from the inside of the boiler tubes. mill (b) Steam production capacity each Boiler 200
scale, oil, paint, preservatives, rust, welding slag’s that would MT/Hr
have entered during the assembly of new tubes. Steam piping (c) Temperature of super-heated steam produced -
must be cleaned by chemicals when either the product can react
with oil left inside of the piping or in case it can lead to adverse
3850C
effect to leave even very small parts of debris inside the piping. 2. Ammonia Plant (Two streams) integrated process
Proper neutralizing and flushing of these systems after the heat recovery unit comprising of:
chemical attack are of utmost importance. After carrying out (a) Reformed gas boilers. Shell & tube
the process, the internal surfaces of the tubes are passivated by construction with water on shell side
means of protective layer to prevent further rusting and (b) Process gas boiler downstream shift converter
corrosion. Proper chemical cleaning removes deposits from the –Shell & tube construction with water on shell
inside of boiler tubes which improves the boiler heat rate, side
reduces tube failures and improves the stability of boiler (c) Process gas boiler downstream ammonia
chemistry. In Dangote Fertilizer Plant all Boilers are High
Pressure boilers. In higher-pressure boilers, the major deposit
synthesis converter, Shell & tube construction
removed is magnetite and some copper. The internal surfaces with water on shell side.
of a boiler in contact with water and steam must be kept clean All three boilers of each Ammonia plant stream are
and free of deposits to assure efficient heat transfer in the integrate with risers and down comers with single steam
generation of steam. This article discusses when and how to drum. The operating parameters for the process boiler
chemically clean a boiler. Several methods can be used to packages are as below:
determine the need to chemically clean a boiler. The high heat Operating pressure -120.5 kg/cm2, Total combined steam
flux boiler tube surfaces mainly consist of magnetite and generation with all 3 process boilers 559 MT/Hr, Steam
copper. The article outlines cost effective cleansing solvents for temperature outlet (steam drum) -324 0C.
chemically cleaning boilers with magnetite deposits and
copper. The chemical cleaning must be thoroughly planned.
Criterion for determining the success of a chemical procedure 3. Very High pressure (KS) and High pressure (HS)
and the effectiveness of the solvent in dissolving the deposit is steam network of the fertiliser complex is having
covered in detail. steam networks at two operating levels. Very High
pressure (KS) steam operating at 113 kg/cm2 and
Keywords-Boiler, Steam lines, Chemical cleaning, Ammonia, 5150C. This network is running in between the
Alkali, acid, effluents. ammonia process boilers to the inlet of the steam
turbines through a convective super heater coils.
INTRODUCTION The chemical scoping shall include the full length
Dangote Fertilizer Project consists in the realization of an of the saturated steam header, convective super
Ammonia and Urea complex natural gas based plants with heater coils including manifolds and up to inlet of
associated facilities. The Project under progress at LEKKI the steam turbines.
Free Zone in Ibeiju-Lekki Local Government Area of Lagos 4. High pressure (HS) steam network operating at 46
State, Nigeria. Ammonia and Urea complex includes: The kg/cm2 and 3850C.This runs from the auxiliary
normal flow rate of natural gas is 208695 Nm 3/hr. 2X2200 boilers runs up to 3 No’s steam turbines generators
MTPD Ammonia Trains based on HTAS technology (and and also in ammonia plant.
BASF technology for CO2 capture in Ammonia 5.
Plants).2X3850 MTPD Melt Urea Trains based on Saipem BRIEF DESCRIPTION OF THE PLANTS
Technology.2X3850 MTPD Urea Granulation Trains based In ammonia Plant ammonia is produced from synthesis gas
on Udhe Fertilizer technology. Associated Utility Units. containing hydrogen and nitrogen in the ratio of
Commissioning activities under progress in which Boiler approximately 3:1. Besides these components, the synthesis
chemical cleaning successfully completed. Three numbers gas also contains inert gases such as argon and methane to a
of auxiliary boilers and six numbers of waste heat boilers in limited extent. The source of H2 is demineralized water
ammonia plants train -1 & Train -2. (steam) and the hydrocarbons in the natural gas. The source
The Pre operational chemical cleaning was carried out for the of N2 is the atmospheric air. The source of CO2 is the
steam generation equipment along with steam grids as hydrocarbons in the natural gas feed. Product ammonia and
detailed below: CO2 is sending to urea plant. The main function of the plant
1. 3 No’s gas fired auxiliary boilers with the following is illustrated in the figure-1
operating parameters

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Fig.-1

The hydrocarbon feed is de sulphurized to the ppb level in The main users of KS steam in normal condition are here
the desulphurization section. The de sulphurized reported:
hydrocarbon feed is reformed with steam and air into raw 1. Synthesis Gas/Recirculation Compressor Steam
synthesis gas (process gas). The gas contains mainly Turbines
hydrogen, Nitrogen, Carbon monoxide, Carbon dioxide and 2. Ammonia Compressor Steam Turbines
steam. In the gas purification section, the CO is first 3. CO2 Compressor Steam Turbines.
converted into CO2. Then the CO2 is removed from the The KS header is dedicated and limited to Ammonia Plant.
process gas in the CO2 removal section. The CO and CO2 High Pressure (HS) Steam Turbines (Ammonia Compressor
residues in the gas outlet of the CO2 removal unit are Steam Turbines) and (Synthesis Gas/Recirculation
converted into methane by reaction with H2 (methanation) Compressor Steam Turbines) produce HS steam by
before the synthesis gas is sent to the ammonia synthesis discharging to the HS header: NH3 Compressor Turbines are
loop. The purified synthesis gas is compressed and then back pressure type, exhaust going to the high pressure
routed to the ammonia synthesis loop, where it is converted network, Syngas compressor turbines are condensation type
into ammonia. In order to limit the accumulation of argon and extracting steam to the same HS network. The produced HS
methane in the loop, a purge stream is taken. The liquid Steam delivered to the high pressure steam grid together
ammonia product is depressurised during which the with the steam produced by three 100% Auxiliary Boilers
dissolved gases, let-down gas and inert gas, are flashed off. are available for the other Turbine Users (STG generators;
The complex contains three numbers of auxiliary boilers Process Air Compressor Turbines) and for process steam
includes Boiler Feed Water preparation for Boilers feeding make-up requirements (Urea and Ammonia Plants). HS
and for steam de-superheating, Very High Pressure Steam steam production/consumption depends on the working
(KS), High Pressure Steam (HS) and Low Pressure Steam condition of complex, i.e. running condition of Ammonia /
(LS) generation and distribution plus a dedicated steam sub- Urea Plants and the associated power requirement.
network) inside Urea Plant only, Condensates system, and 1. High Pressure Steam is produced at the
Steam Power Generation System. The system has been following conditions:
conceived considering the maximum reliability and to allow 2. Normal Pressure: 45.5 kg/cm2 (g)
the operation of plant on full range of ambient conditions. 3. Normal Temperature: 385 °C
The steam system network for each plant is independent and 4. Design Pressure: 48/FV kg/cm2 (g)
it can be segregated; two independent very high pressure 5. Design Temperature: 415 °C
steam header are provided (one for each ammonia/urea train) The total power requirement of the complex is produced by
and, similarly, two independent high pressure steam header three Steam Turbine Generators. The capacities of STGs
are provided (one for each ammonia/urea train) with a cover the power requirement of Ammonia Unit, Urea Unit
possibility of interconnecting. and Granulation Unit plus Utility facilities. Each Steam
Very High Pressure (KS) Steam KS steam is produced in the Turbine Generator produce approximately 41 MW (rated
Waste Heat Boilers (Ammonia Process) at the following point) at 11 KV (island Mode); STGs use HS steam as
conditions: motive fluid and work at the following operating conditions:
Normal Pressure: 112 kg/cm2 (g) 1. Normal Inlet pressure = 44 kg/cm2 (g);
Normal Temperature: 515 °C 2. Normal Extraction pressure = 4.0 kg/cm 2
Design Pressure: 128 kg/cm2 (g) (g);
Design Temperature: 530 °C

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3. Maximum Exhaust pressure = 0.2 kg/cm 2 other substances which might impede the normal unit
(a). operation or damage the equipment (valves, pumps,
compressors, turbines, etc.), The layers of corrosion product
WHY REQUIRED CHEMICAL CLEANING? are made on pure iron as shown in the figure- 2, that layers
Lines and equipment cleaning is intended to eliminate welds must be removed by chemicals cleaning.
rods and slags, abrasive dusts, oxides grease and in general

Fig -2

CHEMICAL CLEANING OF BOILERS

Preparation of Temporary Circuit. Gauges: Temperature, Pressure, level, Necessary Pipes for
The cleaning carried out by circulating the specified fabrication of temporary circuit, Necessary valves, flanges,
chemical solutions in the specified sequence and conditions. bends and gaskets, Tool & Tackles, all required Personnel
Temporary piping, pumps and suitable capacity, fittings, Protective Equipment’s, Hoses, Bolts, nuts and gaskets, Air
flanges, tanks, gaskets, heating arrangement, valves, test compressor, Electricity or diesel generator, Diesel fuel,
coupons, spares, laboratory facilities with all accessories Consumables, Scaffolding where required, Waste water
required for conducting tests during cleaning operation, tanks, HDPE sheets for waste water tanks.
chemicals and safety accessories for operation, personnel Provision was made to establish a circulation path through
etc., made available at site prior to cleaning operation. the steam generating section. Integrated chemical cleaning
Quantity of chemicals required calculated based on the hold- for high pressure and medium pressure headers considering
up volume of the temporary circuit. one as the feed header and the latte as return header within
ammonia plant having a separate cleaning loop for the
Material and Method. medium pressure header from auxiliary boilers to steam
All Chemicals used for chemical cleaning was inspected on generators and yard piping. Hook up temporary piping to
receipt. Method for transportation of materials, storage, these connection points. An external circulation pump
checked as per Material Safety Data sheet. The Batch / Lot required to circulate the chemicals through these steam
No, Expiry Date of Chemicals was verified with Batch generators and steam network in separate circulation paths.
Certificates. Temporary boiler for heating /Heating Provision also made for the necessary atmospheric vent
Tank/mix Tank: Capacity 20 M3 lines, sampling connection with valve which was installed
Circulation Pump: Capacity 200 M3 /hour, Head: 50 m and appropriately tagged (as per figure No.-3) All pressure
Temporary waste water Pond: 2200 M3 parts were carefully inspected for obstructions and the
Potable Analytical Laboratory: pH meter, Conductivity necessary hydrostatic tests were made.
meter, Turbidity meter etc. Balance and test coupons,

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QUANTITY OF CHEMICALS CONSUMED.

Sr. No. Chemicals Quantity
1 Non Ionic wetting Agent 180 kg
2 Inhibitor 270 kg
3 Citric Acid 3600 Kg
4 Ammonia (NH4OH) 2110 Kg
5 Sodium Nitrite 650 Kg
6 Anti-foaming agent 20 Lit
7 Sulphamic acid(NH2SO3H) 750 Kg
8 Caustic Soda Flaks(neutralization) 1750 Kg
9 Lime(Neutralization) 300 Kg
Table-1

RO WATER CONSUMPTION FOR THE ENTIRE PROCESS

Sr. No Description RO water m3
1 Temporary pipe leak Test 70 m3
2 Cold RO water Flushing 360 m3
3 De greasing and citric Acid pickling 120 m3
4 Passivation 60 m3
5 Ammoniated RO water rinse 240 m3
6 Neutralization pit Dilution 90 m3
Total 940 m3
Table-2

Fig. 3

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CHEMICAL CLEANING OF BOILERS. 6. Excellent results after cleaning with citric acid and
The cleaning was done by circulation technique using sodium nitrite passivation.
external pumps in a “SINGLE FILL METHOD”. The
sequence of the cleaning step like Degreasing, inhibited SEQUENCE OF OPERATION
Citric acid cleaning and Passivation is done in one single fill The cleaning of piping was carried out in the
method. following sequence in a Single fill method.as
Each system was done in sequence in separate circulation shown in the figure-4
path. 1. Cold water Flushing with potable water to remove
The advantages in Single fill method when compared to dirt, dust, loose rust and foreign matter.
other multiple fill method is 2. Degreasing with Non-ionic wetting agent.
1. Reduce DM water quantity. 3. Circulating with ammoniated inhibited citric acid.
2. Reduce Waste water volume. 4. Circulating with Sodium Nitrite (NaNO2).
3. Reduce cleaning time. 5. Drain.
4. Safe Operations. 6. Rinse with Ammoniated water.
5. Reduce chemical cost. 7. Drying & Inspection

Fig-4

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Fig.-5

COLD WATER FLUSHING & LEAK TEST connection to endure that there were no leakages to
Closed all drum manhole. Filled the system with the ambient or adjacent systems.
Demineralised water drum Normal working level. 4. Ensure no leaks in temporary system via full walk
1. Once the boiler is filled start open flushing to flush down. Walk down was conducted from bottom to
out temporary bottom Header stubs connecting top to make sure all critical points are inspected and
lines, return line and drain lines (Economiser, water signed.
tubes & bottom header) till the drain water is 5. After the completion of the hydro test, the boiler
visually clear. At completion of flushing close was depressurized and walk down to inspect casing
temporary drain valves. (external and internal side) thoroughly for any
2. Circulate water in the system by temporary leaking tube, sweating tube or weeping tubes.
chemical cleaning pump Temporary system along 6. The flushing of the sections to be cleaned was
with Boiler was hydraulically tested by using executed with the maximum possible flow rate. The
temporary Chemical cleaning pump at head minimum velocity of the flow was 0.5m/s in each
pressure for 30 mins. part of the system and 1 m/s in vertical pipes with
3. The mentioned flushing and leak test was flow going upwards.
performed for all temporary piping and its

Analysis report Cold water Flushing

Date/ Time(Hrs) 14/02/2020 Outlet pH Conductivity(µ/s) outlet Turbidity(outlet)
09.45 7.15 57 61
10.15 7.07 51 47
10.45 6.47 46 29
12.45 6.91 45 18
13.30 6.89 42 10
14.30 6.87 44 7
14.45 6.85 44 3
15.05 6.83 44 1
Table-3

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Fig.-6

DEGREASING: 2. Added 0.15% Non-ionic wetting agent to prepare

Immerse the piping in a caustic bath at a temperature of the surface for Pickling. For degreasing added 4.6
about 70/80°C for a period of at least 30 minutes, depending kg/m3 of tri sodium phosphate and 3.1 kg/m3 of bi-
on the condition of the material, to remove all grease, dirt, sodium phosphate.
oil or paint. Piping and/or solution is agitated to ensure the 3. The circulation was continued for min 4 hours.
flow of solution through the piping. The batch may be a 4. The chemical was dissolved with DM water in the
solution of 6 % wt. of sodium hydroxide in water with main circulation tank. Ensure proper mixing of
detergent. Remove piping from caustic bath and chemicals.
immediately rinse with cold water. For degreasing added 4.6 5. All Operators and workmen was involved in
kg/m3 of tri sodium phosphate and 3.1 kg/m3 of bi-sodium chemical cleaning process was born all PPE, rubber
phosphate. For passivation Fill the boiler with BFW using aprons, Protective Boots, Face shields, and Hand
filling up valve up to normal. Ensure that passivation gloves and to avoid contact with chemical.
chemicals (Hydrazine) is injected in the line between 6. The chemicals were filled solution through the
deaerator and boiler in order to treat also the economizer. external piping on the economiser inlet for each
The suggested concentration is 1.0 litre of hydrazine per section. When the economiser is full, close the
cubic meter BFW. vents.
1. The system was Fill with Demineralised water 7. Circulation was established with the external pump
drum Normal working level. Heated up the from the inlet connection on the Economiser and
circulating water by temporary auxiliary boiler or the connections on the manifold drains. The water
Heating system to approximately 65 oC - 70 oC. level in the drum was kept from going out of sight
Insert to chemical circulation tank the desired in the gauge glasses. The readings tabulated as per
chemicals. table No. 4

De- Greasing Analysis Report

Date/Time Outlet pH Total Oil & grease ppm Temperature(0C)
alkalinity(ppm) as
CaCO3
inlet outlet

04/02/2020
22.00 8.41 37.5 9.6 75 70
23.00 8.36 42.5 76 72
05/02/2020
00.00 8.31 45 22.4 76 73
01.00 8.36 47.5 74 71
02.00 8.40 47.5 30.2 73 70
03.00 8.37 47.5 75 72
04.00 8.6 47.5 30.4 74 71
Table-4

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INHIBITTED CITRIC ACID PICKLING drained into neutralization pit and the effluent well
For inhibited citric acid pickling the R.O water heated by neutralized by caustic flaks up to pH about 7.06. during the
electric heater up to 72-750C in the tank and then inhibitor process pH and temperature were recorded as shown in the
added about 270 kg, Citric acid also added to control the table No-5
solution pH. Following chemicals were added. First the citric 1. Inhibitor-270 kg.
acid pickling was carried out up to 6 hrs with closed 2. Citric acid -3600 kg.
circulation. After that the system was partially (30-40%) 3. Ammonia -70 kg.
Date & time pH Outlet Citric Acid Fe3(ppm) Fe2(ppm) Total Iron Temperature(0C)
outlet(%) (ppm)
In Out

5/02/2020
06.30 3.2 3.1 84 783 867 78 75
07.30 3.64 3.43 118 2256 2374 77 74
08.30 3.66 3.36 223 2430 2653 76 74
09.30 3.68 3.29 223 2831 3044 75 73
10.30 3.69 3.15 223 3295 3518 74 72
11.00 3.70 3.15 223 3323 3546 73 71
11.30 3.69 3.15 223 3323 3546 73 71
12.00 3.70 3.15 223 3323 3546 73 71
Table-5

ALKALINE CLEANING boiler is refilled close to the top of the glass after each blow.
Alkaline cleaning (flush/boil-out) solutions are basically tri Super heaters and re heaters are protected by backfilling with
sodium phosphate and surfactant. Tri sodium phosphate a properly treated condensate. Each chemical cleaning stage
concentrations typically range from 0.1 to 1%. Disodium lasts was carried out for approximately 6 to 24 hr. When
phosphate and/or sodium hydroxide may be added. Sodium alkaline cleaning was completed, the unit is slowly cooled,
nitrate is often added when caustic is used, as a precaution the alkaline solution was drained to the disposal area and
against caustic embrittlement. Sodium sulphite is neutralized by acid effluent which was collected in acid
occasionally used to prevent oxygen corrosion. Although cleaning steps and the unit was flushed with good-quality
mill scale removal is not one of the purposes of alkaline condensate. Flushing, with intermediate blowdown, was
cleaning, the addition of chelating agents may remove continued until flush water conductivity is less than 50 mhos
enough mill scale to eliminate the need for further chemical and phosphate is less than 1 ppm. Alkaline cleaning was
cleaning. However, where mill scale removal is specifically repeated if organic or residual oil-based contaminants are
desired, acid or chelant cleaning should follow alkaline found upon inspection of the unit.
cleaning. Commercial alkaline cleaning products may
include chelants and other compounds specifically AMMONIA AND RO WATER RINSE
formulated to provide effective cleaning. Alkaline cleaning System was filled with RO water and added ammonia about
should follow procedures that boiler manufacturers furnish 20 kg, and flushing started again added 20 kg ammonia and
for their specific boilers. During cleaning, boilers are fired system was continued. This flushing was carried out in open
at a low rate, but not enough to establish positive circulation. and spent collected and neutralized with caustic flaks.
Boil-out pressure is usually about half the operating During the process the pH were tested and tabulated in table
pressure. Several times during the alkaline boil-out, half of no.- 6 after that the system was fully drained spent
the boiler water was blown down. Alternate valves was used ammoniated RO water solution was neutralized with
where there is more than one blowdown connection. The Sulphamic acid.

PASSIVATION
Date & Time pH Temperature(0C)
In Out In Out
05/02/2020
17.30 9.86 9.84 58 55
18.30 9.84 9.85 59 56
19.30 9.76 9.79 58 55
20.30 9.7 9.72 57 55
21.30 9.71 9.67 59 56
22.30 9.65 9.61 58 56
23.30 9.58 9.59 59 55
06/02/2020
00.30 9.55 9.56 57 54
Table-6

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NEUTRALIZATION OF SPENT CITRIC ACID & PASSIVATION SOLUTION

Date & time (Hrs) pH neutralization pit Remarks
05/02/2020
12.50 Caustic soda flaks-1000 kg added in the neutralization pit
16.30 5.52
Caustic soda flaks-750 kg added in the neutralization pit
22.00 8.45
06/02/2020
03.00 Sulphamic Acid-400kg added in the neutralization pit
10.15 8.07
15.00 Sulphamic Acid-350 kg added in the neutralization pit
17.30 7.52
07/02/2020
09.30 Lime added -300 kg added in neutralization pit
11.45 8.35
Table-7

Fig-7
PASSIVATION Complete chemical cleaning of your system to ensure piping
To minimize deterioration of the active surfaces produced is ready for operation Complete hydraulic testing of lines,
by acid cleaning, a final passivation stage is an essential part ensure all system parts, components and plates are properly
of the overall cleaning process. Passivation is the process of set up for steam blowing.
treating the metal with acids in order to remove the free iron
from the surface of the metal and coat it with this corrosion- CONCLUSION
preventing oxide layer. This passive layer gets damaged The chemical cleaning of boilers has proved to be rapid and
through heat or chemical cleaning damage due to high efficient method of removing deposits from the water side of
humidity levels. After the steel surfaces have been the boiler. In many boilers this is the only method available
chemically cleaned, they are very ‘active’ and subject to today to clean some areas of the equipment. From a
rapid rusting. It is, therefore, necessary to passivate the corrosion viewpoint, this method can be made a satisfactory
cleaned metal surfaces to prevent their deterioration. procedure when all the factors involved are properly
Operation immediately after passivation is the best means of understood and controlled; however, caution should be the
establishing the protective oxide film. Before steam blowing password at all times. Steam blowing comes with hazards,

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such as high thermal stress on your boiler. We take great care

to use the minimum necessary pressure, closely monitor
every detail and ensure a safe process. we take safety, health
and the environment seriously. After chemical cleaning of
the system "Steam blows" are required on large
industrial/utility boilers prior to commissioning. conducting
and completing "steam blows" The basic concept of a steam
blow is to subject the boiler system to a flow with a "mass-
momentum" higher than that it will ever see during normal
operation. Cleaning is accomplished by a combination of
steps. For some boilers it may not be necessary to use all the
cleaning steps, since the degree of contamination will vary
from one boiler to another.

REFERENCES
[1] Paper Mill Boiler Chemical Cleaning – Why, When and How,
Published September 25, 2016, Valmet
[2] Investigation of Chemical Cleaning of Supercritical Super
Heater Oxide Scale, by Hongfeng Li1, Qingtang Xue1, Xinhui
Nie1, and Yunfei Xu2, MATEC Web of Conferences 238,
02011 (2018)
[3] The Operational and Safety Aspects of Chemical Cleaning of
Thermal Power Plants, Springer India 2016 P. Chanda and S.
Mukhopaddhyay, Operation and Maintenance of Thermal
Power Stations, Energy Systems in Electrical Engineering.
[4] Chemical Cleaning of an Industrial Boiler - An Overview by Mo
D. Majnouni, Aramco Service Company, and Arif E. Jaffer,
Baker Petrolite Corporation, the analyst, the voice of the water
treatment industries fall-2004, Volume-xi, Number-4

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