USRE41859E1 - Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful aquatic nuisance species by simultaneous hypercapnia, hypoxia and acidic ph level - Google Patents
Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful aquatic nuisance species by simultaneous hypercapnia, hypoxia and acidic ph level Download PDFInfo
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- USRE41859E1 USRE41859E1 US11/484,828 US48482806A USRE41859E US RE41859 E1 USRE41859 E1 US RE41859E1 US 48482806 A US48482806 A US 48482806A US RE41859 E USRE41859 E US RE41859E
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- ballast water
- gaseous mixture
- carbon dioxide
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- oxygen
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63J—AUXILIARIES ON VESSELS
- B63J4/00—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for
- B63J4/002—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for for treating ballast water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/931—Zebra mussel mitigation or treatment
Definitions
- the present invention generally concerns shipboard design to combat Aquatic Nuisance Species (ANS) invasion resulting from ballast water discharge.
- ANS Aquatic Nuisance Species
- the present invention particularly concerns ballast water treatment, deoxygenation and carbonation of ballast water, reduction of pH in ballast water, infusion of inert gas into ballast water, control of aquatic nuisance species, bubbling of inert gas through and into ballast water, and elevated CO 2 levels in ballast water.
- ballast water transport is a major vector for introduction of potentially invasive aquatic species.
- BWE Ballast Water Exchange
- Cangelosi (2002) states “ . . . the Coast Guard has set forth a “do-it-yourself” approach, directing interested ship owners to conduct complex shipboard experiments (post-installation) to undertake direct and real-time comparisons between BWE and treatment. If the comparison is favorable and defensible, the Coast Guard will approve the treatment. See Cangelosi, Allegra (Nov. 14, 2002). Testimony Before the Joint Committee on Resources and Science of the U.S. House of Representatives.
- Glosten (2002) provides a review of the numerous treatment systems for the control of aquatic nuisance species in ship's ballast water. These systems include heat, cyclonic separation, filtration, chemical biocides, ultraviolet light radiation, ultrasound, and magnetic/electric field. See Glosten-Herbert-Hyde Marine (April, 2002). “Full-Scale Design Studies of Ballast Water Treatment Systems”, Prepared for Great Lakes Ballast Technology Demonstration Project.
- ballast water dissolved O 2 level was reduced and held to concentrations at or below 0.8 mg/l by bubbling essentially pure nitrogen. See Tamburri, M. N., Wasson K., and Matsuda, M. (2002). Ballast water deoxygenation can prevent aquatic introductions while reducing ship corrosion. Biological Conservation. 103, 331-341. The experiments resulted in a treatment “that can dramatically reduce the survivorship of most organisms found in the ballast water . . . ”
- the process involves the exchange of gases, the extraction of the dissolved O 2 and the introduction of CO 2 .
- Surface contact area and partial pressure differentials permit the gas exchanges to occur.
- the deoxygenation of the ballast water is based on Henry's Law of gas solubility: The relative proportion of any dissolved gas including oxygen in the ballast water is a function of the concentration, equivalent to partial pressure of the gas (e.g. oxygen), within the mixed gases over the ballast water.
- the depletion of oxygen in the ballast water is primarily a function of the shared surfaces and concentrations at the interfaces of the inert gases and water.
- the user of gaseous underpressure in the treatment of ship's ballast water so as to combat Aquatic Nuisance Species (ANS) invasion resulting from ballast water discharge, described in this application, is an extension of American Underpressure System (AUPS) of MH Systems, San Diego, Calif.
- the AUPS utilizes a slight negative pressure in the tank's ullage space, in an inert environment, to prevent or minimize oil spillage from tankers (Husain et al. 2001). See Husain, M., Apple, R., Thompson, G. and Sharpe, R. (2001); Full Scale Test, American Underpressure System (AUPS) on USNS Shoshone, presented to Northern California Section, SNAME, September 2001.
- U.S. Pat. No. 5,156,109 for a System to reduce spillage of oil due to rupture of ship's tank
- U.S. Pat. No. 5,092,259 for Inert gas control in a system to reduce spillage of oil due to rupture of ship's tank.
- U.S. Pat. No. 5,343,822 for Emergency transfer of oil from a ruptured ship's tank to a receiving vessel or container, particularly during the maintenance of an under-pressure in the tank
- U.S. Pat. No. 5,323,724 for a Closed vapor control system for the ullage spaces of an oil tanker, including during a continuous maintenance of an ullage space underpressure
- U.S. Pat. No. 5,285,745 for System to reduce spillage of oil due to rupture of the tanks of unmanned barges. All patents are to the selfsame inventor Mo Husain who is one of the co-inventors of the present invention.
- the AUPS is retrofittable on existing tankers, and has the similar spill avoidance capability as that of a double hull tanker during accidental rupture of the hull.
- the AUPS spill avoidance system creates a slight vacuum (two to four pounds per square inch) in each cargo tank. This vacuum, assisted by the outside hydrostatic pressure of the surrounding water, prevents or minimizes cargo loss in the event of hull rupture. In case of a bottom rupture caused by grounding, nearly all of the cargo can be protected. In the case of side hull damage, cargo below the level of the damage will be lost, while the cargo above the side hull rupture will be protected.
- the AUPS consists essentially of exhaust blowers with their isolation and control valves tapping into the inert gas system.
- a negative pressure of inert gas is created in the ullage space—the volume of gas above the oil. This negative pressure or underpressure is continuously adjusted and prevents oil from spilling if the tanker is ruptured. Stated simply, the oil is held in the tank by the slight underpressure.
- a bottom rupture caused by grounding nearly all of the cargo can be protected.
- cargo below the level of the damage will be lost, while the cargo above the side hull rupture will be protected.
- the first related predecessor application may be considered to teach the control of oxygen in ship's ballast water maintained under a pressure less than atmosphere for the inducement, at different times, of both such (i) oxygen-starved and (ii) oxygen-rich conditions as are respectively fatal (i) to aerobic marine organisms (by action of hypoxia), and (ii) to anaerobic marine organisms (by action of exposure to high levels of dissolved oxygen).
- the present application will be seen to teach the inducement of each of (i) carbon dioxide-rich, (ii) acid-enhanced and/or (iii) oxygen-starved conditions in ship's ballast water—preferably as is continuously maintained under a pressure less than atmosphere pressure—so as to induce, at one and the same time, (i) hypercapnic, (ii) acidic and/or (iii) hypoxic conditions that are fatal to both aerobic, and anaerobic, marine organisms.
- the present invention contemplates the infusion of inert, or combustion, gases into ballast water—preferably as is maintained under less than atmospheric pressure—in order to kill harmful aquatic nuisance species by simultaneous, synergistic, inducement of (1) hypercapnia (elevated concentration of dissolved CO 2 ), (2) hypoxia (depressed concentration of dissolved O 2 ), and (3) acidic pH level.
- the inert combustion gases may be obtained, for example, from (i) a ship's inert gas generator (of the Holec, or equivalent types), and/or from (ii) ship's own flue gases. These gases are highly noxious, having CO 2 significantly increased and O 2 significantly depleted, from normal atmospheric levels.
- the Present Invention starts With Inducing (1) Hypercapnia, and, in Association with Elevated CO 2 , (2) Depressed pH
- the present invention contemplates the control of Aquatic Nuisance Species (ANS) present in the ballast water of ship's ballast tanks by action of inducing hypercapnia (fatally elevated CO 2 levels) in marine organisms present within the ballast water.
- hypercapnia fatally elevated CO 2 levels
- the same elevated CO 2 levels as induce hypercapnia also serve to acidify the sea water.
- This condition of enhanced dissolved CO 2 is of an extreme level such as strongly induces hypercapnia in marine organisms—is, in accordance with the present invention, preferably realized by infusion of a mixture gases into the seawater, which gaseous mixture is preferably enhanced in CO 2 to ⁇ 11% by molar volume and, more preferably, to ⁇ 15% by molar volume.
- these gases enhanced in CO 2 are preferably realized as the gaseous output of a standard shipboard inert gas generator (commonly called a Holec generator, after the major manufacturer thereof) (which output is commonly about 84% Nitrogen, 12-14% CO 2 and 2% Oxygen), and/or as a ship's own flue gases.
- CO 2 concentrations may be compared with, by way of example, published studies of hypercapnia in marine organisms that have generally investigated introduction of gaseous mixtures having CO 2 concentrations in the range from 0.1% to 1%.
- effective delivery of the gases high in CO 2 concentration into ballast water will be realized by bubbling these gases into a ballast water from the bottom of a ballast water tank that is maintained at pressure less than atmosphere (called an “underpressure” in this and in related patent applications)—but this aspect of the invention will be further dealt with later.
- the infusion of the gases enhanced in percentage CO 2 is preferably continued until dissolved CO 2 in the ballast water is raised to ⁇ 20 ppm, and more preferably to ⁇ 50 ppm.
- Dissolved CO 2 of this level serves to acidify sea water.
- the chemical mechanism by which enhanced dissolved CO 2 acidifies seawater is well established, and is: CO 2 +H 2 O ⁇ H 2 CO 3 ⁇ H + +HCO 3 ⁇
- Dissolved CO 2 of the preferred levels of ⁇ 20 ppm reduces the pH of seawater, which is normally 8, to acidic levels of pH ⁇ 7, and, preferably, pH ⁇ 6 and still more preferably pH ⁇ 5.5.
- the present invention contemplates not to stop with simply inducing conditions in ballast water that are both hypercapnic and acidic to ANS—injurious and fatal to ANS as these conditions alone may be—but to continue by depriving these ANS of oxygen at the same time.
- this extension and enhancement of the present invention is based on the recognition that (i) aquatic nuisance species present in ship's ballast water may best be controlled by a combination of hypoxic, hypercapnic and acidic conditions within the ballast water, and that (ii) these conditions may be simultaneously economically realized by bubbling gases from an inert gas generator, and/or the flue gases of the ship, through the ballast water, preferably as the ballast water is maintained under a pressure less than atmosphere.
- the oxygen content of a gaseous mixture that infused with ballast water is preferably ⁇ 4% O 2 , and is more preferably ⁇ 3% O 2 , and this infusion of is continued until a dissolved oxygen level of, preferably, ⁇ 1 ppm O 2 and, more preferably, ⁇ 0.8 ppm O 2 is induced.
- the most preferred method of the invention is managing at least three different conditions—each of two dissolved gases, and acidity/alkalinity—all at the same time.
- hypoxia or lack of oxygen
- hypercapnia an excess of carbon dioxide—nor acidity—a pH less than seven.
- oxygen present in ullage space gases and/or as a dissolved gas in ballast water may be replaced with nitrogen without appreciable effect on either (i) the dissolved carbon dioxide within, or (ii) the pH balance of, the ballast water.
- hypoxia does not mandate hypoxia, nor an acidic pH.
- the carbon dioxide level in the enclosed atmosphere of a submarine can, as a product of human respiration, rise to high levels but that it is “scrubbed” from the atmosphere.
- the build-up of CO 2 can transpire in an enclosed space nonetheless that the atmosphere may constantly contain copious oxygen (derived on a nuclear submarine from the electrolysis of water with electricity).
- the Present Invention Realizes Gaseous Exchange in Ballast Water Efficiency, and Effectively
- the preferred ballast water treatment method in accordance with the present invention consists of (i) bubbling an oxygen-depleted, CO 2 -enhanced, inert gas mixture via a row of pipes (orifices at the bottom of the pipes) located at the bottom of a ballast water tank, while (ii) maintaining a negative pressures of ⁇ 2 psi at the ullage space of the same ballast water tank.
- the bubbling at, and during, an underpressure in the ballast water tanks makes that (some) exchange of dissolved gases is realized by (i) outgassing as transpires over the huge combined surface area of the bubbles, as opposed to (ii) mere slow diffusion of dissolved gases through the ballast water, with gaseous interchange occurring essentially only at the surface layer of the tank.
- the inert gas is preferably from a standard shipboard inert gas generator (commonly called a Holec generator), and is commonly composed of about 84% Nitrogen, 12-14% CO 2 and 2%-4% Oxygen.
- the ballast water is equilibrated with gases from the inert gas generator. As a result, the water will become hypoxia, will contain CO 2 levels much higher than normal, and the pH will drop from the normal pH of seawater (pH 8) to approximately pH 6.
- Ballast water treatment in accordance with the present invention has undergone preliminary laboratory tests at the Scripps Institution of Oceanography, La Jolla, Calif. USA, and has realized the results reported in this specification.
- the present invention is embodied in a method of killing aquatic nuisance species in ship's ballast water.
- the base method consists simply of infusing carbon dioxide into the ship's ballast water at a level effective to kill aquatic nuisance species by hypercapnia.
- the infusing is preferably with a gaseous mixture of ⁇ 11% carbon dioxide by molar volume.
- This infusing with the gaseous mixture of ⁇ 11% carbon dioxide preferably transpires until the ballast water is hypercapnic to ⁇ 5 ppm dissolved carbon dioxide.
- This infusing preferably transpires by bubbling the gaseous mixture through the ballast water, and more preferably by bubbling of the gaseous mixture is through the ballast water that is under less than atmospheric pressure.
- the ballast water under less than atmospheric pressure is preferably located within ballast water tanks of the ship where ullage space gas pressure is ⁇ 2 p.s.i. below atmospheric pressure, or lower.
- the base method is preferably expanded, or enlarged, to include concurrently depleting oxygen in the ship's ballast water at a level effective to kill aquatic nuisance species by hypoxia.
- the infusing is preferably like as in the base method, with the depleting preferably transpiring by substitution of gases, including oxygen gas dissolved in the ballast water, with a gaseous mixture of ⁇ 4% oxygen.
- gases including oxygen gas dissolved in the ballast water
- a gaseous mixture of ⁇ 4% oxygen preferably transpires until the ballast water is hypoxic to ⁇ 1% ppm dissolved oxygen.
- the depleting transpires by bubbling the gaseous mixture through the ballast water.
- This bubbling of the gaseous mixture is again through the ballast water that is under less than atmospheric pressure, and is more preferably through ballast water within ballast water tanks of the ship where tank ullage space gas pressure is ⁇ 2 p.s.i. below atmospheric pressure, or lower.
- the infusing and/or the depleting may be, and preferably is, accompanied by acidifying of the ship's ballast water at a level effective to kill aquatic nuisance species.
- This acidifying is a consequence of the infusing where, as is preferred, the infusing is with a gaseous mixture of ⁇ 11% carbon dioxide by molar volume. In this case the acidifying is then concurrently realized by the chemical reaction CO 2 +H 2 O ⁇ H 2 CO 3 ⁇ H + +HCO 3 ⁇ .
- the infusing with the gaseous mixture of ⁇ 11% carbon dioxide preferably transpires until both (1) the ballast water is hypercapnic to ⁇ 20 ppm carbon dioxide, and (2) the same ballast water is acidic to pH ⁇ 7.
- the infusing and, consequent to the infusing, the acidifying preferably transpires by bubbling the gaseous mixture through the ballast water, and more preferably through the ballast water that is under less than atmospheric pressure, most preferably ⁇ 2 p.s.i. below atmospheric pressure, or lower.
- the infusing (of CO 2 ) preferably transpires the same in the basis, and in the extended, methods, so also does the depleting (of O 2 ) preferably transpire the same even when the consequence of the depleting is measured in the acidification, or the lowering of the pH of the ballast water, instead of, or in addition to, the inducing of hypercapnic and/or hypoxia conditions.
- the depleting (of CO 2 ) and/or the depleting (of O 2 ) preferably transpires by the same bubbling process, most preferably into ballast water at less than atmospheric pressure, when the consequence of the depleting is measured in the acidification, or the lowering of the pH of the ballast water, instead of, or in addition to, the inducing of hypocapnic and/or hypoxia conditions.
- the present invention may be considered to be embodied in a quantitative method of reducing survival of aquatic nuisance species in ship's ballast water that is, in the preferred parameters of its conduct, quite unlike any prior art with which the inventors are acquainted.
- the method of the present invention renders ballast water triply deadly to aquatic nuisance species due to each of hypoxia, hypercapnic and acidic conditions.
- a gaseous mixture consisting essentially of ⁇ 80% nitrogen, ⁇ 11% carbon dioxide and ⁇ 4% oxygen through ship's ballast water until the ballast water is permeated to equilibrium with these gases, at which time the ballast water will be hypoxia to ⁇ 1 ppm oxygen, hypercapnic to a ⁇ 20 ppm carbon dioxide, and acidic to pH ⁇ 7.
- the permeated gaseous mixture is preferably the output of a marine inert gas generator.
- This gaseous mixture that is output from a marine inert gas generator consists essentially of nitrogen in the range from 87% to 84% mole percent, carbon dioxide in the range from 14% to 11% mole percent, and oxygen in the range from 2% to 4% mole percent.
- the permeation is most preferably continued until the ship's ballast water until the ballast water is hypoxic to ⁇ 0.8 ppm oxygen, hypercapnic to ⁇ 50 ppm carbon dioxide, and acidic to pH ⁇ 6.
- the gaseous mixture is preferably permeated to equilibrium within the ballast water by being bubbled through the ballast water, and more preferably through ballast water that is at a pressure less than atmosphere.
- the present invention is embodied in a system for reducing survival of aquatic nuisance species in ship's ballast water.
- the preferred system includes (1) a gas generator producing a gaseous mixture enhanced in carbon dioxide relative to both (i) atmospheric proportion of carbon dioxide, and (ii) proportion of carbon dioxide that is dissolved in sea water, (2) piping having and defining discharge orifices at the base of, and inside, the ship's ballast water tank; and (3) a compressor pressuring the gaseous mixture received from the gas generator sufficiently so that, as delivered to the piping, it will be forced out the discharge orifices and bubble upward through the ballast water.
- gaseous interchange transpires between (i) the gaseous mixture, enhanced in carbon dioxide, that is within the bubbles and (ii) dissolved gases within the ballast water.
- This gaseous interchange transpires until dissolved gases within the ballast water will become enhanced in carbon dioxide to a level inducing hypercapnia in aquatic nuisance species within the ballast water.
- the gas generator preferably produces a gaseous mixture having ⁇ 11% carbon dioxide by molar volume.
- This basic system is preferably expanded and enhanced by causing that the same gas generator producing the gaseous mixture enhanced in carbon dioxide also produces the gaseous mixture that is concurrently diminished in oxygen over both (i) atmospheric proportion of oxygen, and (ii) proportion of oxygen dissolved in sea water.
- the gas generator is thus called an “inert” gas generator.
- the inert gas generator preferably produces a gaseous mixture having ⁇ 11% carbon dioxide by molar volume, and, most preferably, ⁇ 4% oxygen by molar volume.
- a blower preferably evacuates gases from within the ullage space of the ship's tank so as to produce a pressure therein which is at least 2 p.s.i. less than prevailing atmospheric pressure outside the tank.
- the piping preferably includes a matrix of piping in a grid array at the base of, and inside, the ship's ballast water tank. Discharge orifices of this piping are variously directed both upwards toward the top and the tank and downwards towards the base of the tank.
- the compressor preferably produces a pressure more than 2 p.s.i. greater than a hydrostatic pressure then prevailing at the base of the ship's ullage tank.
- the system preferably serves to render the ballast water hypoxic to ⁇ 1 ppm oxygen, hypercapnic to ⁇ 20 ppm carbon dioxide, and acidic to pH ⁇ 7.
- ballast water gaseous infusion system is sized to (i) the task at hand, (ii) the time available for the completion of the task, and (iii) the resilience to die off (from hypercapnia, anoxia and acidic conditions) of the ANS to hand, all at an adequate safety margin.
- ballast water on a ship will be treated so as to reach desired dissolved gas levels in less than, most preferably, one day, and will be held at those levels for, most preferably, at least two days, and more commonly more than four days. It is, or course, totally acceptable and beneficial to hold the conditions that kill ANS for weeks and longer, should the usage of the ship and its ballast tanks so permit. There is no harm incurred in dumping ballast water having those gas concentrations that are, in accordance with the present invention, different from normal seawater into the sea, where the evacuated ballast water is so quickly diluted that it is not deemed capable of harming even the most delicate marine organisms proximate the release point.
- FIG. 1 shows a schematic of an experimental setup consonant with the principles, system and methods of the ballast water treatment of the present invention.
- FIG. 2 is a Table 1 containing data on the effects of an “inert gas”, called trimix and being a commercially available gas mixture of 2% oxygen, 12% CO 2 and 84% nitrogen resembling the gas generated by commercially used marine “inert gas generators”, on marine organisms commonly regionally identified as aquatic nuisance species.
- an “inert gas” called trimix and being a commercially available gas mixture of 2% oxygen, 12% CO 2 and 84% nitrogen resembling the gas generated by commercially used marine “inert gas generators”, on marine organisms commonly regionally identified as aquatic nuisance species.
- FIG. 3 is a Table 2 containing data on the capacities of the ballast water tanks of an exemplary ballast water treatment system in accordance with the present invention.
- FIG. 4a shows an inboard profile, deck plan view, piping layout, nozzle detail and section through a ballast tank part of the ballast water treatment system of the present invention.
- FIG. 4b shows a schematic diagram of the preferred embodiment of a ship's ballast water treatment system in accordance with the present invention the tank of which was previously seen in FIG. 4 a.
- FIG. 5 consisting of FIGS. 5a through 5d , are views of the installation of the ship's ballast water treatment system in accordance with the present invention, previously seen in FIG. 4b , on an exemplary ship.
- FIG. 6 is a Table 3 listing the principal parts and materials together with estimated prices and labor costs, circa 2003, in the exemplary ballast water treatment system in accordance with the present invention.
- FIG. 1 The schematic of an experimental setup in validation of the principles and methods of the present invention (and also, a miniature scale, the gaseous exchange system) is shown in FIG. 1 .
- Three parallel incubations were done for each experiment. Several organisms were incubated in 1.5 l of seawater at 22° C. in large Erlenmeyer flasks. Each incubation was equilibrated with the respective gas using aquarium stones before any organisms were introduced. The aerobic control was bubbled from an aquarium pump for approximately 15 min and left open to the atmosphere after addition of specimens. An anaerobic incubation was bubbled with 99.998% nitrogen for 15 min. After introduction of the organisms, the bubbling was continued for another 10 min and then the container was closed with a rubber stopper or the bubbling was continued.
- the incubation in trimix was treated similarly except that the gas mix was used instead of nitrogen.
- the oxygen concentrations were measured after the initial bubbling period using a Strathkelvin oxygen electrode with a Cameron instruments OM-200 oxygen analyzer. Values of pH were determined using a combination electrode and a Radiometer pH meter.
- the shrimp and crabs incubated in “trimix” were dead after 15 min and 75 min, respectively. Even a transfer into aerated water did not result in any movement.
- the brittle stars incubated under nitrogen started to move again after transferred into aerated water. All the mussels incubated in nitrogen and “trimix” were open after 95 min but only the ones in nitrogen still responded to tactile stimuli by closing their shells.
- the barnacles were judged dead after incubation in “trimix” when they did not withdraw their feet when disturbed, the ones incubated in nitrogen still behaved normally.
- the plankton sample mainly contained copepods. They stopped moving after 15 min and could not be revived in nitrogen and “trimix” incubations.
- Table 1 of FIG. 2 showing the effects of trimix on marine species where the trimix is 2% oxygen, 12% CO 2 and 86% nitrogen.
- Oxygen may not be available to an organism because no water for respiratory purposes is present, e.g., during low tide in the intertidal zone. Oxygen may also be removed in stagnant waters due to bacterial or other “life based” actions, e.g., in ocean basins, fjords, tide pools, or in waters with high organic content and consequently high bacterial counts, e.g., in sewage, mangrove swamps, paper mill effluent. In addition, oxygen can also be removed by chemical reactions, e.g., in hot springs, industrial effluents. The manuscript by Tamburri et al.
- trimix in accordance with the present invention combines both hypoxic and hypercapnic effects on marine organisms, including aquatic nuisance species. Preliminary results demonstrate the effectiveness of this combination in quickly killing a variety of sample organisms. Contrary to methods using additions of biocides or any chemicals in general, nothing is added to the ballast water and, therefore, nothing will be released into the environment when it is released again. Methods using radiation, heating, or filtering ballast water before or during a ship's trip, are much more expensive. The equipment needed to establish a rapid gassing of ballast water is available off the shelf and has been used in the marine environment. The plumbing and gas release equipment has been optimized and has been used in application such as aquaculture, sewage treatment and industrial uses.
- Inert gas generators are available for fire prevention purposes on ships and other structures and are already installed on many ships, mainly tankers. They can use a variety of fuels including marine diesel to generate the inert gas.
- ballast water with “inert gas”. These include a) how are larvae, eggs, and plankton effected and b) what is the effect of trimix type inert gas in fresh water. If ballast water is taken up through a screen, larger animals will not be included. The initial tests were made with adults because of easy access to them. However, if adults of a species are effected by “inert gas” it is most likely that their larvae will also be effected probably even more so.
- Empirical testing can be conducted with specimens from plankton and larval cultures and with incubations of mixed plankton collected from the ocean. Determinations of viability may be made by microscopic observations (e.g. movement of mouthparts, swimming behavior), ATP measurements (the ATP levels rapidly decreases after death of an organism), and the ability to bioluminesce (many planktonic organisms emit light, an ability which ceases after death).
- microscopic observations e.g. movement of mouthparts, swimming behavior
- ATP measurements the ATP levels rapidly decreases after death of an organism
- bioluminesce many planktonic organisms emit light, an ability which ceases after death.
- Fresh water organisms are also of interest because the pH change is not as much as in seawater. Freshwater in its natural environment can have pH values around 5.5. It has to be proven that raised CO 2 concentrations in combination with hypoxia will also affect fresh water species. Only then can the method be used for both, fresh and salt water ballast.
- the system analyzed places a mixture of nitrogen and carbon dioxide with a relatively small fraction of oxygen in contact with ballast water.
- the oxygen level in the ballast water is assumed to have reached equilibrium with air as a result of prolonged contact, and therefore would contain a concentration of oxygen sufficient to support a wide spectrum of life forms.
- the objective is to reduce the oxygen content to a low level by interchange with the gas mixture.
- the gas is bubbled through the ballast water, which assures uniform distribution of dissolved gas throughout the ballast tank. Thus, diffusion within the tank can be neglected. Bubbles are assumed to be small and variation of hydrostatic pressure over the vertical dimension of a bubble is neglected.
- the deoxygenation process is assumed to follow Henry's Law with equilibrium achieved within the residence time of each bubble.
- the composition of the mixture in the bubble changes primarily due to transfer of carbon dioxide, a dynamic chemical process assumed to obey the mass action kinetics.
- solubility of oxygen is reduced by underpressure. This factor becomes even more significant as a bubble rises to the surface, and the pressure inside decreases.
- Concentration of carbon dioxide in water can be determined as the ratio of the number of moles transferred from the bubble to the volume of the tank.
- the number of moles transferred from each bubble can be determined from the value of x as follows.
- x n C ⁇ O ⁇ ⁇ 2 n C ⁇ O2 + n 0 ( 13 )
- pH 5.5 corresponds to 2 ⁇ 10 ⁇ 5 mol/lit of carbon dioxide.
- Equation (16) can be solved for c, with the result substituted into the Equation (7).
- This yields after some tedious, but straightforward algebra the following relationship between the desired molar fraction of carbon dioxide in the bubble and the desired concentration of hydrogen ions in the water: x 1 - ( KN ⁇ n ) C ⁇ O2 0 KN ( n C ⁇ O2 0 + n 0 ) + ( K - h ) ⁇ ( h ⁇ V ) t ( 17 )
- Equation (11) and (17) constitute a closed-form mathematical model of carbon dioxide transfer, usable for design of the treatment system.
- a most preferred ballast water treatment system in accordance with the present invention is next described for a large tanker of the size as 300,000 DWT.
- a tanker of this size may not be the most cost effective candidate for realization of the ballast water treatment features of the present invention.
- the design next set forth can be easily modified for smaller tankers.
- the most preferred ballast water treatment system in accordance with the present invention is a combination of two effective treatment systems: deoxygenation and carbonation.
- the system is analogous of the American Underpressure System (“AUPS”) of MH Systems, San Diego, Calif. (Husain et al. 2001) in that a pressure less that atmosphere, called an “underpressure” is pulled in the ullage spaces of the ballast water tanks.
- AUPS American Underpressure System
- the inert gas that is preferably supplied by a standard marine gas generator is approximately 84%-87% nitrogen, 12-14% carbon dioxide and about 2%-4% oxygen. This inert gas has all the ingredients necessary to combine the two very effective treatments of hypoxia and carbonation at a very reasonable cost.
- Each ballast tank has rows of pipe at the tank floor with downward pointing nozzles.
- the pressurized inert gas is jetted downward out of the piping.
- the jets stir up the sediment for contact with the inert gas bubbles.
- the bubbles then rise through the ballast water to the space above the water surface, which has previously been underpressurized to ⁇ 2 psi.
- a 300,000 DWT single hull tanker was used for design studies of this system to test practicality and affordability. Applicability to a 300,000 DWT double hull tanker was also examined.
- FIG. 4a An inboard profile, deck plan view, piping layout, nozzle detail and section through a ballast tank part of the ballast water treatment system of the present invention is shown in FIG. 4a.
- FIG. 4 b A schematic diagram of the preferred embodiment of a ship's ballast water treatment system in accordance with the present invention—the tank of which was just previously seen in FIG. 4 a—is shown in FIG. 4 b.
- FIGS. 5a-5d Various views of the installation of the ship's ballast water treatment system in accordance with the present invention, previously seen in FIG. 4b , on an exemplary ship are shown in FIGS. 5a-5d .
- the exemplary ship is a 300,000 DWT double hull tanker. This particular ship incurs somewhat less installation cost since the tank bottom is smooth as is best shown in FIG. 5 a.
- this 300,000 DWT tanker there are 8 ballast tanks as follows in Table 2 of FIG. 3 . Table 2 lists the ballast water tank capacities.
- hypoxia and pH conditions can be set in at least 8 hours, even in the largest tanks, B3 Port and Starboard.
- the flow rate is 1350 cfm for each of these tanks.
- Contact time for essentially total lethality may not require more than another 24 hours although the remainder of the 2 to 3 week voyage is available.
- the space above the liquid in each tank is underpressurized to about ⁇ 2 psi and maintained throughout the voyage.
- the gas bubbles rise up to the surface, they are evacuated by a blower to maintain the underpressure of the inert gas blanket at the surface.
- the underpressure further facilitates the solubility of the oxygen (see analysis) and tends to compensate for the oxygen captured in the bubbles as they rise.
- ballast tanks are treated sequentially, only two 700 cfm compressors are required to compress the gas.
- the gas is compressed enough to offset the hydrostatic head plus an additional 25% psi to provide a jet force for stirring the sediment.
- Two compressors are provided for redundancy.
- Sensors are needed to monitor the pH to ensure that it never goes below about 5.5. Sensors will measure dissolved oxygen content to ensure an adequate deoxygenation is established. Sensors will also monitor the underpressure.
- the control system will remotely start and stop the gas generator, the compressor and the blower. The control system also remotely controls the valves off of the inert gas manifold to each ballast tank and the valving for the underpressure manifold.
- the system of the present invention may be controlled by computers, or, more preferably, by a suitably designed arrangement of programmable logic controllers (PLCs). These devices are widely commercially available. They are also easy to program and maintain.
- PLCs programmable logic controllers
- a control console with displays integrates the functions of the inert gas generator and the entire ballast water treatment system of the present invention, as well as providing for monitoring, status displays and manual override, if required.
- Mackey et al. (2000) stated that the economic payback period for conversions is typically 5 years. See Mackey, et al., op. cit.
- ballast water treatment system applicable for ships must have the capacity for treating huge quantities of ballast water. If a system is practical and economical for treating a ship with 8 ballast tanks of 110,823 cubic meters, then it is practical for all ship types. The economics would have to be assessed for ships of other, smaller ballast capacity, as the economics might not scale. But obviously, the effectiveness as well as the practicality of the system would be established.
- Table 3 of FIGS. 6a and 6b lists the principal parts and materials in the ballast water treatment system together with estimated prices and labor costs.
- the total cost is approximately $3,057,100. All tankers already have some type of inert gas generating capability. The newer tankers have generators with a gas mixture discharge similar to the mix used in the above-described experiments at Scripps Institute of Oceanography. Nevertheless, for conservatism, the generator has been included in the cost. Similarly tankers probably have sufficient excess electrical capacity to supply the load of this equipment—the compressors and blower. This is especially true since this is on the return trip in ballast and the machinery will only run about 48 hours each trip. Nevertheless, again for extreme conservation, a 300 KW generator has been included.
- the tanker will operate to 360 days per year. Six (6) voyages per year between Persian Gulf and USA. half of the voyages are return trips in ballast, or 6 trips a year.
- the 2 compressors and blower are assumed to operate 48 hours to obtain hypoxia and carbonation in ail 8 tanks (note that actually the cfm of both compressors is only required for tanks B3 port and starboard and B6 port and starboard.
- Operating costs are primarily the fuel costs for the inert gas generator and the 300 KW generator.
- n 5 years (economic payback period) and i (interest rate) is 8%.
- the total operating time is 288 hours per year for each generator.
- About 6,000 gallons of diesel fuel would be consumed by the electric generator and for the gas generator about 16,500 gallons. This is a total of 22,500 gallons.
- the yearly operating cost will be about $28,125.
- ballast water treatment is 3.7 cents per ton.
- ballast water treatment system is focused on treating the huge amounts of ballast water discharged into US harbors. It has the capacity to readily treat these huge quantities using standard marine components. For tankers that already have the major components on board, it would be very affordable. And for tankers with the AUPS spill containment, the added cost would be even less expensive.
- Ballast Water Exchange leaves sediment and other residue untreated. In fact, only the filtration concept treats sediment, by eliminating it.
- ballast water treatment methods and system in accordance with the present invention will suggest themselves to a practitioner of the gas handling, gas flow, and gas diffusion arts.
- the surface area of the ballast water available for gaseous interchange could be augmented by spraying the ballast water in an enclosed atmosphere of the desired gases.
- the (substantially) inert gases can be brought to the ballast water, or the ballast water to the (substantially) inert gases.
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Abstract
Description
CO2+H2O→H2CO3⇄H++HCO3 −
CO2+H2O→H2CO3⇄H++HCO3 −
Dissolved CO2 of the preferred levels of ≧20 ppm reduces the pH of seawater, which is normally 8, to acidic levels of pH≦7, and, preferably, pH≦6 and still more preferably pH≦5.5.
CO2+H2O→H2CO3⇄H++HCO3 −.
- c concentration of carbon dioxide in the water, including ions produced by electrolytic dissociation.
- g acceleration due to gravity.
- h concentration of hydrogen ions in the water.
- K dissociation constant of carbonic acid (−4.3×10−7 mol/liter).
- k reaction rate constant.
- kH Henry's Law constant for oxygen (=39.79×10−6).
- N total number of bubbles generated.
- n total number of gas moles in the bubble.
- nCO2 number of moles of carbon dioxide in the bubble.
- nN number of moles of nitrogen in the bubble.
- p total pressure inside the bubble.
- PCO2 partial pressure of carbon dioxide in the bubble.
- Q gas weight flow rate.
- t time.
- u bubble speed.
- Vt volume of the tank.
- x molar fraction of carbon dioxide in the bubble.
- Y weight fraction of oxygen in the water.
- y molar fraction of oxygen in the bubble.
- ρ density of the ballast water.
Superscript 0 refers to quantities in the gas bubble when it is first introduced into the tank. Subscript 0 refers to quantities in the water at the time t=0.
By definition nCO2+xn. Differentiating this equation realizes the following:
However, since the reaction of carbon dioxide with water is the dominant cause of change in the chemical composition, it can be written that:
Combining this with the Equation (5) yields the following equation:
In addition, solve n=xn+x0 for n to obtain:
From the Law of Mass Action kinetics:
For the partial pressure of carbon dioxide, according to Dalton's Law pCO2=xp.
This equation can be integrated to obtain:
where
This equation can be used to calculate the parameters of the systems, including residence time of a bubble, required to achieve the desired molar fraction of carbon dioxide in the bubble. The latter quantity is related to the pH and the concentration of carbon dioxide in the water, as shall be seen in the next subsection.
4.4 Concentration of Carbon Dioxide in Water and pH Calculation
Solving for nCO2 gives:
which gives the following answer for the concentration of carbon dioxide in water:
where CRF(i,n) is a capital recovery factor for an interest rate i for n for economic payback years; ΔP is change in Capital Cost; and ΔY is net change in annual operating cost and revenue.
Claims (49)
CO2+H2O→H2CO3⇄H++HCO3 −,
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US12/925,703 US20110132849A1 (en) | 2001-05-25 | 2010-10-26 | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful Aquatic Nuisance Species by simultaneous hypercapnia, hypoxia and Acidic pH level |
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US09/865,414 US6539884B1 (en) | 2001-05-25 | 2001-05-25 | Closed loop control of volatile organic compound emissions from the tanks of oil tankers, including as may be simultaneously safeguarded from spillage of oil by an underpressure system |
US10/120,339 US6722933B2 (en) | 2001-05-25 | 2002-04-09 | Closed loop control of both pressure and content of ballast tank gases to at different times kill both aerobic and anaerobic organisms within ballast water |
US10/366,759 US6761123B2 (en) | 2001-05-25 | 2003-02-14 | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful aquatic nuisance species by simultaneous hypercapnia, hypoxia and acidic ph level |
US11/484,828 USRE41859E1 (en) | 2001-05-25 | 2006-07-10 | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful aquatic nuisance species by simultaneous hypercapnia, hypoxia and acidic ph level |
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US10/366,759 Reissue US6761123B2 (en) | 2001-05-25 | 2003-02-14 | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful aquatic nuisance species by simultaneous hypercapnia, hypoxia and acidic ph level |
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US20110132849A1 (en) * | 2001-05-25 | 2011-06-09 | Mo Husain | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful Aquatic Nuisance Species by simultaneous hypercapnia, hypoxia and Acidic pH level |
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KR101006763B1 (en) | 2002-05-02 | 2011-01-10 | 피터 드러몬드 맥널티 | System and method of water treatment |
CN1197786C (en) * | 2003-06-13 | 2005-04-20 | 大连海事大学 | Method for killing living beings in the course of transmission of ballast water by using ship and its equipment |
US7087804B2 (en) * | 2003-06-19 | 2006-08-08 | Chevron U.S.A. Inc. | Use of waste nitrogen from air separation units for blanketing cargo and ballast tanks |
KR100542895B1 (en) * | 2003-12-22 | 2006-01-11 | 재단법인 포항산업과학연구원 | Method for controlling ballast water using effect of NaOCl produced electrolysis of natural seawater and an apparatus for the same |
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Cited By (1)
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US20110132849A1 (en) * | 2001-05-25 | 2011-06-09 | Mo Husain | Infusion of combustion gases into ballast water preferably under less than atmospheric pressure to synergistically kill harmful Aquatic Nuisance Species by simultaneous hypercapnia, hypoxia and Acidic pH level |
Also Published As
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US20110132849A1 (en) | 2011-06-09 |
US20030167993A1 (en) | 2003-09-11 |
US6761123B2 (en) | 2004-07-13 |
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