LIBYAN IRON AND STEEL COMPANY

POWER BOILER UNIT 1

CHEMICAL CLEANING PROCEDURE

DETAILED OPERATIONAL PROCEDURE

TABLE OF CONTENTS

1. INTRODUCTION

2. OUTLINE CHEMICAL CLEANING PROCEDURE

3. APPENDIX A- SAFETY RULES

4. APPENDIX B – ANALYTICAL METHODS

4.1 ON LINE INHIBITOR TEST

4.2 SULFAMIC ACID

4.3 DISSOLVED IRON

4.4 CITRIC ACID

4.5 Ph MEASUREMENT

4.6 INHIBITOR CORROSION TEST

4.7 COPPER

5. APPENDIX C- OPERATIONAL LOG

1
INTRODUCTION

A chemical cleaning treatment is performed on the boiler water circuits to remove from the
internal surfaces’ impurities such as water hardness scale and treatments, excessive iron oxide
formation, silica compounds, copper-based compounds and other debris, and to establish a
satisfactory magnetite layer.

Such a procedure ensures that optimum boiler water and steam conditions are achieved and
reducing corrosion on heat exchange surfaces.

The method of cleaning on this project is by chemical cleaning and passivation of the
economizer and boiler steam generating sections.

The superheater is excluded from the acid cleaning process and will be protected from chemical
ingress during cleaning by water wedging/plugging.

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OUTLINE CHEMICAL CLEANING PROCEDURE

Item Operation

1 Stage 1 –Preliminary Checks

1.1 Check all chemicals and other materials are present in sufficient quantity and
quality to perform the clean. A sample of the Inhibitor (Aquacure IC 600) to
be retained for corrosion test analysis if required.
1.2 Sample Coupons to be installed into the cleaning circuit at agreed location if
required. (not usually done on in service cleans.)
1.3 Complete erection of temporary cleaning pumps and pipework. Test run pumps.
1.4 Connect up other utilities (demineralized water, compressedair & nitrogen.)
1.5 Fill temporary pipework only with demineralized water. Apply hydraulic pressure
test to the temporary lines to 1 ½ times the system static head. (ca 4,5 bar). Repair
leaks as necessary. Test steam, water, air and nitrogen lines for integrity, and
repair leaks as required.
2 Stage 2- Initial Filling
2.1 Fill boiler with demineralized water to normal working level via economizer
with makeup water pumps. Commence filling superheater with demineralized
water using make up water pumps.
2.2 When at normal working level stop filling, continue back flushing
superheaters until a rise in drum level is observed.
2.3 Fill and prove all temporary and permanent pipework to the system static head (ca
bar). Repair leaks as necessary.
2.4 Establish circulation of economizer and boiler by temporary chemical cleaning
pumps.
2.5 Drain all system.

3 Stage 3 – Iron Oxide Removal

3.1 Fill the boiler via Economiser with make-up water pump and feed water pump of
boiler unit 2. Then stop pumps. Circulate water until water temperature is
measured 72 ⁰C at circulation tank.
3.2 Backflush superheater until a rise in drum level is observed then lower drum
level to accommodate addition of chemicals as required.
3.3 Check the temperature of system has stabilized between 68 and 73⁰C, then inject
chemicals to give concentrations of:

5-6% Sulfamic acid (12000 - 14000 kg)

0,2% Aquacure IC 600 (200kg)
3.4 Backflush superheater until rise in drum level is observed, then continue as
necessary to raise the level in the drum to required cleaning level.
(Approximately up to half drum).
3.5 After two hours add Ammonium Bifluoride (500kg) to give a 0.5% solution.
3.6 Circulate the solution until the dissolved iron concentration stabilises, or to give a
minimum overall contact time of six hours.
If the iron level exceeds 10000 ppm a second iron removal should be
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 considered. If the iron level exceeds 15000 ppm the boiler should be drained
and a second iron removal stage done.
3.7 Stop circulation and drain boiler and economizer to the chemical water pit.
3.8 Neutralize and treat effluent in the pit until acceptable for discharge, then pump to
Effluent point at waste water treatment plant.

4 Stage 4 – Citric Acid Rinse

4.1 Commence filling boiler with demineralized water via economizer and via
superheater with make-up water pumps to open drains for approximately
10 minutes then close drains and fill to NWL.
4.2 Establish circulation of boiler and Economiser and inject chemicals to give:

0.2% Citric Acid (200 kg anhydrous)

Ammonia to pH 3.5-4.0 (approx. 200-250 liters)
4.3 Circulate solution for approximately 1 hour, then stop circulating pumps.
4.4 Drain boiler and Economiser to the chemical waste water pit.
4.5 Neutralize and treat effluent in the pit until acceptable for discharge, then pump
to effluent point at waste water treatment plant.

5 Stage 5 – Flush with Demin Water

5.1 Fill boiler with demineralized water via Economiser to open drains for 10 min.
( or until effluent condition is satisfactory), then close drains and fill to NWL.
5.2 Circulate boiler section only then stop circulation and drain boiler section only to
waste. (leaving economizer)
5.3 Refill boiler with demineralized water to NWL via economizer.
5.4 Circulate boiler section only for 10-15 minutes and check that conductivity of
water is satisfactory. (less than 100µS cm-1)
If water condition is unsatisfactory at this point, drain boiler section, refill,
circulate and check until a satisfactory conductivity is achieved, leave boiler full
and circulating.
If there is a lot of insoluble debris in the boiler it may be necessary to manually
clean the drums.
5.5 Neutralise and treat effluent in the pit until acceptable for discharge, then pump to
effluent point at waste water treatment plant.
6 Stage 6- Copper Removal/ Passivation
6.1 Fill the boiler via economizer with make-up water pump and feed water pump of
boiler unit 2 and circulate water and down temperature of circulating system to
55⁰C and as measured temporary chemical cleaning pumps and stop the take
water from feed water pumps of boiler unit 2.
6.2 Backflush superheater until a rise in drum level is observed then lower drum level
to accommodate chemicals as required.
6.3 Check the temperature has stabilized between 50 and 55 ⁰C, then inject chemicals
to give the following:
1.0% w/w Citric acid (1000 kg anhydrous)
Ammonia to pH 3.5-4.0 (approx. 200 liters 25%)

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6.4 Circulate or up to one hour.
6.5 Add further Ammonia solution (approx. 2200 liters 25%) to raise pH to 9.5 to 10.
6.6 Inject chemicals to give the following:
0.5% w/w Sodium Nitrite (500kg)
Circulate for a further 4-6 hours until the dissolved copper concentration is stable.
6.7 Stop pump circulation. Open vents and drain boiler and economizer to effluent
neutralization tank until completely empty.
6.8 Neutralization and treat effluent in the pit until acceptable for discharge, then pump to
effluent point at waste water treatment plant

7 Stage 7- Ammonia Rinse

7.1 Refill boiler with demineralized water to NWL via economizer.
7.2 Add chemicals.
7.3 25-50 liters Ammonia to pH 10.0-10.2
7.4 Circulate boiler for 15 minutes.
7.5 Stop circulation and drain.

8 Stage 8- Inspection
8.1 Disconnect temporary connections from boiler pressure parts, open both steam
drum doors and allow internal parts to ventilate and dry out from heat in the
metal.
8.2 Inspect at steam drum, remove sample coupons (if used), and manually remove
and debris lying in low-flow areas. Inspect at other terminal points as agreed. On
acceptance, release boiler for pressure parts reinstatement.

9.0 SITE ANALYSIS METHODS

9.1 On-line Inhibitor Test

9.2 Sulfamic Acid
9.3 Dissolved Iron
9.4 Citric Acid
9.5 Ph Measurements
9.6 Inhibitor Corrosion Test
9.7 Copper

NOTE: In order to conduct these Site Analysis methods, we need the support from
LISCO Chemical Laboratory with LISCO manpower

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APPENDIX A SAFETY RULES

Storage
All chemical products must be stored and labelled in accordance with the instructions on the
safety sheet.
Chemicals must not be stored together with inflammable material and gas cylinders.
Do not store acids and alkalis together.
Do not store strong acids and organic substances together.
Do not store strongly oxidizing substances together with oxidizable substances.
Eithers and other peroxide-building substances must be stored in the dark and cool, in tightly
sealed containers.
Chemical containers must be stored with closed lids when they are not being used.
Refrigerators and freezers for storage of chemicals must be of such a type that is specially made
for this purpose. Chemicals and similar items must not be stored in refrigerators or freezers that
are intended to store food.
Chemical stores must not have open floor drains. If there is a floor drain, it must be equipped
with protection to prevent leakage. This means for example tight fitting lids, a manual opening
and closing function in the drain or other comparable arrangement.
Equipment for handling and cleaning up spillage must be in readiness and suitable for the
chemicals that are stored. It is suitable to have equipment placed outside the chemical store.
It is important for the fire classification of storage lockers and rooms to match the types and
amounts of chemicals stored therein.
Combustible material must be stored in fireproof cupboards or in separate spaces.
Labelling
Chemicals must normally be stored in their original packaging. If you need smaller amounts
of a chemical, the new packaging must be suitable for the substance. Labelling must be in
accordancewiththeoriginalpackaging.Itmustalwaysbepossibletoknowwhatsubstancethe
packaging contains and what risks there may be.
Handling of chemicals
Always read the safety data sheet and the text on the packaging carefully when you are about
to use a product with which you are not completely familiar with the risks. Contact the
environmental coordinator if you are unsure about handling methods.
Use personal protection equipment (e.g., gloves, face mask) where necessary.
Surplus chemicals and hazardous waste must be dealt with in accordance with the information
in the safety data sheet.
First Aid equipment must be available.
Workplaces must be cleaned regularly. There must not be chemical spills on the floor.

Personal hygiene
Smoking is forbidden in the factory area outside specially assigned smoking areas. If you
smoke, remember to wash your hands before lighting up a cigarette. Otherwise, chemical
substances can be transferred by skin contact or breathed in.
Immediately wash off chemical traces from the skin. Read the safety data sheet or ask your
immediate superior if you are not sure what needs to be done.
Food products must not be stored or eaten in premises where chemicals are handled.
Work clothes must be kept clean. If you have been in contact with chemicals, take a shower
before you go home.

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APPENDIX B ANALYTICAL METHODS

SYSTEM: Site Analysis Method

TOPIC: ON-LINE INHIBITOR TEST
REFERENCE: Inhibit/S/01
METHOD: Qualitative test for Inhibitor efficiency in acid cleaning solutions.

Introduction
Inhibitors are added to acids during chemical cleaning to reduce the rate at which the
acid attacks the metal in the system, normally to negligible levels (say 1-2% of uninhibited
corrosion rate). Normally the only metal normally requiring protection in chemical cleaning is
iron, in the form of carbon steel.
When an acid e.g Hydrochloric Acid, reacts with iron it produces hydrogen gas.
2 HCI+Fe àFE CI₂ + H₂
Thus the production of appreciable amounts of hydrogen indicate that the acid is attacking
the steel in the system.
The inhibitor test consists of the addition of a small ball of clean steel wool to a sample of
the acid solution. If the inhibition is poor then hydrogen will be evolved. The hydrogen
bubbles formed will normally adhere to the surface of the wire or become trapped in the
body of the ball. Since the ball of steel wool has a very large area for its weight, once a few
bubbles have formed it will tend to float to the surface.

Equipment
Steel Wool NOTE: The most suitable grade is 00 (fine). Coarser grades have a lower
surface area to weight ratio and are therefore less sensitive. New steel wool is normally
covered by a protective layer of grease or oil and this must be removed before use. This is
most easily done by washing several times in a volatile solvent. e.g., Acetone or Genklene.
After cleaning the wool is highly susceptible to rust and must be stored in a dry sealed
container with some silica-gel dessicant.

Procedure
Tear off a portion of the clean steel wool and roll into a ball about the size of a small
pea. Drop the ball into a beaker containing 50-100 cm³ of the hot acid solution, ensure the ball
is fully wetted and observe for two minutes. (NOTE: For citric acid solutions, the test
temperature should not be more than 80⁰ C as above this the ball may float even in a fully
inhibited solution.)

Evaluation of Results
In normal conditions if the ball remains submerged then the inhibition is satisfactory.
If it rises to the surface, or refuses to sink, then the inhibition is not satisfactory, the most
frequent causes being-
9.7.1 Poor mixing of inhibitor with the acid solution.
9.7.2 Too high and acid strength due to poor mixing or excessive acid addition
rates.
9.7.3 Wrong inhibitor for the acid being used.
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 9.7.4 Wrong materials being handled, caused normally by using unmarked or
wrongly marked containers.

The preliminary action to be taken if the inhibitor test fails is as follows

Stop acid addition.

Carry out another test on a fresh sample.

Check for causes.
Notes
It should be appreciated that as there are so many variables involved in this test, the
results should not always be treated at face value.
For more accurate estimations chemical analysis for metal or corrosion tests on sample metal
coupons should be undertaken for a particular system. The following points should be noted
in particular.
Citric Acid cleaning solutions sometimes give rise to misleading results, floating and/or
bubbling at1-5minutes after addition of the ball is not necessarily indicative of poor inhibition,
although addition of extra inhibitor to the system should be considered. Quite often at high Iron
concentrations, i.e. >5000 ppm a ‘’Ferric iron corrosion’’. Reaction occurs at the metal surface
which restricts the normal inhibitor bonding thus allowing some acid attack on the surface
giving a rise to hydrogen gas, even in a fully inhibited solution. This phenomenon is normally
quiteindicativeoftheconditionsinthesystembeingcleanedandthereforeshoulditoccur,the acid
solution should be drained as rapidly as possible.
Thetestisonlyindicativeoftheinhibitionofthesteelwoolinthebeaker.Care should be taken that the
solution flow in the cleaning system does not exceed the maximum flow velocity for acid
cleaning of 5 feet (1.5 meters) per second in any area; even a fully inhibited solution will be
very corrosive to carbon steel at velocities above this.
The test temperature is not necessarily that in the whole system. The test would not give
warning of, for instance, break up of inhibition on boiler furnace tubes should be inadvertently
fired during an acid clean.

SYSTEM: Site Analysis Method

TOPIC: DISSOLVED IRON

REFERENCE: Fe/S/01
METHOD: Colorimetric determination of Total Iron in process solutions using
thioglycollic acid.
Theoretical Considerations
Thioglycollic Acid (HS.CH₂COOH) reacts with ferrous ions in alkaline solution to give a
magenta coloration, the intensity of which is directly proportional to the Ferrous Iron
concentrationofthesolution.Thioglycollicacidalsoactsasareducingagent,convertingferric
ions(Fe³⁺)toferrousions(Fe²⁺).Hencethetotalironconcentrationofasolutioncanbefound using
the following method.
Chemical Reagents
Concentrated Ammonia solution (0,880 Analar)
Thioglycollic Acid (Mercaptoacetic) G.P.R
Standard Iron Solution (1000 ppm Fe)
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Apparatus
Spectrophotometer capable of measuring at approx. 550 nm (550x10⁻⁹m) e.g
WPA E1 colorimeter fitted with No. 5 filter at Hi-intensity.
WPA HC 600 with 560 filter or Lovibond Comparator with cells and a 3/6 standard disc.
100 cm³ volumetric flasks
Micromaster or Eppendorf pipettes and disposable tips.
Plastic filter funnel
No. 1 filter papers

Wash bottle for demineralised water

Procedure
If a colorimeter is to be used switch on and allow to warm up for at least 15 minutes.
Filter the sample if necessary to remove suspended solids and allow to cool.
Take 100 microliter of sample (or other quantity-see Notes below) using micromasterpipette
and transfer to 100 cm³ volumetric flask.
Add 20-30 cm³ water, then 2 drops of Thioglycollic Acid and mix.
Addanexcess(approx.0,5cm³)ofAmmoniasolution,makeuptothe100cm³mark with water and
mix thoroughly. The colour should develop almost immediately.
Transfer sufficient quantity of the colour solution to a 1cm. glass cell. Zero the colorimeter to
0(%absorbance)or100(%transmittance)withasimilarcellcontainingdemineralisedwater, then
measure the transmittance T or absorbance A as per the colorimeter instructions.
At the end of sampling session, switch off the colorimeter.
For the Lovibond Comparator add the colour solution to one glass cell to approx 2/3 full and
add demineralized water to the other cell. Place the cells in the instrument with the
coloured cell in the centre. Holding the device up to the light rotate the disc until the nearest
match is made between the two coloured circles. Read off the absorbance A from the
bottom right- hand number hole.

Colorimeter Standardization
For the first in a set of readings it is recommended to standardize the colorimeter as follows:
Conduct the above determination but using a suitable volume (often 200ul) of Standard1000
ppm Fe solution to give a midpoint reading. Read the transmittance Ts or absorbance As.

Calculation

Calculate the Standardization Factor Q by the formula:

2000 2000
Q= ---------- or --------------
(2-logTs) As
From the standardization factor the Iron concentration of the sample may be calculated as:
For 100 ul sample taken
Ppm Iron = (2-logT) x Q
Or ppm Iron = A x Q x 100/V
For the Lovibond Comparator fitted with 3/6 disc the reading corresponds directly to mg. of
iron in the coloured solution. To calculate Iron concentration in the sample.

9
For 100ul sample taken:
ppm Iron = A x100000
For a volume V ul sample taken:
Ppm Iron = A x 100000000/ V

SYSTEM: Site Analysis Method

TOPIC: CITRIC ACID

REFERENCE: CA/S/01
METHOD: Determination of % Citric Acid in process solutions by Cation
Exchange / Volumetric technique.
Theoretical Considerations
Citric Acid (C. OH. COOH. (CH₂COOH)₂) is a complexing acid and finds wide use in chemical
cleaning.Inprocessesitisnecessarytodetermineitsconcentrationinbothacidicandalkaline solutions.
As citric acid is rarely employed on its own, but usually as a salt, e.g. monoammonium citrate (in
acidic processes) and tri ammonium citrate (in alkaline
passivations/copperstripprocesses),thenallcitratesmustbeconvertedbacktothefreeacid
form.Thismaybeachievedbyusingacationexchangeresinwhichhastheeffectofremoving ammonium
ions and replacing them with hydrogen ions, thus giving free citric acid.
Likewise, iron citrates are converted to citric acid by the absorption of the ferrous and ferric
ionsbytheresin.Thereforethetotalcitricacidcanbefoundbystandardtitrationwithsodium
hydroxide using phenolphthalein indicator. If ammonium bifluoride, sodium bromate or
sodium nitrate are present the ion-exchange treatment will result in the formation of HF,
HBrO₃ and HNO₂ respectively, and these acids will contribute to the overall acidity acting
against the NaOH, hence corrections need to be made if necessary.

Chemical Reagents
Cationic exchange resin (in Hydrogen H⁺ form)
e.gZerolit 325, Dowex 50-W-X8(H)
Standard Sodium Hydroxide solution 0.5 molar (0.5N)
Phenolphthalein indicator
Apparatus
250 cm³ & 100 cm³ conical flasks
Reservoir bottle & 10 cm³ auto burette for 0.5M
NaOH. Pipettes 10 & 20cm³ and safety pipette filler
2 x Plastic filter funnel
No. 1 filter papers
25 cm³ plastic measuring cylinder
Glass wool
Wash bottle for demineralized water

Procedure
Filter the sample if necessary, to remove suspended solids and allow to cool.
Add a slurry of resin to the measuring cylinder until, after settling, the resin volume reaches
approximately 10 cm³. Transfer the resin to a clean 100cm³ conical flask, rinsing a few times
10
with demineralized water if necessary. When all the resin has been transferred, decant off
excess water from the resin.
Using a safety pipette filler, pipette 10cm³ (for 2-3% acid cleans) or 20 cm³(for citric rinses
and passivation’s) of the sample on to the resin in the flask. Swirl gently to mix and allow to
stand for 5 minutes, occasionally swirling the flask to thoroughly mix the contents (Flask A.)
Place a small plug of glass wool lightly in the mouth of another clean plastic filter funnel or a
filter paper and place the funnel in a 250 cm³ conical flask(Flask B). Decant the solution from
Flask A through the funnel into Flask B taking care to keep as much resin as possible in Flask
A. Rinse the walls of the funnel with 2-3 cm³ water into Flask B.
Add 10-20 cm³ water to Flask A, swirl briefly and again decant through the plugged funnel as
above info Flask B. Rinse funnel again with 2-3 cm³ water.

Wash the resin twice more as above. If any beads of resin have collected in the funnel , rinse
them thoroughly, allowing the funnel to empty between rinsing’s. Finally place the empty
funnel in Flask A.
Add 3-6 drops phenolphthalein indicator to the solution in Flask B, zero the auto burette and
titrate against the standard sodium hydroxide solution. Allow the solution to just turn pink
andthenstoptitrating.PlacethepluggedfunnelinFlaskB,addafurther10-20cm³waterinto the
resin in Flask A, swirl briefly and again decant through the funnel into Flask B. Continue
titrating dropwise as above until the solution turns pink once more. If three drops or less of
Sodium Hydroxide solution are required the end point has been reached, if not perform
another 10-20 cm³ rinse. Note the final burette reading Vcm³.
Empty Flask B of the solution and rinse out well. Once again rinse the resin in Flask A and
discard the rinse water. Finally discard any resin in the funnel, then place the empty funnelin
Flask B. Drain excess water from the resin. The resin may be used for the next
determination.

Calculation
For a solution containing only citric acid, ammonia and dissolved iron, the cidric acid
concentration is found as follows:
Total Citric Acid (%w/v) = V cm³ x 0,32 (for 10cm³ sample)
Total Citric Acid (%w/v) = V cm³ x 0,16 (for 20cm³ sample)
Free Citric Acid (%w/v) = Total Citric Acid – (3,4 x Iron*)
* See notes below.

Ammonium Bifluoride present

TOPIC: pH MEASUREMENTS
REFERENCE: pH/S/01
METHOD: Determination of pH of Chemical Cleaning solutions.

Theoretical Considerations
The pH of a solution is a measure of its acidity or alkalinity. The pH scale runs from O (very
acidic) to 14 (very alkaline). At pH 7 acidity is equal to alkalinity, i.e. the solution is neutral.
TechnicallypHisdefinedasminusonemultipliedbythelogarithmtobase10oftheHydrogen ion
concentration, i.e.:-

Since it is a logarithm, it is a pure number and therefore has no units.

11
The precise measurement of pH is conveniently carried out electrically and many commercial
electronic pH meters are available. The method used relies on placing two different electrodes
in the solution to be measured and measuring the voltage produced between them. One
electrode is known as a "reference" electrode while the other is a "glass" electrode. The glass
electrode is the one which produces a varying output, depending on the pH of the solution. In
most modern meters the two electrodes are combined in a single unit often referred to as a
"combination pH electrode". This is the type used with the WPA E1 Suitcase Laboratory kit.
Due to ageing effects in the electrode(s) it is essential to set up a pH meter to read correctly by
using solutions whose pH is accurately known. Such solutions are known as buffer solutions.
Once set up, the calibration will last for about 24 hours, but less if the instrument is repeatedly
switched on or off.

Accuracy
When ammonium bifluoride has been added to cleaning solution, there in will convert it to
HF acid which contributes towards the total titration value.
The correction is 2,244 x (%w/w Bifluoride added.) The correction is as % Citric Acid and is
to be subtracted from the Total Citric Acid as calculated above.
For 10 cm³ sample containing 0.5% w/w Ammonium Bifluoride
Total Citric Acid (%w/v) = (V cm³ x 0,32)- 1,122
Notes
The calculation for free citric acid is based on the reaction between iron scale and citric acid
producing Ferrous Hydrogen Citrate (monoammonium Fe II citrate):

CH₂---------COO⁻
HO --------C ------- COO⁻ Fe²⁺
CH₂--------COO⁻ NH₄⁺
This is certainly what is formed with an excess of citric acid. Calculations based on forming
thisproductshowanIronsaturationlevelof8820ppm(0.87%w/w)for3%citricacidsolution.
However,thisisnotthesaturationlimitforcitricacidasfurtherreactioncantakeplaceleading to the tri
ferrous dicitrate salt. This gives a true saturation level of 13000 ppm Fe (1.3% w/w) for a 3%
citric acid solution.
In addition to the above in the presence of oxidizing conditions a corrosive reaction known as
‘’ferric ion corrosion’’ can occur. This is particulary severe in solutions of high Iron
concentrations, say above 6000-7000 ppm (0,6-0,7 % w/w) when it tends to become self-
supporting.
Fe(III) citrate + 0₂ àFe(III) citrate
2(Fe(III) citrate) + Fe à3(Fe(II) citrate)
The first reaction above occurs more easily the higher the pH of the solution becomes. The
overall reaction is unaffected by the presence of inhibitors and in fact as it is a metal surface
reaction it can, in some cases, interfere with normal ‘’surface coating’’ action of the inhibitor
giving the appearance of inhibitor breakdown.
For the above reasons it is not good practice to exceed 7000 ppm Fe during a 3% w/w citric
acid clean, nor to allow the free citric acid level to fall below 0.5% w/w. It is neither good
practicetosupplementthestrengthof‘’dirty’’acidsolutionsbyadditionoffurthercitricacid, as has
been common practice in the past. The solution should be drained and the acid stage
repeated, if agreed with the client.

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SYSTEM: Site Analysis Method

There is a theoretical maximum accuracy for pH measurements of about± 0.01. With an

analogue indicator such as that fitted to the WPA meter, the reading accuracy is only about ±
0.1. This is probably the highest accuracy that could be expected from such an instrument and
a figure of± 0.2 is more realistic. Temperature has a marked effect on the measurement of pH
andwithasimpleapparatusitisimportanttomakemeasurementsonsolutionsatapproximately the
same temperature as the buffer solutions used for calibrations.
CertainpHmetersarefittedwith"Temperaturecompensated"electrodesorhaveaTemperature
adjustmentscale.Forthebestaccuracy,however,itisalwaysbesttouseasettemperature(say 20°C)
for all readings.
Apparatus and reagents
Suitable pH meter and electrode such as WPA Suitcase Laboratory with E1/F pH module and
pH electrode.
100cm3 glass or plastic beakers
Wash bottle for demineralized water
pH Buffer solutions, pH 4, 7 & 10
Thermometer
Procedure
Standardization
(This normally only needs to be done once at the start of an analysis session or if a new pH
range is being measured.)
ConnectpHelectrodetothepHmeter.Switchonandperformbatterycheckifnecessary.Allow to
stabilise for 10 minutes before taking readings.
Select the pH buffer nearest in pH to the sample to be measured and pour approx 50 cm3 in a
clean 100 cm3. Remove the electrode cover, fit protective skirt if necessary, then rinse the
electrode with a jet of demineralized water.
Place electrode gently in the Standard Buffer solution, stir gently and allow the meter reading
tosettleforabout30seconds.UsingtheadjustingknobonthepHmodulesetthemetertoread the
correct pH value on the meter scale. Record also the solution temperature.
Sample Reading
Pour about 50 cm3 of the sample into another clean 100 cm3 beaker and measure the
temperature.Coolifnecessarytogiveatemperatureof±5°Cofthebuffersolutiontemperature. Place
electrode gently in the sample solution, stir gently and allow the meter reading to settle for
about 30 seconds. Read the pH directly on the meter scale. If the reading is more than ± 2 pH
units away from the buffer reading, then it is likely that a better choice of buffer can be made.
Remove the electrode, rinse thoroughly with demineralized water then immerse in a beaker
containing demineralized water.
Care of Electrodes
CombinationpHelectrodesaresensitive,fragileandexpensive.Wheninuse,theglassbulbon the
electrode tip must never be touched and the protective plastic skirt around the tip must always
be fitted. The glass tip must never be allowed to dry out and when not in use the plastic skirt
should be removed and replaced with the rubber cap supplied, filled with demineralized water
or pH 7 buffer solution for storage (take care not to touch the glass bulb with the fingers when
doing this). If necessary clean the tip carefully by wiping gently with a fine paper tissue, then
rinse thoroughly with demineralized water. Store with the bulb facing downwards if possible.

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SYSTEM: Site Analysis Method

TOPIC: INHIBITOR CORROSION TEST

REFERENCE: InhibCorr/S/01
METHOD: Quantitative evaluation of corrosion rate of an Inhibited Acid cleaning
solution.
Introduction
Inhibitors are added to acids during chemical cleaning to reduce the rate at which the acid
attacks the metal in the system, normally to negligible levels (say 1 - 2% of uninhibited
corrosion rate). Normally the only metal normally requiring protection in chemical cleaning is
iron, in the form of carbon steel.
When an acid e.g. Hydrochloric Acid, reacts with iron it produces hydrogen gas:-
2 HCI + Fe ---> Fe Cb + H2
Thus the production of appreciable amounts of hydrogen indicate that the acid is attacking the
steel in the system.
Abriefmethodtocheckforthisreactioninapoorlyinhibitedsolutionisthesimple"wirewool" test
(ref. Method sheet lnhib/S/01). However when a batch of inhibitor is of suspect quality, or its
identity cannot be certain (e.g. missing or defaced labels on containers), then the following
laboratorymethodmaybeusedtoestablishthecorrosionrateoftheacid/inhibitorcombination.
The following method is given for a standard cleaning solution, i.e. Hydro chloric Acid
inhibited with Armohib 28 at 70°C, however it may be adapted for other combinations, e.g.
Citric Acid inhibited with Stannine LTP at 90°C (further details available on request).
Apparatus

Combination Magnetic stirrer/hotplate with thermostatic control*

Thermostatic immersion type contact thermometer (adjustable +20 -+100°C)*
(*iftheabovearenotavailableastandardtemperatureadjustablestirrerhotplatecanbeused,
however the temperature should be checked and adjusted continually to be in the required
range)
Magnetic stirrer follower
Weighing balance (accurate to 4 decimal places, i.e. to 0.0001g, 0.1mg)
800cm³ glass beaker
Retort stand, 2 x bosses & clamps
Eppendorf Micropipette, 100 - 1000µ1 + disposable tips
Stainless steel wire
Wash bottle for demineralized water
Carbon steel standard test coupons
Reagents
Hydrochloric Acid 5% w/w solution
Armohib 28 inhibitor (taken from batch to be tested)
Acetone or Methanol (50ml)
Method
Set up the stirrer/hotplate and stand with the beaker & magnetic follower. Set the contact
thermometer to 70°C and suspend using one of the clamps in the beaker.
Add Hydrochloric Acid to the 500ml mark (or sufficient to fully cover the test coupons)
ensuring the tip of the thermometer is immersed. Commence heating and stirring slowly.
14
Allow the solution temperature to balance at 70°C +/- 5°C. In the meantime prepare a new
corrosion test coupon by degreasing thoroughly with a little acetone or methanol, drying
thoroughly and weighing on the balance, recording the initial weight.
Add 0.2%w/w of the inhibitor to be tested (1000µ1 using the micropipette) and allow to mix
thoroughly.
Suspend the coupon in the stirring solution by means of a piece of stainless steel wire attached
to the retort clamp. Ensure the coupon is fully immersed and does not interfere with the
magnetic stirrer follower. Note the start time.
Continue heating & stirring as above checking the liquid level. Occasionally add water to the
500ml mark to make up for evaporation loss.
After 4 hours exactly, remove the coupon and wash immediately with demineralised water
followedbyacetoneormethanolanddryagain.Reweighimmediately(orwithin5-10minutes) and
note the final weight.
Measure the dimensions of the coupon and calculate its surface area (in m²)

Calculation & Evaluation of Results

The corrosion rate of the acid/inhibitor combination can be found as follows:-
Corrosion rate in gm⁻²h⁻¹ = (Initial weight (g) - Final weight (g))
Surface area (m²) x 4
A satisfactory corrosion rate would be less than 2 gm⁻²h⁻¹, in practice less than 1 gm⁻²h⁻¹
may be achieved.
If the corrosion rate exceeds 2, the inhibitor may not be satisfactory and should not be used
for thechemicalclean.Inthiscasethechemicalsuppliermustalwaysbeinformed.Iftheevaluation is
uncertain, repeat the test on a separate sample of the inhibitor with a new test coupon.

SYSTEM: Site Analysis Method

TOPIC: Copper
REFERENCE: Cu/S/01
METHOD: Colorimetric determination of Copper in process solutions using
Biscyclo hexanone Oxaldi hydrazone Reagent
Theoretical Considerations

BiscyclohexanoneOxaldihydrazone(BCHorBCODH:C₁₄H₂₂N₄O₂)reactswithcopperionsin
ammonical solution to give a blue coloured complex. The intensity (depth) of colour is
proportional to the amount of copper ions in solution(i.e. the copper concentration). High iron
contentinthesamplewillpreventtheformationofthecoppercomplex,henceafluoridebuffer is
added to overcome this.
Chemical Reagents
BiscyclohexanoneOxaldihydrazone. Dissolve 0.25g BCH in 100 cm³ of 50%w/w Ethanol
(Ethyl Alcohol C₂H₅OH) - water solution. Allow to cool.
Buffer solution. Dissolve 50g Citric Acid (A.R. Grade) in 200cm³ distilled water. Solution
(Solution A). Dissolve 25g ammonium fluoride, NH4F (A.R. Grade) in 100cm3 in a plastic
beaker(Solution8).AddsolutionAandBto150cm³0.880Ammonia(A.R.Grade-35%w/w); mix,
cool and dilute to 500cm³ with distilled water.
Caution: Ammonia is Toxic, Fluorides are toxic and corrosive.
Standard Copper Solution (1000 ppm Cu)

15
Apparatus
Spectrophotometer capable of measuring at approx. 595nm (595 x 10⁻⁹₅ m) e.g:-
E1 colorimeter fitted with No. 7 filter at Lo-intensity
100cm³ volumetric flasks
Micromaster or Eppendorf pipettes and disposable tips
Plastic filter funnel
No. 1 filter papers
Wash bottle for demineralised water

Procedure
If a colorimeter is to be used switch on and allow to warm up for at least 15 minutes.
Filter the sample if necessary to remove suspended solids and allow to cool.
Take 100 microlitres (µI) of sample (or other quantity - see Notes below) using micromaster
pipette and transfer to 100cm³ volumetric flask.

Add 20 - 30cm³ water, then 1Ocm³ buffer solution and mix.

Pippette 5cm³ of BCH reagent into the flask, mix and make up to 100cm3 with distilled water.
Allow to stand for 1O minutes exactly before measurement.
Transfer sufficient quantity of the colour solution to a 1 cm. glass cell. Zero the colorimeter to
O (% absorbance) or 100 (% transmittance) with a similar cell containing demineralized
water, then measure the transmittance T or absorbance A as per the colorimeter instructions.
At the end of a sampling session, switch off the colorimeter.

Colorimeter Standardization
For the first in a set of readings it is recommended to standardize the colorimeter as follows:-
Conduct steps to 4.7 above but using 100µ1 of Standard
1000 ppm Copper solution. Read the transmittance Ts or absorbance As.

Calculations
Calculate the Standardization Factor Q by the formula:-

Q = 1000 or 1000
--------- ----------
(2 - log Ts) As

From the standardization factor the Copper concentration of the sample may be calculated as:-
For 100µl sample taken:-ppm
Copper = (2 - log T) x Q or:
ppm Copper = A x Q
For a volume V µI of sample taken:-
ppm Copper = (2 - log T) x Q x 100/V
or: ppm Copper = A x Q x 100/V

Notes
For initial Copper removal stage (500-2000ppm) take 100µl sample
For Second Copper removal stage (20-400ppm) take 500µl-5c

16
 CHEMICAL CLEANING PROCEDURE / Operational Log

Time/Date
Sign of
Stage Activity Comments/ Deviations
Start Finish Initials

1 Preliminary activities and checks

Check all chemicals and other materials are present
1.1 in sufficient quantity and quality to perform the
clean.
Retain a sample of inhibitor (Armohib 28) for
corrosion test analysis if required. For analysis
1.2 method refer to ''Corrosion'' Test analysis of
inhibitor'' in Appendix B ''Analytical Methods''
Complete erection of temporary cleaning pumps
1.3 and pipework according to Schematic Diagram and
test run pumps.
Connect up electrical supplies to pumps, test run
1.4
pumps to check rotation.
Connect up other utlilities (steam, demineralised
1.5
water)
Test steam, water, lines for integrity, repair leaks as
1.6
required.
Ensure that the emergency shower and safety wash
1.7
down hoses have been commissioned.
Ensure that chemical clean working area and the
1.8 chemical storage areas are barriered off and
labelled satisfactorily.

1.9 Ensure that permanent valves have been set up.

Ensure that all temporary valves are clearly and

1.10
correctly labelled.
Ensure all analytical equipment is tested, checked
1.11
and ready for use.
Set up filling temporary pipework only for initial
leak test. Fill temporary pipework only with water
1.12 by slowly opening water supply valve. Repair leaks
as necessary.

Set up apply hydraulic test on temporary pipework

as follows. Start up make up water pumps or
1.13 temporary chemical cleaning pumps commence
water from make up water tanks or mixing tank and
monitoring the pressure at the pressure gauge.

Pressure the temporary pipework to 4.5 5 barg and

maintain at this pressure. Check for and rectify leaks
1.14 necessary.
Stop hydraulic test when satisfied with the integrity
of the system. Shut down temporary Chemical
1.15 cleaning pump or make up water pump and release
pressure.

2 Initial Filling
Set up valves for filling boiler. Fill boiler tonormal
2.1 working level (monitor at steam drum temporary
gaugeglass).

Start up make up water pumps and commence

2.2 backflushingsuperheaters. (Modified line make up
water pump to superheater for chemical cleaning)

When at approx. 1/2 level in the drum, stop filling.

Continue filling and backflushingsuperheaters until
2.3 a rise in drum level (of at least 50mm) is observed
on the gauge glass, then stop superheaterbackflush
pump.

Recheck entire system for leaks at static head. In

particular check terminal point flanges on the boiler
2.4 side of TP valves, also temporary drum door and
nitrogen injection connections. Rectify leaks as
necessary. Record test pressure.

Establish circulation of the economiser and boiler

2.5
system using .

17
 Start up 1x temporary Chemical cleaning pump and
2.6
commence pumping into system.

Inject 20 litres Ammonia solution to mixing tank for

2.7
circulation.
Check for returm of ammonia at boiler return
2.8
sample point and note the ''residence time''.
3 Iron Oxide Removal
Establish circulation of the economiser and boiler
3.1
system using pumps.
Take demineralised water from feed water pumps
3.2
of Unit II boiler and start circulation of boiler.

When the desired temperature is reached, stop

3.3
pumps of feed water.

Back flush the superheater until a rise in drum level

is observed. Open drain valves to lower drum level
to accommodate the chemicals, approximately
3.4 18000 litres required. (reduce to approximately
bottom of steam drum-this may be below bottom of
gauge glass.)

Recheck that all safety equipment and procedures

detailed in appedixA are available and
implemented.Ensure that the emergency shower
3.5 and safety washdown hoses are operational, all
barriers are in place and non-essential personnel
are evacuated from working area.

Check that the temperature of the system has

stabilisedbetween 68⁰-73⁰C. Start up temporary
3.6 chemical cleaning pump and commence pumping
into system.

Commence addition of Armohib 28 inhibitor to

mixing tank and to give approximately 0.2% w/w in
3.7 solution. (approx 200 litres total required). Inject
the first 100 litres into the system over a 20 minute
period.

Fill the Hydrochloric Acid into the mixing tank,

together with the remainder of the Armohib 28
3.8 inhibitor. Approx 180000-21500 kg hydrochloric
Acid 28% solution required.

During the above addition, take samples at and

3.9 check for free acid strength and inhibitor
effectiveness every 20 minutes.

Backflush the superheater until a rise in drum level

is observed, using make up water pump, then
3.10 continue as necessary to raise the level to the
required cleaning level (approximately to the top of
permanent gauge glass, approx 1/2 drum)

Take samples at regular intervals and monitor.

Continue circulation of the boiler and economiser
until the dissolved iron in solution is constant, then
3.11 for a further 2 hours. Measure every 30 minutes for:
Total iron, Free&Total Hydrochloric Acid, Inhibitor
Effettiveness.

After two hours circulation add: 0.5%Ammonium

3.12
Bifluoride.

At end of acid clean period, stop main circulation

3.13
and set up for draining to chemical Waste WaterPit.

Add sufficient Caustic Soda Liquor and mix the tank

3.14
with temporary pumps until neutralised.

18
 4. Citric Acid Rinse

Set up valves for refilling boiler and economiser

4.1
initially to open drains.

Start pumps and commence filling economiser and

4.2 boiler. Commence backflush the superheater with
make up water pump.

Fill boiler to normal working level (1/2 drum). When

4.3
at desired drum level stop make up mater pump.

Establish circulation of the economiser and boiler

4.4
system.

4.5 Start up temporary chemical cleaning pumps.

Inject chemicals to give; 2g/l (0.2% w/w) Citric Acid

4.6 (200 kg anhydrous), Ammonia to achieve pH 3.5-4.0
(approx. 200-250 Litres, check by sampling)

Take samples at regular intervals and monitor .

4.7 Continue circulation depending on analysis for at
least 1 hour, but no more than 2hours.

Stop circulation and set up for draining to Chemical

4.8 Waste Water Pit. Drain boiler and economiser to
Chemical Waste Water Pit.

When boiler is empty, backflush to drains. Continue

until clear and free of bulk chemical contamination
4.9 (Check drain sample) then stop make up water
pumps.

5. Flush with Demineralised Water

Set up valves for refilling boiler and economiser
5.1
initially to open drains.

Start up pumps and commence filling economiser

5.2 and boiler. After 10 minutes flushing, close drain
valves.

Fill boiler to normal working level (1/2 drum). When

5.3
at desired drum level stop.
Establish circulation of the economiser and boiler
5.4
system.
Continue circulation as above for 10-15 minutes
then open drains to drain boiler only to Chemical
5.5
Waste Water Pit. Check and record water
conductivity on draining.

Set up valves for refilling boiler and economiser

5.6
initially to open drains.

Commence filling economiser into boiler. After 10

5.7
minutes flushign, close drain valve.

Fill boiler to normal working level (1/2 Drum). When

5.8
at desired drum level stop make up water pumps.

Continue circulation of the boiler. After 15 minutes,

check and record water conductivity (from a
suitable sampling point on the boiler). If
conductivity is above 100uS/cm, drain boiler section
5.9 only, refill, circulate and recheck conductivity.
(repeat steps 5.5 to 5.8 above) If conductivity is
satisfactory (below 100us/cm) leave boiler full and
circulating and continue from step 6.1 below.

5.5 (repeat) Draining boiler.

5.6 (repeat) Flush to open drain.

5.7 (repeat) Refill boiler to NWL.

5.8 (repeat) Circulate boiler for 15 minutes. Conductivity check.

19
5.5 (repeat) Draining boiler.

5.6 (repeat) Flush to open drain.

5.7 (repeat) Refill boiler to NWL.

5.8 (repeat) Circulate boiler for 15 minutes. Conductivity check.

6 Copper Removal

Establish circulation of the boiler using temporary

6.1
pumps.

Take demineralised water from feed water pumps

6.2
of Unit II boiler and start circulation of boiler.

When the desired temperature is reached, stop

6.3
pumps of feed water.

Backflush the superheater until a rise in drum level

6.4
is observed, using make up water pump.
Check that the temperature of the system has
stabilized between 50⁰-55⁰C. Start up temporary
6.5 Chemical cleaning pump and commence pumping
into system.

6.6
Inject chemicals to give: 10g/l (1.0%w/w) Citric Acid
(1000 kg anhydrous), Ammonia to achieve pH 3.5-
Take samples every
4.0 (approx.200 20check
litres, minutes and monitor.
by sampling)
Continue circulation depending on analysis for at
6.7 least 1 hour, but no more than 2 hours.

Raise the solution pH to 9.5-10.0 by injection

of further Ammonia solution (approximately
2200 litres Ammonia 25% solution required-
6.8 check by sampling.

Inject Sodium Nitrite to mixing tank to give(0.5%

6.9 w/w). On completion pump out mixing tank until
empty.

Continue circulation by pump &air injection for a

6.10 further 4-6 hours. Take samples every hour and
monitor.

Stop circulation and set up for draining to Chemical

Waste Water Pit. Stop pumps. Drain boiler and
6.11 economiser completely to Chemical Waste Water
Pit.

7. Ammonia Rinse
Start pumps and commence filling economiser and
7.1
boiler. Commence backflush the superheater into

Fill boiler to normal working level (1/2 drum). When

7.2 at the desired drum level stop make up water
pumps.

Establish circulation of the economiser and boiler

7.3
system.

Start up temporary chemical cleaning pumps and

7.4
commence pumping into system.

Inject chemicals to give: Ammonia to achieve pH

7.5
10.0-10.2 (25-50 litres).

7.6 Maintain circulation and temperature for 15 mins.

8. Inspection
Disconnect temporary connections from boiler
pressure parts. Open steam drum door and allow
8.1 internal parts to ventilate and dry out from residual
heat in the metal.

20
 Inspect at drum, manually remove any debris
lying in low-lying areas. Inspect at other terminal
8.2 points as required by client. On acceptance
release boiler for pressure parts reinstatement.

The List of Chemicals required for Boiler Chemical cleaning according to the above procedure is given below:

S.No Chemical Quantity ( Approx.)

1 5-6% Sulfamic Acid 12000 - 14000 Kg

2 0.2% Aquacure IC 600 200 Kg

3 Ammonium Bifluoride 500 Kg

4a 0.2% Citric Acid 200 Kg anhydrous

4b 1.0% w/w Citric Acid 1000 Kg anhydrous

5 Ammonia Solution 2750 Liters

6 0.5% w/w Sodium Nitrate 500 Kg

21