Professional Documents
Culture Documents
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INDEX
CHAPTER CONTENTS
1.
INTRODUCTION.
2.
3.
4.
5.
6.
7.
8.
9.
10.
WALLWASH TESTS
11.
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1.
INTRODUCTION
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Sept 1999 09 01
AGGRESSIVE CARGOES (MISCELLANEOUS) IN EPOXY COATED CARGO TANKS
Epoxy coated cargo tanks and the influence of aggressive cargo on the epoxy tank lining in general.
The epoxy coating film will be influenced by all type of liquid cargoes, but aggressive cargoes are those with greatest
influence.
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150C.
17 days
200C.
250C.
300C.
13 days
9 days
6 days
4 days
17 days
9 days
6 days
4 days
17 days
12 days
8 days
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OF CARGO
Phenolic epoxy is resistant to solvents, such as Ketones, low molecular weight alcohols, Ethers and
Esters.
However, caution must still be used when cleaning the tanks and selecting the next cargo.
After containing these types of solvents, the tank should be well ventilated to remove all traces of the:
chemical prior to cleaning.
The next cargo should not be any water ballast or diluted aqueous solutions such as liquid fertilizer solution or latex
emulsions.
Reference notes:
a) ESTERS. PHTHALATES. ETC.
Certain products such as esters (acetates, phthalates etc.) and chlorinated or brorninated materials can react with water to
form acidic compounds.
These products are suitable for storage in PHENOLIC EPOXY 373 coated tanks, but the presence of any moisture will
make them aggressive and unacceptable. Such products must therefore be dry, free from acidity and carried in completely
dry tanks. Water contamination must be avoided and water content of the cargo should not exceed
0.02% (200 PPM).
b) KETONE. ALCOHOLS. NITRITES AND ESTERS.
These aggressive cargoes can only be carried when the coating is fully cured and this will be obtained after a service period
of 3 months with non-aggressive cargoes (without notes).
After transportation of cargoes marked with a note, the coating has to be restored to its original condition.
This will be obtained by ventilating the tank thoroughly until the tank is in a gas-free condition, followed by carriage of
non-aggressive cargoes without a note (in the resistance list) for a period of at least 10 days.
c) AGGRESSIVE WATER MISCIBLE CARGOES.
Before loading these aggressive, water miscible cargoes, it is essential to remove all traces of water from the tanks.
After carriage of these cargoes, no steam, ballast water, wash water, slops or aqueous cargoes must come into contact with
the coating before its original coating condition is restored.
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The coating will be restored by thorough ventilation until the tank is gas-free, followed by the carriage of non-aggressive
cargoes (without a note) for a period of at least 10 days.
Ventilation of the tank must be carried out after an aggressive/water miscible cargo has been discharged.
This is to ensure the removal of any cargo which may have been absorbed into the coating.
THIS MUST BE DONE PRIOR TO ANY TANK CLEANING PROCEDURES BEING CARRIED OUT.
Any residue left in the tank after cleaning must be removed immediately and drying completed by venting.
Cargo residues or absorbed cargoes in the coating, is a potential source of contamination of subsequent cargoes.
Cargo residue and absorbed cargo in the coating film may cause a chemical reaction, and produce products, which could
cause breakdown of the coating system.
There is also a category of aggressive cargoes, which can only be stowed in epoxy coated tanks for a limited number of days.
This number of days must not be exceeded, as the coating will be softened and the absorption of chemicals will increase,
which will obviously damage the tank coating.
The limitation of days is mentioned in the cargo resistance list for the cargo in question. Explanation of absorption.
When a liquid cargo is loaded into a tank coated with an organic coating (Phenolic epoxy), part of the liquid will be absorbed
by the binder phase of the coating through a diffusion process. Absorption will continue until the binder phase is saturated
with the liquid.
When the cargo is later discharged from the tank, desorption will take place, again by diffusion process and will ideally
continue until all absorbed liquid has been removed from the coating.
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SEPT 1999
99.09.01
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4.
TANK CLEANING
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4.3.4 VISCOSITY.
Substances with a high viscosity also require a higher temperature wash water.
If possible the temperature of the wash water should be such that the viscosity of the pure substance is low, at least below 20
to 60 mPas (cp.) at that temperature.
4.4 REACTIVITY.
For the cleaning procedure relevant reactions of the substance are:
- Self reaction
- Reactions with water
- Reactions with oxygen
- Inhibited cargos
- Smell producing cargos
4.4.1 SELF-REACTION.
Examples of a self-reaction is the polymerization of monomer substances i.e. styrene and acrylic acid. Higher temperatures
increase the reaction speed of this type of reaction, washing with hot water may result in polymerized material being left in
the tank, which is very difficult to remQve. Polymerization may also take place when a tank is not cleaned and left dirty for
a few days. Because the inhibitor is not as volatile as the monomer substances , condensation of the vapor will allow
inhibitor free liquid to be formed.
Cleaning of these cargoes should always start with a cold wash.
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INHIBITED CARGOS.
nhibitor is not properly removed , then this will have a negative effect on the PTT test. mmon inhibitors are fully soluble in
water.
Libited cargoes must be thoroughly pre-washed with cold Fresh or Seawater, followed by warm (Use an alkaline I caustic
solution)
water wash alone is not sufficient.
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The specification of the substance to be loaded has also influence on the required cleanliness of the cargo tank.
Jo Tankers is transporting:
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A forced circulation of the cargo during transportation prevents sedimentation in the tanks and a minimum of sludge
is therefore left after discharging the tanks.
Circulation of Vegetable oil and Animal oil in coated cargo tanks is in fact a must to prevent not only sedimentation
but also avoid creating a difference in the FFA content between the lower and upper pai of the tanks.
The heating instructions are to be followed and too high temperature of Vegetable oil and Animal oils should be
avoided.
A too high moister content will cause extensive increase of the FFA during transportation.
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In general tank cleaning operations must be carried out in accordance with the 1SGOTT. manual chapter 9.2.4. Cleaning in
undefined atmosphere.
The procedure for tank cleaning may include the following stages:
6.1 PRE-CLEANING.
The purpose of pre-cleaning tanks with tank cleaning machines using either salt or fresh water, is to remove residues from
bulkheads, tank bottom and underdeck,(Bulk cleaning)
The sooner the pre-cleaning is carried out after the discharge, the easier residues will be removed. During pre-cleaning the
tank cleaning machines should be moved frequently, in order to cover the entire surface.
After pre-cleaning the tank should be inspected and, if residues are found, the tank cleaning machines should be centered
over the areas for further cleaning.
6.2 CLEANING.
Cleaning is carried out with the aid of water or water and cleaning chemicals. In most cases we recommend 0,05% of the
detergent.
The cleaning solution can be applied cold or hot, using tank cleaning machines.
When applying a solvent cleaner by spraying it will be obvious that after the reaction time (mm 30 minutes) the residues
have to be washed away.
~ Tank cleaning machines with cold or warm water should be used for this, not too hot, otherwise the applied solvent will
evaporate.
The machines must be lowered down into the tank at recurring intervals in order to obtain an effective cleaning throughout
the tank.
Throughout the cleaning operation the tank bottom has to be kept as dry as possible by constantly pumping out the water.
When using recirculation, the cleaning solution can be used two or three times iE light petrodiemical products are to be
removed.
However, precautions have to be taken in order to prevent build up of static electric charges.
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Cleaning of Mineral Oils can be carried out with water and detergents or water and a solvent cleaner. Petrochemicals and
Solvents are removed by one of the following (general) procedures:
Substances with a low boiling point and a high vapor-pressure (50 mbar or more) at ambient temperature can be removed
by evaporation or a light cleaning. In case of evaporation the pre-cleaning step may be omitted, however evaporation of
substances from lines and pump is difficult. Flushing with fresh water of the lines is recommended.
Substances with a lower vapor-pressure are removed by water washing and steaming.
~
In the first stage cold water is recommended; volatile substances show a higher solubility in cold water.
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SEPT 1999
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6.3
RINSING.
Directly after the cleaning operations the tanks should be rinsed with warm or cold water by means of tank cleaning
machines.
It is most important that the cleaning solution should not allowed to dry as this will effect the outcome of the tank cleaning.
Rinsing should nonnally continue until no residue can be found in the tank.
6.4. FLUSHING.
The tank has to be flushed thoroughly with fresh water to remove salts from seawater.
6.5 STEAMING.
Steaming is an important step in removing traces of volatile substances by evaporation,
Also traces of less volatile material are often successfully removed by steaming.
During steaming condense water has to be continuously pumped out from the tank.
Steaming should be performed in a gas free tank.
6.6
DRAINING.
Tank line, venting system, stripping line and pump must be well drained.
All plugs etc. should be removed.
6.7
DRYING.
After the cleaning procedure the wet surfaces of tank, lines and pump have to be dried by ventilation. During this stage of the
cleaning procedure absorbed volatile substances will evaporate from the coating of coated tanks.
CONCLUSION.
Tank cleaning effective solutions?
From the previous pages we have seen that a lot of factors influence the tank cleaning process.
Only when sufficient information is available of the substance to clean from, can one develop a correct
tank Cleaning procedure.
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8.0
An extra freshwater flush of the cargo line to remove remaining liquid in pockets is advisable.
CLEANING PROCEDURE 2
B/W with cold to warm (30 deg C) seawater
Freshwater rinse
Steaming
Gas-free tank and Ventilate
Visual inspection tank
Mop and dry
1.5
0.5
1.0
2.0
0.5
1.0
6.5
CLEANING PROCEDURE 3
B/W with warm and ending with hot
Bw hot water with detergent / degreaser
1-lot fresh water rinse
Steaming
Gas-free and ventilate
Visual inspect tank
Mop and dry
2.0
2.0
0.5
2.0
2.0
0.5
1.0
10.0
Before starting BW seawater some Lube. Additive requires roundwash with MDO or light mi peral oil
- direct after discharge. Do not use hot-water first
If next cargo is sensitive to Hydrocarbons use HCF cleaner.
If ijecessary a final spray tank with an Ethanol / Methanol / Ketones.
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Sept 1999
CLEANING PROCEDURE 4
BWcold.
BW warm I hot seawater with detergent I degreaser
Fresh water rinse
Steaming
Gas-free / ventilate
Mop and Dry
99.09.01
2.0
4.0
0.5
2.0
0.5
2.0
11.0
In case of cleaning from an edible oil, first ascertain if the oil is drying or non drying.
Start to preach at discharge temperature.
Another option after the preach is to spray tank with a degreaser.
CLEANING PROCEDURE 5
B/W with warm freshwater
Steam
Gas-free and ventilate tank
Mop and Dry
1.0
1.0
2.0
1.0
5.0
CLEANING PROCEDURE 6
B/W with warm to hot seawater
2.0
Freshwater rinse
0.5
2.0
1.0
5.5
CLEANING PROCEDURE 7
I
131W with cold seawater
13/W with warm to hot with detergent or degreaser
B/W warm seawater
Fresh water rinse
Gas-free and ventilate
Mop and dry
1.5
2.5
0.5
0.5
2.0
1.0
8.0
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1.5
1.5
2.0
0.5
3.0
1.0
-----9.5
CLEANING PROCEDURE 9
Substances with a vapor pressure higher than 50 mbar at 200C.
The non -volatile matter content indicated in the Cargo specification can be used to
evaluate the possibility to perform only ventilation.
Inhibited cargoes are excluded.
B/W with cold I ambient seawater
1.0
1.0
0.5
2.0
1.0
5.5
CLEANING PROCEDURE 10
B/W with hot seawater
2.0
2.0
0.5
2.0
Mopanddry
1.0
7.5
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2.0
1.0
0.5
2.0
1.0
6.5
CLEANING PROCEDURE 12
B/W with lukewarm seawater
B/W with hot seawater
Fresh water rinse
Gas-free I ventilate tank
Mop and dry
1.0
2.0
0.5
2.0
1.0
6.5
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PHOSPHORIC ACID
First a cold butterworth wash for 2 - 3 hours.
Use extra tank cleaning machines to increase the water flow.
Take care of clogged lines.
If sediments remain, hand hose to pumpwell as soon as possible using fresh water.
Note the TANK ENTRy procedures.
F~fW cold water. If seawater has been used, rinse directly after with fresh water.
Passivate whenever possible. Never leave slops and water in the tanks, this will become concrete.
Tampa Phosphoric Acid. After the usual washing, hard concrete like layers remain on bulkheads, ladders, stiffeners etc.
Even high pressure wash does not work.
A recirculation with Phosphoric Acid will work (COW procedure).
Based on a tip from captain Hoogerbeets, Jo Brevik, tried following procedure:
Mix 500 It. phosphoric acid and 5/6 Mt. Freshwater, recirculate this solution around for 2/3 hrs. Result was very gQod,
everything removed and tank very shiny/smooth.
500 liters phosphoric acid seems to be on the high side, may be 200 liters will work as well.
SULPHURIC ACID
Preferably fresh water to be used. If not possible then seawater.
A~ much as water as possible should be pumped into the tank (via cargo lines and butterworth
machines), which should be pumped out immediately as well.
If not possible to pump wash water away immediately tank should be left untouched and
Completely closed avoiding entry of moisture.
This situation however should be as short as possible.
Followed by direct B/W with freshwater.
Gas-free / Ventilate.
Mop and dry.
Passivating providing time available.
MDI AND TDI
Pre-washing with preferably METHYLENE CHLORIDE (max 50 PPM water)
Monochlorobenzene as second choice (max 50 PPM water)
MDI and IDI are completely soluble in Normal Propanol as well.
Load first batch (quantity depending ott pump suction), then recirculate, via B/W machines cow-head two cycles and pump
slop back to shore facility.
Load second batch and repeat earlier procedure. After completion clean tank for MEC.
Avoid at all times moisture/air entering the tank(s).
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FISH OIL
B/W with Cold seawater.
B/W with hot sea or freshwater. (Solution 0.5% Teepol or Caustic/detergent mix).
Good result with Lead Clean CP with extra Citronella (inject or recirculate).
Rinse with fresh water.
Vent and dry tank.
Inspect, if still fish oil remains, than spray lead clean and hot Bw.
Rinse with fresh water.
Vent, mop and dry.
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SMELL KILLERS
Especially after cleaning of acrylates etc. HENKEL P3/NA, VECOM AIR FRESH and NILODOR may be used.
Cleaning cq washing with f.e. Methanol of tank hatch and BIW hatch gaskets may be required as these usually accumulate
strong odors.
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1)
Direct after hot pre-wash for 2 hours.
Recirculate with a solution of 2,5 cbm. fresh water and 3 bags of caustic soda flakes
(or pro rata), add 5-10 liters Metal Brightner, heat the solution up to
50-60C recirculate the solution for about 4 hours.
Fresh water rinse.
Ventilate, suck and dry.
Other cleaning media: Coaltar cleaner - Grato 14 - Grato 50 - CTC Cleaner in combination with
Caustic soda.
Myrcene - (Di) Pentene - Nonene.
2)
Hot pre-wash for 3 hours.
Recirculate 2 hours with a solution of 2,0 cbm freshwater and 100 kg caustic soda, 150 ltrs myrcene,
start washing at 500C and increase slowly to 800C Fresh water rinse.
Ventilate, suck and dry, result ok.
3)
Hot 800C pre-wash for 2 hours, followed by freshwater rinse.
Recirculate 2 hours with a solution of 3,0 cbm freshwater and 50 kg. caustic soda, 1 can of CTC
cleaner, start washing at 500C and increase slowly to 800C recirculate solution for about 3 hours.
Fresh water rinse.
Ventilate, suck and dry, tank ok.
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Creosote.
After Pre-wash
Prepare 2 cbm FW. and add one drum of coaltar cleaner. circulate solution 3 / 4 drops, each drop one hour.
After recirculation start washing at discharge temperature increase to hot seawater 800C, 3 drops one hour.
During hot seawater wash steam vapor line, steam PV, flush drop line, clean through stripping line. Lally
connect freshwater pump to clean back through lines and tank with
a thoroughly FW rinse. Steam cargo lines with Metal brightner if necessary.
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Slack Wax.
Adjacent tanks should be empty in order to have the temperature of the bulkheads abowe the melting point.
Preheat washing water to 800C !!! direct after discharge flush cargo lines from both sides of manifold back into tank for
about 10 minutes.
Clean with SW for 30 minutes hot, leave water in tank and keep heating on. Untill discharging of the wash water keep live
steam slowly into tank. than BW.SW. 3 drops of 45 min. 800C, freshwater rinse, ventilate suck and dry. Do not clean with
toluene.
In case cargo in adjacent tanks, a recirculation with Gas oil could be another option. Injection 10% solution in hot water of
CTC - VLC cleaner during hot wash.
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Tank cleaning chemicals are used to improve the cleaning effect, they may help to reduce the amount of
time and the quantity of water to be used.
Not in all cases the addition of chemicals improves the cleaning effect, the addition of the wrong type of
chemicals may leave the tank in such a condition that the tank may only be cleaned with
a lot of effort.
In general the use of cleaning chemicals is restricted to the final washing stage, after the bulk of the
substance has been removed from the tank by washing with water.
Addition of tank cleaning chemicals is often not accepted when discharging slop water to reception
facilities.
8.1 DETERGENTS.
The surface tension of water is lowered by the addition of detergents.
As a result water insoluble substances are washed away more easily from the tank walls.
An emulsion of the substance and water is formed, depending on the nature of the detergent. the emulsion
is more or less stable.
Some manufacturers of detergents have developed emulsion breakers, which may be added to the slop
water to separate the emulsion.
Detergents can be used for cleaning of water insoluble substances.
Pure detergents are used in concentrations of 0.05%, commercial preparations may require higher
concentrations.
Solutions of detergents may foam very strongly, addition of a small amount of a higher alcohol (i.e.
bu~anol) breaks down the foam.
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The solvents in this type of cleaners are mineral oil based with a flash point of approximately 600C, two main types are
used:
- with a high aromatics content
- with a low aromatics content
The best solvents are the high aromatic type hydrocarbon solvents, which unfortunately have a disdgreeable smell.
The solvents, which are very low in aromatic compounds often, are designated as odor free When mixed with water this
type of solvent cleaners will form a milk like emulsion because the solvent is not soluble in water.
They are best suited to clean from heavy mineral oils, especially the high aromatic type. Their purpose is to dilute the
substance to clean from and lowering the viscosity. Occasionally the hydrocarbons are of vegetable origin i.e. orange oil.
The transport of methanol and other substances requires hydrocarbon free tanks, after washing with a solvent cleaner traces
of hydrocarbons may be left in the tank, for that reason hydrocarbon free solvent cleaners were developed.
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SEPT 1999
8.3.
99.09.01
ALKALINE CLEANERS
Alkaline cleaners are historically used to clean from fats and oils, good results are obtainable but a word of
caution is important.
When these cleaners are used with seawater a white solid material (magnesium and calcium carbonate) will
be formed, only a diluted acid removes this. material.
Strong alkaline cleaners may be used in steel, epoxy coated and stainless steel tanks. Strong alkaline
cleaners will dissolve zinc coating.
To avoid attack of zinc coatings buffered alkaline cleaners are used, the PH. value is about 10, on mbst zinc
coatings his type of alkaline cleaners can be used.
The oils and fats are partly saponified by the alkaline cleaners.
Fats with a high melting point will form hard soaps when caustic soda is used in the cleaner, when
potassium hydroxide is used softer soaps are formed.
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Colour standard.
Distilled water Chloride free.
Distilled
KMNO4 crystals in brown bottles (30 ml. or 100 ml).
Hydrochloric Acid (as cleaning agent).
Additional material.
Safety labelled (Methanol) Wash Bottle 1000 ml
Safety labelled (Distilled water) Wash Bottle 1000 ml.
Safety labelled (Hydrochloric Acid) Wash Bottle 500 mL
Safety labelled (Toluene) Wash Bottle 500 ml.
Measuring cylinder 50 ml. long form with stopper.(4x)
Bath / Cooling container.
Approved clean chemical gloves.
Paper filters.
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WALLWASH TESTS
ACID WASH COLOUR TEST OF
Industrial Aromatic Hydrocarbons
(Benzene-Toluene-Xylene) Astm D848 method
APPARATUS
Nessler tubes short form.
Colour Standards
REAGENTS
Sulphuric Acid (concentrated)
PROCEDURE
NOTE
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APPARATUS
Nessler tubes I OOml. short form.
Pipette 2m1.
Dropping bottle.
REAGENTS
Distilled water Chloride free.
Silvernitrate.
Standard Chloride solution (1 ml 0.025 mg CL).
PROCEDURE
Transfer 25 mls DI water from wall wash sample into one of the Nessler tubes and fill to the
upper mark, with distilled water.
Fill a second tube to the upper mark with distilled water, and add 1 ml. standard chloride
solution.
Mix both tubes and add abt. 5 drops Silvemitrate.
Compare the cloudiness of the standard against the sample tube by viewing downward through
the tubes toward a dark background.
Add as much mls Chloride standard as necessary to the second tube to compare the cloudiness
of the sample.
CALCULATION
NOTE:
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CHLORINATED AROMATICS
Methylene Chloride
Carbon Terachloride
Ethylene Dichloride
Perchloroethylene
Trichioroethylene
Trichioroethane
Chloroform
Monochlorobenzene
Orthonitrochlorobenzene
Orthonitrotoluene
Paradichlorobenzene
Paranitrotoluene
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OK
Bottom will work as a miror .
Wrong
NOTE: use clean equipment to perform the test.
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STANDARD
Cylinder 50 ml.
For colour standard: Cobalt Chloride 0.170~1
Uranyl Nitrate 0.280g/l
Distilled water 20 ml.
Mix thoroughly and add distilled water till upper mark.
This standard represents the final colour, to which the sample solution in the KMnO solution
discolour.
REAGENT
One litre fresh boiled distilled water.
Add 2m1. of KMNO4 (0.200 gIl) solution.
The Potassiumpermanganate solution should be stored in brown bottles and in the dark.
The solution should be prepared fresh and every fortnight or monthly.Clean glass or bottles must
be used.
METHOD
Clean a 50 ml. measuringcylinder with concentrated hydrochloric acid
(37 % vol hcl) to remove all possible contaminants.
Remove all Hcl with water,also the vapours by filling the cylinder
complete for several times.
Wash several times with Methanol or the product as such.
A
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To have a Ptt test performed on board you must keep in mind that the circumstances are not ideal.
Try to keep and hold the right temperature.
Is the required time of the wall wash equal to the final product.?
Purity of the Methanol used and tested with same Ptt solution?.
Equipment used clean?
No fluctuation in temperature from wall wash samples.
Even if the Ptt test taken on board before arrival passed, gives no quarantee to have the same result from
the surveyors test. (Different spots taken by surveyor).
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The reason for acid pickling is to achieve a clean steel surface that has the corrosion resistant one may expect from the steel
grade in question.
The attainment of surface that are free from iron, metallic deposits and other contamination depends on combination of
proper design, fabrication methods, cleaning and descaling and protection, preventing the recontamination of clean surface.
Note: Oxidizing agent (air) must be present and replenished regularly to maintain passivity. Passivating
is not a constant state, it only exists in certain environments or under certain conditions. In circumstances
favorable to passivity, Stainless steel has a solution potential approaching that of noble metals. If
Dassivity is destroyed, the Dotential aDDroximates that or ordinary iron. Most corrosion problems can
be traced back to this fact.
Before stainless steel is subjected to acid pickling, it is important to know the composition of the alloy. On Jo Tankers
vessels we are only using two (2) standard compositions. One composition is to a standard (acid resistant stainless steel)
AISI 316 LN and the other standard type of acid resi~tant steel is Duplex Steel 2205.
The acids most commonly used for scale removal are nitric acid, hydrofluoric acid and sulphuric acid. But there exist no
single acid solution or process that is equally effective for removing oxide scale form all grades of stainless steel.
Acid picking is usually carried out in a mixture of acids containing hydrofluoric. It is in particular the best process for
Stainless Steel. Mixtures of nitric acid and hydrofluoric acids have the advantage of being only mildly corrosive to the
majority of stainless steel. The attack is uniform and the corrosion rate can be predicted easily.
Acid Pickling
All repair jobs such as welding, grinding etc., shall be pickled. All welding of pipes should be pickled and the most practical
execution of pickling a piping system is to circulate the pickling media via a tank or container. Fluid velocity must not be too
slow. Low ambient temperatures may be a problem, partic~ilarly winters in northern countries.
Never pickle more than 20-30 minutes without inspection.
Passiviation
In principle passivation of stainless steel surface helps build up the natural oxide layer. A passivation with nitric acid will,
on a clear surface, rapidly build up a sound oxide layer.
The same oxide layer will also form in air but this takes somewhat longer and it will not be as thick.
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