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Wall-Wash tests on Chemical Tankers

nautraj.blogspot.com/2011/04/wall-wash-tests-on-chemical-tankers.html

Wall Wash Test Procedures on Chemical Tankers

Preparation
-Reagent-
v Pure Methanol (500 ml/bottle)
v Pure Water (DI Water)
v 2% Silver Nitrate Solution (500 ml / bottle)
v 20% Nitric Acid Solution (500 ml / bottle)
v 10 ppm (0.01 mg/ml) Chloride Standard Solution (500 ml / bottle)
v 0.02% Potassium Permanganate solution (100 mg in 500 ml of DI Water) – to be stored in
a dark bottle in a dark bottle and cool temperature.
v Concentrated Hydrochloric Acid (500 ml / bottle)

-Instrument-
v Funnel x 1
v Plastic Bottles (500 ml x 2 bottles for collecting wall wash samples)
v Nessler Tube (100 ml x 6 nos.)
v Pipette (5 ml x 4 nos. for Nitric Acid / Silver Nitrate/Chloride Solution / KmnO4
v A petridish or Shalle x 2 nos. (for testing Non-volatile matters)
v Disposable Vinyl gloves (200 sheets / case)
v Disposable Shoe covers
v A.P.H.A. Color Standard (No. 3, 5, 8 & 10) for color test.
v Black colored plate (for testing turbidity of Hydrocarbon / Chloride)
v White colored Plate (for testing of turbidity of color)
v Flash Light.

Wall Wash Sample Collection

v Before entering into the tank for sampling, ensure that the tank has dried up completely
and has no humidity on the wall and gas freed.
v Check for toxic gas /combustible gas / oxygen prior entry.
v One man standby – in attendance
v Carry the test kit for WWT in a closed bag or wooden box and keeping in mind not to drop
the same in the tank while going into and coming out of tank.
v Put the shoe covers and wear the vinyl gloves.
v Wash the equipment to be used for WW sample collection by methanol.
v A sample of test methanol is sprayed on the bulkhead and collected in a sample bottle by

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using half cut funnel.

v Take sample from four parts of forward / aft / port / Stbd bulkheads and in the area of 1
meter in height x 30 cm in width at the position of 1.5 m from the bottom by methanol wash
on the wall.
v The necessary quantity of sample from each tank is about 200 to 250 ml (50 ml for color,
50 ml for Hydrocarbon, 50 ml for Chlorides & 50 ml for PTT).

Sample Analysis

Colour
This is represented by APHA from 1 to 30 where >APHA5 is the most stringent. The number
is determined in the lab by passing light through the sample. Most ships do not have this
equipment but if you hold the sample against a white sheet of paper and it appears
absolutely colorless you can be quite sure that the number is less than 5. For this fill up
sample about 50 ml and add 50 ml methanol into a 100 ml Nessler Tube.

Suspended matter
Switch of all light and hold torchlight at the bottom of the tube containing the sample. Any
suspended matter will be clearly visible.

Hydrocarbon Test
Hydrocarbons together with water will form a milky solution. To 50 ml of wall wash methanol
add 50 ml of DI water. The mixture is shaken and allowed to stand for 20 minutes. Initially
turbidity will appear and the same will reduce in a few seconds. Compare this to a nessler
tube containing 50 ml of pure distilled water and 50 ml of pure methanol (as a standard
solution for comparison) on the black plate or background. Switch off the lights and using a
flashlight shine the beam first from one side and then from other. Look into the tubes from
the top for turbidity. If the sample appears cloudy or not completely clear then hydrocarbons
are too high and the tank needs to be washed with methanol.
NOTE :- The proportion of methanol to distilled water for testing will depend on the terminal
where the product is to be loaded. Includes, where available, the required wall wash
specifications of terminals. If a terminal's required specification reads "hydrocarbons pass
(10/90)" this means that the surveyor conducting the wall-wash test will use a mixture of
10ml of methanol to 90ml of distilled water. The responsible officer conducting the test
onboard his vessel may then use the same proportion of methanol to distilled water, however
the proportions of 30/70 will provide a more accurate picture of the tank wall.

Chloride Test
Normally 10ppm standard chloride solutions are available on board:
v To make a 2 ppm standard solution add the following:
§ Pure methanol 50 cc

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§ 10ppm standard chloride solution 8 cc

§ Distilled water 38 cc
§ 20% nitric acid solution 2 cc
§ 2% silver nitrate solution 2 cc
v To make a 0.5 ppm standard solution add the following:
§ Pure methanol 50 cc
§ 10ppm standard chloride solution 2 cc
§ Distilled water 44 cc
§ 20% nitric acid solution 2 cc
§ 2% silver nitrate solution 2 cc
The principle of the test is that chloride together with a silver-nitrate solution gives a milky,
cloudy solution.
In a clean, graduated Nessler-tube transfer 30ml of the methanol and top up to 100ml with
certified distilled water, add 5 drops of nitric acid * and then 5 drops of silver-nitrate solution
and mix the contents thoroughly.

* Before adding the silver nitrate, take a reading as well. If there is a reaction between the
nitric acid and wallwash sample there is something else left on the coating which are not
chlorides and will reject the tank also. Then add the silver nitrate and take a reading again.
The difference in readings before and after is due to the actual chlorides. Prepare a standard
solution of 30ml certified methanol and 70ml certified distilled water with 5 drops of silver-
nitrate solution. In a dark room, and preferably against a dark background shine a penlight
through the contents and compare against the standard solution. If turbidity in the test
Nessler-tube is observed then chlorides are present.

Permanganate time test(PTT)

Make a standard solution with 0.1 gm of potassium permanganate in 500 ml of water.
· This method serves as a means of detecting the presence of impurities in alcohols or
ketones that reduce potassium permanganate and is applicable to Methanol, Propanol,
Butanol, Methyl Ethyl Ketone and Methyl Isobutyl Ketone.
· Substances reacting with potassium permanganate in neutral solutions reduce it to
manganese dioxide, which colours the solution yellow. In the PTT the time required for the
colour of the test solution to change to that of a standard solution is measured. The colour of
the test solution changes from pink-orange to yellow-orange. For shipboard testing the time
for the colour to differ from a test solution measured against a standard solution of certified
methanol is sufficient.
· The equipment required for PTT are as follows:-
1 Cylinders, glass-stoppered, 50ml.
2 Constant temperature bath, capable of maintaining a temperature of 15.0 +/- 0.5
degrees C or 25.0 +/- 0.5 degrees C. If a constant temperature bath is not available then a
bucket of water cooled with ice is an acceptable shipboard substitute.

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3 Pipette, capable of delivering 2ml of solution.

4 Clock or stopwatch.
5 Potassium Permanganate Solution (0.100 g of KMnO4 per 500ml of water).
Fill a 50ml glass-stoppered cylinder beyond the mark with certified methanol and place it in
the same bath.
When the samples have reached the bath temperature (about 5 minutes) add 2ml of
potassium permanganate solution with a pipette, invert once to mix the contents and return
to the bath.
Keep the samples in the dark, and check about every 10 minutes.
Determine the time from the addition of the KMnO4 until the colour differs (fades) from the
standard of certified methanol.
Violet à Light Violet à Orange Color à Light Yellow
When the test is finished wash the tubes with tap water and fill with concentrated
hydrochloric acid. Use protective gloves and goggles for this and preferably do it in the
open.

Non-Volatile Matter
NVM can only be checked in a lab. A small portion of the test sample is placed in a petridish
or shalle and allowed to evaporate by applying heat to it. The weight of the dish when the
entire methanol has evaporated will determine the quantity of NVM in sample. It is preferable
to carry out this test with Acetone rather then methanol i.e. the sample should be taken using
Acetone.

Acid Wash Test

Pour 7ml concentrated laboratory grade Sulphuric acid into a test tube. Add 21ml of the
wallwash sample (toluene). Shake vigorously for 30 seconds. Place in the dark for 15
minutes. Look for colour (haze) in the Sulphuric acid layer. Compare with colour standard if
one is available on board. When toluene is used as a test medium, acceptable haze/colour
of the acid is 2 on the standard scale.

Wallwash test precautions and some causes of failure

v Always use disposable plastic gloves when wall washing - the human hand
contains more salt than normal requirements and is a common cause of chloride
contamination.
v Wear clean clothes and do not allow working gloves in the tank, avoid all contact of
clothing with the tank, wear protective disposable shoe covers.
v Use a clean bucket on a clean line for transferring test equipment into the tank.
v Wash the funnel and sample bottles with certified methanol prior to collecting the
sample.
v Always test the distilled water and certified methanol prior to use for testing and
always run a standard against the test sample.

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v The glue used for the seals on some types of sample bottles have been known to
cause sample contamination.
v When using acids for washing wear the proper protective equipment.
v Take your time, sampling in a hurry or rushing through the test procedures cause
failure.
v If the sample passes all tests, be suspicious, and test again.
v Never test a wet tank, the tank wall must be dry.
v Allowing a tank to "rest" after prolonged washing (especially hot washing) can
often turn a failed tank into a passed tank.
v Keep a record of your wallwash results, especially if testing multiple tanks.
Consulting this record over days of tank cleaning may provide a useful indication of
which washing procedure is working best.

Removal of Hydrocarbon
If HC < 2 ppm Spray Methanol in the tank
If 2 ppm < HC < 3 ppm Toluene Steaming (Only in inert atmosphere) for 3
hours & Methanol Spray
If 3 ppm < HC < 5 ppm Toluene Wash à Steaming (within LEL) à Methanol
spray
If HC > 5 ppm Re-cleaning with detergent or solvent depending upon
tank coating

Removal of Chloride
If Cl < 2 ppm Steaming or Spray DI Water and then Methanol in the tank
If 2 ppm < Cl < 5 ppm Methanol Steaming (Within LEL)
If Cl > 5 ppm Hand wash by Fresh Water à Steaming à Methanol Spray

Removal of Oxide Residue (PTT)

If 30 min < PPT < 50 min Methanol Spray
If 15 min < PPT < 30 min Methanol Steaming à Methanol Spray
If PPT < 15 min Re-tank cleaning with detergent or solvent

Removal of Color
No. 5 < APHA < No. 10 Treatment with Rust Remover in case of rust &
Methanol spray
No. 10 < APHA < No. 15 Treatment with Rust Remover in case of rust
&Steaming & Methanol Spray
APHA > No. 15 Treatment with Rust Remover in case of rust &Hot water
butterworth à Methanol Spray

Removal of NVM Residue

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Almost Nil NVM Methanol Spray

Normal Toluene wash à Methanol wash
Too much Re-tank cleaning by detergent or solvent

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