Cargo Operations

Product and chemical cargo tank coatings:compatibility with different cargoes and preparing tanks to take the next cargo

Dr. Michael AamodtGlobal Product ManagerTank CoatingsGroup Marine Marketing23 November 2015

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o Carriage of chemicals in bulk is covered by regulations in SOLAS Chapter VII - Carriage of dangerous goods and MARPOL Annex II - Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk.

o Both Conventions require chemical tankers built after 1 July 1986 to comply with the International Bulk Chemical Code (IBC Code), which sets out the international standards for the safe carriage, in bulk by sea, of dangerous chemicals and noxious liquid substances.

o The IBC Code sets out a list chemicals and their hazards, and identifies both the ship type required to carry that product and the environmental hazard rating.

o All approx. 1800 cargoes in the IBC Code & MARPOL must be in a marine resistance list

Carriage of chemicals by ship

23 November 2015

Chemical tankers – IBC Code types

The IBC Code defines three types of chemical tankers “intended to carry chapter 17 products”:

o Type 1 ship:o Products with very severe environmental and safety hazards which require

maximum preventive measures to preclude an escape of such cargo

o Type 2 ship:o Products with appreciably severe environmental and safety hazards which

require significant preventive measures to preclude an escape of such cargo

o Type 3 ship:o Products with sufficiently severe environmental and safety hazards which

require a moderate degree of containment to increase survival capability in a damaged condition

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o A product tanker means from a classification point of view an oil tanker engaged in the trade of carrying oil other than crude oil, i.e. products like naphtha, gasoline, gas oil, jet fuel and other fuel oils.

o From a classification point of view a chemical tanker means a ship constructed or adapted and used for the carriage in bulk of any liquid product listed in MARPOL, Annex II, Chapter 17. Some of the vessels are also able to carry cargoes, which are incompatible with coatings such as sulphuric acid, phosphoric acid, nitric acid.

Cargoes carried by chemical and product tankersChemicals and products account for 25% of global liquid cargo trade

PRODUCTS (19%)

o refined oil products;

o clean petroleum products (CPP)

owhite oils & aliphatic hydrocarbons

omethyl tert-butyl ether (MTBE)

o naphtha’s

o clean condensates

o jet fuels (paraffin)

o kerosene

o gasoline (contains alcohols)

o unleaded gasoline (contains MTBE)

o gas oils

o diesel

o dirty petroleum products (DPP)

CHEMICALS (6%)

o organic chemicals (40%);

o methanol, styrene, xylene, benzene

o alcohols, esters, phenols

o halogenated compounds, ketones

o saturated hydrocarbons, nitrogen compounds

o inorganic chemicals (40%);

o inorganic acids (H2SO4, H3PO4)

o other acids (nitric acid),caustics (caustic soda)

o - vegetable & animal oils;

o palm, sunflower, rape seed, coconut oil, tallow & grease (form fatty acids)

o - miscellaneous chemicals;

o molasses, alcohol, lubrication oil23.11.20155

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o Phenolic epoxy – all cargoes except strong acids (chemicals)

o Pure epoxy – alkalies, aromatics, most alcohols, oils, crude oil (products)

o Zinc silicate – all cargoes within pH 6-9, hardly any acids, alkali and veg.oils

Cargo needs to be compatible with coating if not risk of coating failure or risk ofdamage to cargo from the coating

Tank coatings compatibility with different cargoes

23 November 2015

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A ship cargo list

23 November 2015

o Coating must be resistant to cargoes intended to be carried

o Consult coatings cargo resistance guides

No tank coating fullfill all user needs

epoxy zinc

silicate

vinyl

ester

novolac siloxirane bimodal

Minimal operational

restrictions

χ χ X OK OK OK

Resistant to all cargoes χ χ X OK OK χ

Easy to clean χ χ X OK OK OK

No conditioning/recovery χ χ X χ χ OK

No/few cycling restrictions χ χ X χ χ OK

No post-curing OK OK X χ χ χ

Easy post-curing method NA NA OK OK OK OK

Long life-time χ χ OK χ χ χ

High VS / low VOC X X OK X OK OK

Few coats OK OK OK χ OK OK

Proven performance OK OK OK OK χ χ

Simple application χ OK X χ χ χ

Low temp. application, 5°C OK OK X OK X X

High temp. resistance X OK OK X X X

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Chemical resistance ”Big Mover” cargoesCompany Hempel Advanced Polymer

Coatings

PPG / Sigma PPG / Ameron Chugoku Jotun International

Coating HEMPADUR 15500 MarineLine 784 Sigma Phenguard Amercoat 253 Epicon T-800 Tankguard Special Interline 994

Inorganic chemicals

Caustic Soda + A + S A R + 3

Phosphoric acid - A** - U N NR -

Sulphuric acid - A** - U N NR -

Organic chemicals

Acetone + 19 A + 4 LS-1, 14 (X30) N R 15, 16 + 1, 20B, max 90 d.

Acrylonitrile - A - U N R 4, 16 -

Acrylonitrile, 30°C - N result of STS testing - U N NT -

Acetic acid - A - U N NR -

6% Acetic acid, 25°C - N result of STS testing - U N NR -

Benzene + A + S A R + 12

Cumene + A + S A R +

EDC + 13,19 A + 1, 4, 11 LS-1, 4, 14 LA4 R 15, 16 + 20B, 4, max 90 d.

Ethylene Glycol + A + S A R +

Methanol + 19, 28, 35°C A + 4, 11 LS-1, 14 LA1, 12, 15 R 16 + 1, 20B, 45°C, max 90d.

Methanol, 30°C + 19, 28, 35°C N result of STS testing + 4, 11 LS-1, 14 LA1, 12, 15 R 16 + 1, 20B, 45°C, max 90d.

MTBE + A + S A R +

Phenol - A - U N NR -

Styrene + A + LS-9 LA1, 12 R 1 +

Toluene + A + S A R +

UAN + A + S A R + 12, 22

Xylenes + A + S A R +

Veg. Oils & Fats

Castor Oil + 29 A + 3 S A R 3, 60°C + 2, 60°C

Coconut Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Corn Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Cottonseed Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Fish Oil + 29 A (100) + 3, 60°C S A R 3 + 2

Lard + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Groundnut Oil + 29 A (100) + 3, 60°C A R 3, 60°C + 2, 60°C

Linseed Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 50°C

Olive Oil + 29 A (100) + 3, 60°C LS-6 A R 3, 60°C + 2, 60°C

Palm oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Palm Kernal Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Rapeseed Oil + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Soyabean oil + 29 A (100) + 3, 50°C S A R 3 , 60°C + 2, 60°C

Sunflower oil + 29 A (100) + 3, 60°C LS-6 A R 3, 60°C + 2, 60°C

Tallow + 29 A (100) + 3, 60°C S A R 3, 60°C + 2, 60°C

Miscellaneous

Molasses + 10, 50°C A (100) + , 60°C S A R , 60°C + 10

23.11.20159

Chemical resistance agressive cargoesCompany Hempel Advanced Polymer

Coatings

PPG / Sigma PPG / Ameron Chugoku Jotun International

Coating HEMPADUR 15500 MarineLine 784 Sigma Phenguard Amercoat 253 Epicon T-800 Tankguard Special Interline 994

Other aggressive cargoes

Aniline + 13, 19 A + 4, 8 U LA1, 12 NR +21B, max 90 d.

Ammonia solu., 28% + A + LS-1, (X30) A R -

Butanol, 1- + A + S A R + 45°C

Butyl ether + A + 4 S LA12 R 2 +

Citric acid, 25% NT A + + A R +

Crude oil + A (100) +, 70C S A R, 70°C +

Diethanolamine + 19 A + 2 S LA1, 4, 12 NR +

Ethyl acetate + 13, 19, 28 A + 1, 4, 11 LS-1, 4 LA4 R 4 + 21B, 4, max 60 d.

Ethyl amyl ketone + 35°C A + S LA12 R 1, 15 +

Butoxyethanol, 2- + 19, 28, 35°C A + 4, 11 S LA1, 12 NT + 1, 21B, 45°C, max 60 d.

Fatty acid, C12+ + 19, 29 A (100) + 3, 8 LS-15 LA1, 3, 12 NR + 2, 20B, 50°C, max 30 d.

Formaldehyde, 37% - A - U LA1, 12 R -

Gasoline, standard + A + S A R + 16

Heptanoic acid + 19 A + 3, 8 LS (X30) N NR + 2, 20A, 50°C, max 60 d.

Hexanoic acid - A + 3, 8 S N NR -

Isopropanol + 19, 28, 35°C A + 4, 11 S LA12, 15 R 1 + 1, 21B, max 90 d.

Lubricating oil + A (100) + 16 S A R +

Methanol, 1% water + 19, 28, 35°C A - result of STS testing LS-1, 14 LA1, 12, 15 NR -

Methanol, 1% water,30C + 19, 28, 35°C N result of STS testing - result of STS testing NT NT NR -

Methoxyethanol, 2- - A + 4, 11 S LA1, 12 NT + 1, 21B, 45°C, max 60 d.

Methylene Chloride + 13, 19 A - U N NR -

Methylene Chloride, 35C + 13, 19 N result of STS testing - U N NR -

Methyl Ethyl Ketone + 19, 35°C A + 4 LS-1 (X30) LA1, 12 NR + 1, 21B, max 60 d.

Methyl Methacrylate - A + 1, 4 X N R 4 + 4, 21B

Nitrobenzene + 19 A + S A R +

Octanoic acid + 19 A + 3, 8 S N NR + 2, 20A, 50°C, max 60 d.

Oleic acid + 19, 29 A (100) + 3, 60°C LS-15 A NR + 2, 21A, 50°C, max 90 d.

Palm fatty acid destillate + 19, 29 A (100) + 3, 60°C LS-15 LA1, 3, 12 NR + 2, 60°C, max 60 d.

Potassium Hydroxide, 50% + A (100) + , 60°C S A R -

Propyl acetate + 13 A + 1 LS-1, 4 LA4 R 4 + 4

Propylbenzene + A + S A R +

Sodium hydroxide, 50% + A (100) + , 60°C S A R + 50°C

Talloil fatty acid + 19, 29 A (100) + 3, 70°C LS-15 LA1, 3, 12 NR +2, 50°C

Trichloroethylene + 13, 19 A + 1, 4 LS-1, 14 LA4, 12 R 1, 4 + 4, 21B, 45°C, max 90 d.

VAM + 13, 19 A + 1, 4, 11 LS-1, 9, 14 (X30) LA1, 4, 12 R 4, 16 + 4, 20B, 45°C, max 90 d.

23.11.201510

Cargo absorption/desorption in coatings

Ml ethanol (C2H5OH) per 100g coating

Max absorption

Residue after

4 days ventilation (20°C)

(7)

10

5.5

0.5 2

Zinc silicate Epoxy Phenolic epoxy

Ca

rgo

ab

so

rbe

dVoyage time Reconditioning

Time

Conditioning time of coatings

The conditioning time is used to restore the coating after aggressive cargoes which tend to be

absorbed in the coating film. During conditioning the cargo is desorbed by a time-dependent diffusion

The conditioning time for phenolic epoxy (HEMPADUR 15500) is 5-10 days after transportation

of cargoes with notes 19 and 28. Conditioning is obtained by either carry non-aggressive cargo

or mineral/vegetable/animal oil at 50ºC for 5 days or 60ºC for 3 days

Important to vent the tank

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o Depending on tank coating technology a certain fraction ofagressive small molecule cargoes (methanol, ethanol etc.) will be absorbed during voyage

o To avoid cargo contamination, the tank needs to be vented a certainnumber of days to condition the tank to carry the next cargo

o Ventilation to – gas free, visibly dry, completely dry

o Last cargo compatibility – incompatible cargoes (examples);

o Methanol not to be carried in tanks that has just carried ACN or monomer

o Careful with carrying water-containing cargoes in tanks that has just carried Methanol

o Careful with loading Methanol in tank that has carried Completely Denaturated Alcohol

o Odor sensitive cargoes not to be carried in tanks that has just carried strong smell or offensive cargoes

o Careful with carrying edible cargoes in tank after having carried toxic cargo

o

Cargo absorption & Conditioning

23 November 2015

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o Cargo list

o Previous carried cargo

o Conditioning time

Cargo sequencing

23 November 2015

Chemical tankers - cleaning procedures

o Cleaning with tank cleaning machines (Butterworth machines)

o Recirculation method

o Rock and roll method

o Hand spraying

o Tank steaming

Portable Butterworth machine

Fixed Butterworth machine

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o Use fixed tank cleaning machines or portable

o What was the last cargo carried?

o What is the next cargo to be carried?

o What to clean from and what to clean to?

o Water or solvent for the pre-wash?

o Reaction of the previous cargo(s) with the cargo tank coating

o Cold water or hot water and for how long?

o Tank cleaning chemicals or not?

o Removal of mineral oils – use solvent-based cleaners

o Removal of veg.oil/fish oil/fat – use alkaline / water-based cleaners

Tank cleaning the basics

23 November 2015

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To avoid contamination of following cargo and prolonglifetime of the tank coating;

o Always clean tanks after discharge of cargo

o Ventilation of tank to «gas free» state

o Wash for debris with SW or fresh water

o Consult tank cleaning guides and suppliers

o Wash with detergents/chemicals to remove residues

o Keep washing time to as short as possible and temperature of wash water as low as possible

o Ventilation to «dry state»

Tank cleaning

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o Methanol

o Methanol + Water

Be aware that water from tank cleaning or from condensing air in a tank to carry Methanol can be a problem. There are different maxwater content tolerances for different coatings

Carriage of agressive cargoes

23 November 2015

16 hours cure at 60°C

Phenolic EP Phenolic EP Phenolic EP Resorsinol EP

Hempel PPG Jotun APC

MeOH+1%

H20 + 30ºC

MeOH+1%

H20

MeOH+

> 0.1% H20

MeOH+1% H20

+ 30ºC

OK NO NO NO

Tank coating advice during service

Advice during serviceo Proper tank cleaning

Possible defectso Cargo contamination

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Surface contamination may result in cargo contamination

Tank coating advice during service

Requiremento Adhere to resistance guide

Possible defectso Premature break-down

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Tank coating advice during service

Advice during serviceo Avoid mechanical abuse

Possible defectso Premature break-down

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Do not drop tools from ladder Mobile tank cleaning machine hits bulkhead

New low temperature fast curing high functionalityepoxy tank coatingHEMPADUR 15600

Dr. Michael AamodtGlobal Product ManagerGroup Marine Marketing23 November 2015

Owners requirements for tank coating

o Both at NB and Maintenance the tank coatings should be:

o Easy to use

o Practical without strict temperature limitations at application

o Under Operation the requirements are:

o Chemical resistance according to trade

o Easy cleaning between cargoes

o Low cargo absortion and retention

o Short conditioning time between cargoes

o Long service lifetime of coating

Hempel is proud to introduce HEMPADUR 15600 – moving boundaries for epoxy tank coatings

o Allowing for Low Temperature Curing down to -5ºC(LTC)

o Very fast drying and curing (fully cured 3 days/20ºC)

o Excellent chemical resistance

o Allowing for two coat system applied in one day

o PSPC type approved both for COT and WBT

The choice of amine curative chemistry in HEMPADUR 15600 secures higher crosslink density almost on level with epoxy novolac’s so overall chemical resistance is higher than for a normal pure epoxy tank coating.

Normal epoxy tank coatings are not resistant to ethanol and methanol, since the small molecules can penetrate the crosslinked epoxy network. 15600 is resistant to FAM A & FAM B, containing ethanol and methanol.

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Amine cured epoxy ↔ LTC fast cure ↔ Phenolic epoxy

6 months exposure

in methanol

PHENOLIC EPOXY

Post-cured

Short time exposure

in methanol

Pure EPOXY

amine curedAmine cured LTC fast cure Phenolic cured

Epoxy –

epoxy

distance

“4” “4” “1”

Functionality 2 ~ 4 4

Network

Curing 7 days, 20ºC 3 days, 20ºC 10 days, 20C + heat

15400 15600 15500

Crosslinking

density, mEq/L

2,17 3,82 4,20

LTC fast cure epoxy is resistant to 3 months exposure in FAM B

containing 15% Methanol & 4 % Ethanol

IMO Resolution MSC 288.(87)Test protocol outline

o 180 days immersion testing of coated test panels immersed in a model crude oil test liquid at 60°C

o 90 days gas cabinet testing at 60°C, simulating the gas phase in the crude oil tank

MODEL CRUDE OIL COMPOSITION

Marine Fuel

Naphtenic acid (to 2.5 mg KOH/g)

Benzene/Toluene (1:1ratio) (to a total of 8% of the Fuel)

Artificial seawater (to a total of 5%w to the mixture)

H2S dissolved in a liquid carrier (5ppm in the total test liquid)

Test panels coated with 2 x 160 µm DFT epoxy on blasted Sa 2½ carbon steel

and on 2 months weathered shopprimer

HEMPADUR 15600 – keeps colour in crude oilallows for visual inspection with ROV’s

MSC 87/26 Add 1.Annex 2 – states the following about coating type;

“The topcoat shall be of light colour to facilitate in-service inspection”

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15600 after 6 months immersion testing in PSPC/COT

model crude oil, panel in middle unexposedStd. epoxy after 6 months immersion testing in PSPC/COT

model crude oil, panel in middle unexposed

Unexposed

panel

Unexposed

panelExposed panel Exposed panel Exposed panel Exposed panel

HEMPADUR 15600 - Benefits and Features

o Pure epoxy

o High volume solids

o VOC < 250 g/l (Volatile Organic Compounds)

o Hard glossy surface

o Fast drying & curing

o Wide application window

o Two coat tank coating system

o Passed IMO PSPC for cargo oil tanks

o High Tg for high temperature resistance

o Keeps color shade immersed in crude oil

o Passed IMO PSPC for water ballast tanks

o Suitable for both newbuilding and repair situations

o Reliable all year round applications from -5C and upwards

HEMPADUR tank coatings proven performers for over 30 years

Hempel offers tailor made technical advice for cargo resistance, tank cleaning, conditioning time, application, products suitability for trade pattern and cargoes carried, training etc.

HEMPADUR TANK COATINGS ARE USED ON MORE THAN 1000 SHIPS WW

THANK YOU FOR YOUR ATTENTION !

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