Petroleum Coke – Tank Washing

Petroleum Coke – Tank Washing



Petroleum Coke Bulk Cargo: Tank washing,  Cleaning products, and Discharge implications

Comments … concerning the discharge of Petcoke hold washings.

Petroleum coke (petcoke) ia a bulk by – product of oil refining.
Among other end-uses,  it is traded as a form of fuel  (e.g. for cement manufacture)  or  an input to other industrial applications (e.g. smelting).
It is commonly transported at sea in bulk carriers.
As with most other bulk cargoes,  after discharge there remain residues in the holds and on deck   which must be cleaned before new cargoes can be loaded.

The cleaning process typically entails:
(1) dry sweeping,
(2) high pressure water washing,
(3) the application of a chemical cleaner and,
(4)  a final high pressure water wash.

In theory the dirty wash water is either
(a) disposed of at sea  or
(b) discharged for treatment  land – based reception facilities.

However,  given increasingly stringent national and international legislation  e.g. MARPOL,  it is becoming ever more important to ensure that a proper disposal route is followed.
It is also possible for vessels carrying petcoke to be involved in an incident which results in a loss of the cargo at sea.
The purpose of this bulletin is to briefly describe the physical properties of petcoke,  the environmental implications of this discharge  or  loss at sea,  the properties and effects of petcoke cleaning agents and some of the national and international policies relating to it’s disposal.

Physical Properties
Petcoke is a black powder,  granular  or  needle-like substance (see Table. 1),  consisting of carbon (74 -97%),  produced during the thermal decomposition of heavy oils in refining.
It exists in various forms,  including green coke (also known as raw  or  delayed petcoke),  calcineable, spongeneedle  or  regular petroleum coke.
Green petcoke is the product of delayed coking and contains significant hydrocarbon content.
It has a distinctive hydrocarbon smell and,  depending on the heating rate of the refining process,  can contain from 4 to 15% volatile material,  including Polycyclic Aromatic Hydrocarbons (PAH)

Table 1: Properties of Petcoke

Property1       Fuel-Grade greenAnode          Grade-Calcined
Sulphur(wt%) 2.5-5.5 1.7-3.0
Ash (wt%)   0.1-3.03 0.1-3.0
Nickel (ppm)    Not Determined    165-350
Vanadium (ppm) Not Determined   120-350
Residual 9-12 <0.25
Bulk density (g/cm3) Not Determined 0.8
Real densiity Not Determined 2.06

Calcinated petroleum coke is derived from green coke by heating to high temperature (> 1,200°C). This process removes virtually all of the hydrocarbon content  (i.e. to < 0.1%).
However in order to suppress (κατακρατω) dust a small amount (< 0.3%) of oil might be added to the cargo. This may have implications in the case of loss or disposal at sea  as the added oil may result in surface sheens. – γιαλάδα.
It is also common to use a fine water spray containing surfactants (επιφανειοδραστική ουσία)  to suppress dust.
The surfactant reduces the surface tension of the water,  thus making it more effective at wetting the cargo and reducing the volume of water necessary.
It is commonly applied in a dilute (αραιώνω)  (between 100:1 and 3,000:1) form and normally classed as non-hazardous.
The exact properties of petcoke depend on  the source of the crude oil feedstock and the heating process used.
However major components would be expected to be within the ranges illustrated in Table 1.
Trace metals such as nickel and vanadium may be present at ppm levels.
The specific gravity of petcoke ranges from  0,8 – 2,1 relative to water.
Therefore, the product specification for each cargo must be consulted to determine if it will float  or  sink. As a  rule of thumb,  most petcoke products will sink in seawater,  Petcoke is stable and insoluble αδυάλυτο in water and is therefore likely to form a slurry κοπριά / κόνιαμα if discharged at sea.

Environmental  effects of Petroleum coke
Petcoke  Material Safety Data Sheets (MSDS) the classification of petroleum substances according to the  EU  dangerous goods directive and the GESAMP / EHS composite list of hazard profiles 2003 / 20004 all state that petcoke is not considered a hazard to the marine environment.
It is also worth noting that,  although petroleum coke Is described as non-hazardous,  there are potential human health effects relating to the small particulate matter within the powder  or  granules as inhaled  (i.e.  airorn) dust.
As previously mentioned, the hydrocarbon content of green  or  raw coke may form a sheen  on the water surface although this is likely to be localized and non – persistent. ανυποχώρητος / συνεχης The greatest concern following a bulk release of petroleum coke (e.g.  in a ship casualty scenario) is the potential for smothering effects particularly in low energy  or  shallow waters where spreading and dilution is reduced.
A release near the shoreline may also cause a negative visual effect if significant black solids are washed onto the shore.
Any increases in PH  or  sheen will be short lived, given sufficient water depth and water exchange. As far as  the discharge of small quantities of petcoke within otherwise clean wash waters is concerned, it is not expected that there would be harmful effects to the marine environment as long as the hydrocarbon content of the cargo is sufficiently low.  However this comment should be read in the context of the governing legislation referred to below.

Cleaning products
As described above, the hold washing process typically also involves the use of chemical cleaning agents.  A number of specialist cleaning products are available for this purpose.  These may be general cleaning  agents  or  marketed specifically for particular cargo residues.  Some may contain hydrocarbon solvents,  while others cleanse on the basis of their caustic properties.
As such,  they too must be considered when studying the environmental implications of wash water disposal,  particularly at sea.
All cleaning products evaluated by the working group on the Evaluation of Safety and Pollution Hazards of chemicals (ESPH) and which were found  by the Marine Environmental Protection Committee to meet the requirements for potential discharge are listed in  Annex 10  of the MEPC 2 circular.. Thus,  because of their potential dilution in use and propensity to dissolve in the sea, the key to understanding the potential for environmental impact of any of such cleaning agent is the concentration profile over time following the loss  or  discharge at sea.
In other words,  the quantity involved,  the spill rate  and  the potential water exchange.

National and International guidance and restrictions on discharge
It is beyond the scope of this bulletin to outline the national and international rules on cargo related discharges,  in particular for petcoke. However, a brief note on the rules in the UK  and  US,  as well as those promulgated through the IMO,  may be useful for understanding the issues at hand.

Table 2: Summary of MARPOL discharge provisions for petcoke wash water (modified to include oily mixtures)

Type of Discharge Ships Outside Special Areas Ships within Special Areas
Non recoverable cargo residues  contained in wash water Discharge permitted >nm from the nearest land and as far as practicable  Discharge only permitted ≥12nm from the
nearest land and as far as practicable if departure and destination are both within the special area and no adequate reception facilities are available at those ports  or in an emergency situation
 Cleaning agents and additives7 contained in cargo hold wash water  Discharge permitted  Discharge only permitted ≥12nm from the nearest land and as far as practicable if departure and destination are both within the special area and no adequate reception facilities are available at those ports or in an emergency situation
 Mixed garbage   When garbage is mixed with or contaminated by other substances prohibited from discharge or having different discharge requirements, the more stringent requirements shall apply
 Oily mixtures from non tankers >400GT  Discharge is only permitted if the oil content of any bilge water discharged is below 15 parts per million (ppm); the Ship must be more than 12 nautical miles from nearest land and it must have in operation an approved oil discharge monitoring and control system, oily water separating equipment or oil filtering equipment  Discharge is only permitted if the oil content of any bilge water discharged is below 15 parts per million (ppm); the Ship must be more than 12 nautical miles from nearest land; and it must have in operation an approved oil discharge monitoring and control system, oily water separating equipment or oil filtering equipment with an alarm and automatic stopping device

Cargo residues and cleaning agents from tank washing are defined as “garbage” within the International Convention for the Prevention of Pollution from Ships (MARPOL).
Table 2 offers a simplified summary of the relevant MARPOL regulation.
The differentiation between ships within  and  outside  “special areas” is important because the discharge of petcoke cargo wash water is prohibited not only in close proximity
to the shore (12nm) but also within 6 IMO named “Special Areas” –  these include:
(a) the Mediterranean,
(b) the Gulf of Mexico,
(c) the wider Caribbean,
(d) the Baltic Sea,
(e) the North Sea,  and
(g) the Antarctic where the disposal of garbage at sea is heavily restricted.

(1) The reasoning behind the universal 12 nautical mile limit is the reduced potential for dilution and mixing in shallow coastal areas,
(2)  the reasoning behind the prohibition in special areas is that they are deemed  to be highly vulnerable to pollution and have a reduced capacity to recover.
Further any hydrocarbon “sheen” produced by discharged tank wash water would constitute a violation under MARPOL Annex 1  (concerning oil pollution).
Discharge from bilge tanks in areas where permitted must pass through an oil water separator and monitoring system,  plus the oil content of the discharge must not exceed 15ppm.

in the United States such as the Clean Water Act  (CWA),  the Act to Prevent Pollution from Ships (APPS) and several Coast Guard regulations,  implement the standards imposed by MARPOL and prohibit discharge of oily residues  or MARPOL  defined garbage within 12 nautical miles from shore.

In its guidance on the  at-sea  disposal of cargo tank washings and hatch washings, the  United Kingdom  Maritime and Coastguard Agency (MCA) states that
“… after unloading some bulk cargoes many ships will wash their holds   or  decks to remove this excess   or   split material as it could contaminate the next cargo.
In such cases this material can be disposed of at sea so long as it is inert αδρανη,  has been minimized  by removing as much cargo residue as possible and any disposal complies with the 2008 Regulations and any other relevant regulation.
If the material is a marine pollutant ,  a hazardous  or  noxious material  or  a material that could cause secondary pollution on contact with the sea  ( such as petcoke which if disposed at sea,  can cause  a sheen on the surface,  which will put the ship in contravention of Annex 1 of MARPOL 73 / 78 ),  then any washings should be disposed of on shore through appropriate reception facilities”.

Although petcoke is not officially classed as harmful to the marine environment  ( through the seven – 7 – criteria in paragraph 3.2 of the 2012 guidelines for the implementation of MARPOL Annex V and it could in theory be discharged while a vessel is en route and at last 12 nautical miles from the nearest land,  petcoke cargo residue and wash water can contain a number of harmful components such as residual hydrocarbons,  cleaning agents  or  dust suppressants.
The presence of such components in sufficient quantity could therefore result in a particular cargo residue be considered as harmful to  the marine environment.
Generally, the impacts of a discharge of petcoke residue and cleaning products within hold wash water will depend on the (1) volume and the (2) location of the discharge.
However the most likely impact is that an oily sheen / γιαλάδα  may be visible on the water surface for a short time in the immediate vicinity of the discharge, with a localized and short term increase in the PH of the seawater.
If the discharge is undertaken in (3) sufficient depth of seawater with (4) currents allowing a good water exchange,  it is likely that any residues will quickly dissipate.
Finally it is worth noting that the legislation regarding the discharge of any hold wash water from vessels is complicated,  whether nationally  or  internationally.
The minimum requirements worldwide tend to be in line with the MARPOL, recommendations ( for example as outlined in Table 2 ),  but may be more stringent in certain locations.
As a result, operators are finding it ever more prudent to transfer tank wash water to shore side facilities for processing rather than discharge at sea in order to avoid potential environmental issues and possible litigation or fines. This is also true for petcoke wash water.