5.Outline

1. 5.Outline Cleaning System in Shipping Chlorinated Solvent Degreasing Introduction to Aqueous Cleaning in shipping The Disadvantages of Semi Aqueous in Shipping Problem Associated with Aqueous Cleaning System in Shipping

2. Cleaning System in Shipping • The ship cleaning or wash-down water produced when cleaning vessels may contain chemicals such as chlorine, copper, zinc, phosphates, ammonia, bio fouling, fish waste, paint chips and introduced or invasive pest species. All of these have accumulative impacts on water quality • Hull cleaning aims to ensure boats maintain their hull speed, fuel efficiency and appearance. Diver cleaning, using manual or power tools, is the most common form of in-water hull cleaning. Scrubbing hulls coated in antifouling paints releases toxic metals and possible pest species, which may contaminate the water • Cleaning and degreasing of metal parts in the metal finishing and metal working industries has traditionally been accomplished by the use of chlorinated solvents in vapour degreasers or immersion systems. • Due to concern over the ozone layer, and worker health, increasingly strict environmental regulations have been promulgated on the use of chlorinated solvents.

3. Types of Ship Cleaning • Deck Wash down Deck wash down means clean and stain a deck includes anchor cleaning and de-rusting. The wash-down water produced when cleaning vessels may contain chemicals such as chlorine, copper, zinc, phosphates, ammonia, biofouling, fish waste, paint chips and introduced or invasive pest species. All of these have detrimental and accumulative impacts on water quality. Biofouling occurs when marine life, such as algae or barnacles, attaches to any surface, including hulls, anchors or fishing gear. If the detergents or chemical used in cleaning the spillage control equipment must be used such as absorbent sausage in order to control the wash down water from discharge overboard. The wash down water need to be disposed into sewer or septic system. Deck wash down is normally be done on board ship by using soft brushes and jet water with high pressure. There are few products being used for the cleaning such as Degreaser Kleen, Enviro Spill Kleen, and Oil Spill Kleen.

4. Types of Ship Cleaning • Hull Cleaning Hull cleaning means to clear all the growth which may become friction and the cleaning enables the ship to travel efficiently through the water. Cleaning can be done either in water or in dry dock In dry dock cleaning process is using sand blasting. In water cleaning, a diver is required and by using manual or power tools. Hull Surface Treatment (HST) is a NEW environmentally friendly treatment for removing growth from a ship’s hull HST utilises thermal shock to instantly kill the growth and spores. The system does not employ paints, chemicals, detergents or any other substances that are harmful to the marine environment HST does not immediately remove the growth. When the ship sails, the dead material is stripped away from the hull by accelerated hydraulic forces and wave action. After a few weeks the hull surface is completely clean without any damage to existing antifouling or contamination to marine ecology

5. Types of Ship Cleaning • Hull Cleaning Why should consider HST

6. Types of Ship Cleaning • Propeller Polishing Propeller Polishing means to clean the propeller for better propulsion. This includes rudder Various methods are used for cleaning such as scrubbing, manual scrapping and power tool. A properly polished propeller is a necessity and must be carried out by a competent organization. Failure to do so could lead to deterioration of the propeller leading to additional problems A properly polished propeller will reduce slippage and increase vessel efficiency. If left untreated it will result in an increase of power absorption and for a fixed pitch propeller will result in a reduction of service rotational speed If not polished correctly, the fouling quickly re-establishes itself on a rough propeller. Because the cost of the underwater polish will only be a small proportion of the fuel savings, the most important factor to be considered is the quality of the polishing

7. Types of Ship Cleaning • Propeller Polishing

8. Types of Ship Cleaning • Tank Cleaning A tank cleaning means cleaning the enormous variety of chemical cargoes. Chemical tankers transport an enormous variety of chemical and oil products in global and short sea trade. Due to this variety the next cargo is almost never identical with the previous cargo. Thus tank cleaning is essential on chemical and product tankers Tank cleaning machines wash out the internal surfaces of a storage, marine or process tanks. Tank cleaning machines often use a spray washing systems. Some systems can have automated retraction or extension mechanisms to automate moving the spray head and lance into the tank In the manual tanking cleaning method, an operator must enter the tank and manually clean the internal surfaces. Operator can be exposed to toxic fumes, hazardous liquid chemicals and suffocation risks. Tank cleaning systems are safer and can be more than 10 times faster than manual methods

9. Types of Ship Cleaning Deck Wash down Propeller Polishing Hull Cleaning Tank Cleaning

10. Cleaning Product ***Solvents and Cleaners A solvent could be defined as any substance that can dissolve another substance. For example, pure water is a solvent for many polar and ionic compounds. Petroleum hydrocarbons are good solvents for many nonpolar organic compounds. In most of the industrial trade literature the term solvent refers to non-aqueous substances, whereas the term cleaner refers to substances that use water. Cleaners are water-based and generally contain additives that allow them to remove contaminants.

11. Cleaning Product

12. Cleaning Product

13. Chlorinated Solvent Degreasing Solvent degreasing is a process in which a cleaning agent is applied directly to the surface by spraying, brushing, or wiping. This process removes oil, grease, dirt, loose particles, and any other contaminants that may exist on the surface of the material Chlorinated solvents are a large family of chemical compounds that contain chlorine, carbon tetrachloride, trichloroethylene (TCE), or methylene chloride Workers can be exposed to chlorinated solvents through the absorption of solvents, through inhalation and skin contact It have been used for degreasing because they quickly dissolve organic soils such as oil, grease, and dirt from parts and residual solvent on parts evaporates rapidly, leaving them clean, dry, and ready. However, use of most chlorinated solvents is being phased out by increasingly stringent state and federal air regulations Some solvents used are ozone-depleting and global warming compounds and have risks they pose to human health. Numerous aqueous, or water-based, cleaning chemicals are now available that are significantly less toxic than chlorinated solvents

14. Reasons for Replacing Solvent Degreasing with Aqueous Cleaning : • Comply with federal and state regulations • Eliminate solvent storage and handling • Eliminate potential for accidental releases • Create safer working conditions • Eliminate air regulatory compliance costs • Eliminate solvent purchase and disposal costs • Eliminate emissions of ozone-depleting, global • Warming, and hazardous compounds

15. Alternative to Chlorinated Solvent Degreasing Mineral spirits is a solvent commonly used for part cleaning because of its ability to quickly dissolve oil, grease, and heavy lubricants. Although it is effective for cleaning, mineral spirits raise significant environmental and human health concerns: • Mineral spirits contain volatile organic compounds (VOC) that contribute to smog formation and may be toxic when inhaled. • Mineral spirits evaporate quickly, making worker exposure difficult to control. • Spent mineral spirits is a hazardous waste and the shop owner is responsible for proper disposal of all hazardous wastes. • Some areas of the country have already restricted the use of solvents in parts cleaning operations. Using solvents creates unnecessary environmental, worker health, and fire liabilities for your shop. Minimize your costs and liabilities by switching to aqueous solutions. These include aqueous cleaning, media blasting, carbon dioxide blasting, and supercritical carbon dioxide

16. Alternative to Chlorinated Solvent Degreasing • Media Blasting Is the process of removing unwanted material with an air blast that throws abrasive particles against the surface of the parts as they are cycled on a conveyor. It is often used for general maintenance and for making repairs. For example, it is often used on ships and bridges to remove paint and various coatings. • Carbon Dioxide Blasting (CO2) CO2 blasting is an alternative process to chemical cleaning and stripping. There are two basic types of CO2 blasting systems, pellet blasting for heavy cleaning and snow blasting for precision cleaning. • Supercritical Carbon Dioxide The Supercritical carbon dioxide is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure. Supercritical CO2 is becoming an important commercial and industrial solvent due to its role in chemical extraction in addition to its low toxicity and environmental impact

17. Alternative to Chlorinated Solvent Degreasing Media Blasting Carbon Dioxide Blasting (CO2) Supercritical Carbon Dioxide

18. Introduction to Aqueous Cleaning in shipping Aqueous cleaners are water-based solutions. Instead of dissolving grease and solids, aqueous cleaners rely on heat, agitation, and soap action to break dirt into smaller particles. Although they clean differently, aqueous cleaners perform as well as solvents. Aqueous cleaners are defined as water based cleaners that contain less than 5% of VOCs These agents provide multiple degrees of freedom in formulating, blending, and concentrating, and also provide useful synergistic effects. Aqueous cleaning solutions can last longer than solvents Health risks associated with aqueous cleaners are relatively low. However some aqueous cleaners contain organic substances that may be hazardous. Material Safety Data Sheets (MSDSs) for individual products should be consulted before use Aqueous cleaning is more effective at higher temperatures, and normally is performed above 120°F using suitable immersion, spray, or ultrasonic washing equipment. Good engineering practices and process controls tend to be more important in aqueous cleaning to achieve optimum and consistent results

20. Types of Aqueous Cleaning Unit Spray: Parts are sprayed with cleaning solution at high pressure in an enclosed cabinet Immersion: Parts are immersed in cleaning solution agitated by mechanical oscillation submerged spray nozzles, or ultrasonic Wet Blast: Parts are blasted with a water and abrasive medium slurry at extremely high pressure Sink-Top: Parts are manually scrubbed in a sink, and cleaning solution is applied via a nozzle or flow through brush

21. Semi-Aqueous Cleaning Semi-aqueous cleaners are made of natural or synthetic organic solvents, surfactants, corrosion inhibitors, and other additives. Water is used in some part of the cleaning process (washing and/or rinsing), hence the name, semi-aqueous The aqueous based cleaning systems addressed in this report can be divided into three cleaning methods: immersion, spray, and ultrasonic The primary pollution prevention benefit of semi aqueous cleaners is that they are non-ozone-depleting. Their use commands substantially more concern about aquatic toxicity and human exposure than does the use of aqueous cleaners. Most semi-aqueous cleaners are reported to be biodegradable. Distillation and membrane filtration technologies are being developed that will permit recycling and reuse of the products In general, the semi-aqueous cleaners have excellent, solvency for a number of difficult contaminants, such as heavy grease, tar, and waxes. Semi-aqueous cleaners are noncorrosive to most metals and generally are safe to use with most plastics

22. The Disadvantages of Semi Aqueous • While rinsing may cause corrosion of the assemblies • Material compatibility with plastics and rubbers used in equipment should guide equipment selection • Use of spraying that results in the formation of mist or finely atomized droplets can increase hazard of flammability or loss of the hydrocarbon to the exhaust. This can result in a major source of loss of the hydrocarbon. This selective loss of hydrocarbon can increase the concentration of surfactant in the wash tank • Limonene-based terpenes have a strong citrus odor that may be objectionable • Concentrated rinse water should not be discharged without prior treatment • Some hydrocarbons could be classified as volatile organic compounds which contribute to the formation of smog an air quality concern in some areas • The reproductive health problems associated with glycol ethers are a cause for serious concern • Their strong odors may become objectionable to workers, thus requiring additional ventilation in areas where they are used • Limited testing of d -limonene has yielded positive carcinogenicity results in male rats • Although semi-aqueous cleaners are biodegradable, the capacity of treatment facilities to treat wastewater must be understood. In such cases, an add-on treatment system should be considered

23. Problem Associated with Aqueous Cleaning System in Shipping • Pollution hazards Cleaning agents referred to in regulation 13.5.2 of MARPOL Annex II fall outside the scope of these guidelines and their data should not be submitted for evaluation. MARPOL Annex II regulations for the discharge of Noxious Liquid Substances include restrictions on the types of cleaning additives allowed to be used in tank washing operations as follows: "13.5.2 When small amounts of cleaning additives (detergent products) are added to water in order to facilitate tank washing, no additives containing pollution category X components shall be used except those components that are readily biodegradable and present in a total concentration of less than 10%. No restrictions additional to those applicable to the tank due to the previous cargo should apply."

24. Problem Associated with Aqueous Cleaning System in Shipping The Annex II Regulations for the control of pollution by noxious liquid substances in bulk define a four-category categorization system for noxious and liquid substances. The categories are: Category X: Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a major hazard to either marine resources or human health and, therefore, justify the prohibition of the discharge into the marine environment Category Y: Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses of the sea and therefore justify a limitation on the quality and quantity of the discharge into the marine environment Category Z: Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a minor hazard to either marine resources or human health and therefore justify less stringent restrictions on the quality and quantity of the discharge into the marine environment Other Substances: substances which have been evaluated and found to fall outside Category X, Y or Z because they are considered to present no harm to marineresources, human health, amenities or other legitimate uses of the sea when discharged into the sea from tank cleaning of deballasting operations. The discharge of bilge or ballast water or other residues or mixtures containing these substances are not subject to any requirements of MARPOL Annex II.

25. Problem Associated with Aqueous Cleaning System in Shipping • Managing aqueous cleaning wastes Do not dump waste solution in the sewer or septic system Skimmed Oil. Oil skimmed from an aqueous cleaning solution can be managed as used oil and recycled. Most recyclers will accept skimmed oil with used motor oil as long as it is not contaminated with solvent Simple sludge management little or no sludge will accumulate in aqueous cleaning units with filtration, but units without filtration may accumulate sludge at the bottom. This sludge may be disposed of along with waste solution Used filters may be recycled along with spent engine oil filters with the permission of the recycler. Contact your oil recycler to determine if they will take your filters

26. Managing aqueous cleaning wastes

27. Problem Associated with Aqueous Cleaning System in Shipping • Safety Issues in Aqueous Cleaning Worker safety issues, for aqueous cleaners, involve skin exposure, eye exposure, ingestion, inhalation, and chronic systemic exposure. Consult the label and material safety data sheet on the cleaner for warnings and safety precautions. When cleaning by hand, it is always good practice to wear protective gloves It is also considered a good industrial practice to wear safety glasses or other eye protection when working with aqueous-cleaning solutions. Particularly hazardous aqueous cleaners should have warnings and recommended eye protection on the label It is considered a good industrial practice to have some respiratory protection when working with sprays and mists in open-spray cleaning Some semi aqueous cleaners may contain volatile solvents that require special ventilation and possibly even flammability controls. The cleaner’s material safety data sheet should disclose any long-term chronic exposure concerns relating to carcinogenicity

28. Conclusion Chlorinated hydrocarbon solvents made their appearance in industry and trade at the end of 18th century. Carbon tetrachloride was the first chlorinated solvent produced for industrial purposes The primary critical effect of occupational exposure to organic solvents is the neurotoxic effect and risk of brain damage; chronic, cerebral injury. For a long time however, chlorinated solvents have been associated with a broader range of toxic effects The used of chlorinated solvent will give a risk of developing a broad range of health injuries amongst workers occupied with metal degreasing Many industries are rediscovering water (H2O) as the ideal cleaning medium, the only universal solvent truly non-toxic to both humans and the environment