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MTS2010-0207 EMERGING TECHNOLOGIES for TREATING CONTAMINANTS in MARINE WASTEWATER Don Nguyen Coffin World Water Systems Irvine, CA, USA ABSTRACT Contribution

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MTS2010-0207 EMERGING TECHNOLOGIES for TREATING CONTAMINANTS in MARINE WASTEWATER Don Nguyen Coffin World Water Systems Irvine, CA, USA ABSTRACT Contribution Proceedings of the ASME/USCG 2010 2nd Workshop on Marine Technology and Standards MTS2010 July 29-30, 2010, Washington, DC, USA MTS2010-0207 EMERGING TECHNOLOGIES FOR TREATING CONTAMINANTS IN MARINE WASTEWATER Don Nguyen Coffin World Water Systems Irvine, CA, USA ABSTRACT contribution. Historically, oily bilge water has been treated using Oil/Water Separator technology (OWS) Contaminants in marine wastewater facing current or or discharged with minimal treatment. Bilge water is near-future regulations can be broadly categorized to not exactly water but a mixture of varied amounts of Downloaded from http://asmedigitalcollection.asme.org/MTS/proceedings-pdf/MTS2010/99397/58/2520471/mts2010-0207.pdf by guest on 01 October 2021 free oil & suspended solids, emulsified oil and fresh water, sea water, oil, sludge, chemicals and dissolved solids, and biological organisms. The first various other fluids. Sea water and fresh water can category of contaminants has been treated by find its way to the bilge wells due to leakage in the commercially available OWS systems. The second pipe lines, leaky pump and valve glands, from class of contaminants, emulsified oils and dissolved machinery, propulsion system, over flowing of tanks solids, has been effectively treated by UF membrane and even due to accidental spills. All these substances filtration and to a less extent by biological oxidation get accumulated in the bilge wells and the mixture and surface modified filters. A survey of recent formed is known as bilge water. Currently all advances in physical and chemical demulsification overboard water has to strictly comply with MEPC technologies to enhance emulsified oil removal with 107/49 as specified by IMO and MARPOL, which sets reduced loads on membrane was conducted. The the limit for all oil discharges, free and emulsified, to study also identified new applications for treatments of less than15 ppm. biological organisms in ballast water. A variety of technologies have arisen to fill the gap NOMENCLATURE between OWS Capability and discharge standards. Among these are systems based on gravity separation, BOD Biological Oxygen Demand, mg/l or size separation, chemical affinity separation and ppm flocculation. There has also been a gap between COD Chemical Oxygen Demand mg/l or regulation and enforcement. Unregulated discharges ppm have been problematic. There have been significant CM Coalescent Media advances in the ability to detect such discharges in the DAF Dissolved Air Flotation past few years; the most significant is Synthetic HLB Hydrophile – Lipophile Balance Aperture Radar (SAR). This paper will review IMO International Maritime Organization developments in oily bilge water treatment. IAF Induced Air Flotation MARPOL Marine Pollution, International REVIEW OF BILGE WATER PROPERTIES Convention for the Prevention of Pollution from Ships, 1973 as AND ESTABLISHED TREATMENT modified by the Protocol of 1978 TECHNOLOGIES MEPC The Marine Environment Protection 1. Survey of Bilge Water Composition Committee OWS Oil Water Separator TDS Total Dissolve Solids, mg/l or ppm A survey of more than 40 bilge samples indicated that TSS Total Suspended Solids, mg/l or ppm most solids are in dissolved form (average TDS= TO&G Total Oil & Grease or n-Hexane 18008 ppm). TDS includes dissolved oil, the majority extractable materials, mg/l or ppm of emulsified oil, dissolved COD & BOD, salts, and a US Ultrasound small fraction of dissolved metals. TSS is derived from of silt, rust, sand, grits, and even red clay. INTRODUCTION Some major Bilge Water compositions are listed in Table A. There is lacking of any typical values for A bilge is the lowest space of a ship. It is the area bilge properties. For example, TSS can vary between where two sides of the ship meet. Of the oil released 1000 ppm and 38,000 ppm, depending on the ages, by vessels, 25% is reported to come from spills and sizes, and crew practices of the vessels. The average 75% from operational discharges. Oily bilge discharge fraction of emulsified oil can be estimated to be about is second only to oily ballast tank discharge in its 30% of the total TO&G. 58 Published with permission. Table A: Properties of Bilge Water Based on Table B: Surfactant Activity Based on HLB more than 40 Bilge Samples Appearance in Water HLB Range Average , Range, No Dispersability 1-4 ppm ppm Poor Dispersion 3-6 TDS 18000 1000 - 38000 Milky Dispersion After 6-8 TSS 900 40 - 16000 Agitation Downloaded from http://asmedigitalcollection.asme.org/MTS/proceedings-pdf/MTS2010/99397/58/2520471/mts2010-0207.pdf by guest on 01 October 2021 TO&G 1100 20- 46000 Stable Milky Dispersion 8-10 C6 N D 200-400 Translucent To Clear 10-13 C10 250 0-8000 Clear Solution 13+ C22 0-18000 Fe 15 1.4-43.4 As oil droplets coalesce from smaller to bigger sizes, COD 70-11000 they impart significant color change from gray, bluish- BOD 5-15000 white, to milky white. The color change can be used to classify into broad categories of water-oil mixtures Size distributions of solids from limited number of such as gray, bluish, or white oily water (Table C). samples were found to vary from normal to bimodal distributions with the median vary between 15 µm to Table C: Color of Emulsion Based on Particle 60 µm. Sizes Bilge water is a chemically complex mixture of Particle size (µm) Emulsion appearance solvents, surface active agents (surfactants, i.e. soap), Macro globules Droplets may be visibly metal salts such as greases and lubricants and tramp >150 µm distinguished oils (i.e. compressor condensate). Some of the above 10 µm-100µm Milky white emulsion are polyaromatic hydrocarbons and chlorinated 1.0µm-10µm Bluish-white emulsion aromatic hydrocarbons. Others such as aromatic 0.05µm-1µm Smoky gray, semitransparent hydrocarbons and oil, copper, iron, mercury, zinc and <0.05 Transparent micro emulsion nickel, organic metal salts in addition to detergents and solvents are aquatic toxins. 2. Review of principles of OWS (Oil Water Generally speaking organic non-polar compounds Separator technology) (oils) are not soluble in water. However if solids, solvents or surfactants are present, oils will tend to Oil water separators are gravity separation devices emulsify in water. The degree of emulsification is which utilize a difference in buoyancy of two inversely proportional to the buoyancy of the micelles. immiscible liquids to achieve separation. For oily bilge If sufficient emulsification occurs to achieve neutral or water, the separation is of the dispersed oil droplet closed to neutral buoyancy gravity separation devices from the continuous water phase. All chemical and lose their effectiveness in separating the organic mechanical methods of oil separation conform to compounds from water. One way to gauge the relative Stoke’s law: solubility of a surfactant and thereby the type and stability of the emulsion is the HLB (Hydrophile – 2 Lipophile Balance) method (9). In this method a V = [2(ρo- ρw) g R ] / [9µ] number between 1 and 40 is assigned to many V = oil droplet rise velocity commercial emulsifying agents, which is indicative of ρo- ρw = Oil –water density differential the balance of hydrophilic to lipophilic portions of the R = Mean radius of oil droplets molecule. The higher the HLB, the more water-soluble µ = Water viscosity the material becomes (Table B). The water solubility o of an emulsion or a surfactant can be used to make an Typical properties of water and oil at 30 C were used approximation of its HLB which is indicative of the to estimate the rising velocity of oil droplets as a stability of the emulsion. function of droplet sizes. The following graph indicates that the rise velocity becomes much faster for larger droplet sizes (Figure 1). 59 Figure 2: Coalescent Media (CM) Manufactured by Figure 1: HD-QPAC and Brentwood Downloaded from http://asmedigitalcollection.asme.org/MTS/proceedings-pdf/MTS2010/99397/58/2520471/mts2010-0207.pdf by guest on 01 October 2021 Traditional OWS equipment is mostly effective when oil and water are presented in two discrete phases. Oil particles have a natural tendency to aggregate on contact. The momentum for collision has to be minimized to prevent the breakup of the larger oil droplets since oil surface tension is much lower than water. It is therefore important to maintain a laminar flow with a Reynolds number within 50 for the separation based on Stoke’s law to be dominant. Oil aggregation is enhanced by coalescing media. The coalescent media (CM) has surface properties that are not only hydrophobic but also oleophilic. As the oil droplets contact the CM surface, a new CM-oil interface is preferred to oil-water interface. The media provides oleophilic surfaces for a deposit of oil droplets as long as the surrounding flow is gentle or laminar. Oils droplets increase in sizes by absorbing Brentwood CM has cross-hatched channels at angles each other to minimize the droplet surface areas. A of 600 to 90o to vertical (Figure 2). Channeling threshold is reached when the droplets are large occurs if the connecting holes between cross hatched enough for the buoyancy force to overcome the media channels are plugged up over times. CM close to the surface affinity. This happens when the droplet inlet can be under-utilized if this occurs. CM should diameters are in the ranges of 40-60 µm. The oil have as high as possible surface area/volume. Too droplets rise to the water surface to be separated. high surface area can lead to plugging because of When emulsification or solvation occurs buoyancy grease and sludge blocking of the narrower flow differences are too small to be separated by the gravity channels. HD-QPAC CM is designed to have flow o differences. Upstream pretreatment or downstream channels at 90 to vertical dripping rods.
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