This application is directed to integrated systems having a Venturi quencher and a rotating packed bed device, and processes using the integrated systems, for removing sulfur oxide contaminants from marine exhaust gas onboard of ships.
Combustion of 3.5 wt % high-sulfur bunker fuel oil in marine two- and four-stroke diesel engines generates sulfur dioxide emissions that can lead to acid rain and is an environmental hazard. International Maritime Organization (IMO) has mandated use of 0.5 wt % Low-sulfur bunker fuel starting October 2020 or equivalent emission reductions. One of the equivalent solutions to 0.5 wt % sulfur fuel is to continue to burn 3.5 wt % Sulfur bunker fuel in two-stroke and four-stroke marine diesel engines and then scrub out the sulfur oxides from the marine exhaust gas to meet the equivalent of 0.5 wt % sulfur fuel use. While many dry and wet flue gas scrubbing processes have been demonstrated commercially to remove up to 98% of the sulfur oxides present in marine exhaust gas, seawater scrubbing emerges as a natural solution on board a ship due to its low cost, ample availability, alkalinity (pH˜8), ease of use, and demonstrated performance record over fifty years on land-based applications.
The shipping industry has gravitated towards the seawater spray tower as the ideal contacting device for scrubbing SO2 on board a ship. This is a low pressure drop gas-liquid contacting device that can be used for both, quenching the hot gas as well as subsequently scrubbing SO2 from the cooled gas. Spray towers must be quite tall to achieve 98% sulfur removal with seawater. The primary challenge to spray towers is space constraint on board a ship. These towers are tall, require considerable footprint, and cannot always be retrofitted inside the funnel of the ship. The adoption of seawater scrubbing to meet the mandated IMO specification has not progressed as rapidly as anticipated.
To address this space constraint, U.S. Patent Application 62/520,660 disclosed a compact rotating packed bed (RPB) device for scrubbing Marine Exhaust Gas (MEG) with seawater to meet the IMO mandated specification while burning 3.5 wt % High Sulfur Fuel Oil. RPB devices were introduced in the 1970s as compact mass transfer devices that enable intense gas-liquid micro-mixing. This intensive gas-liquid contacting is accomplished by flows of gas and liquid across the packing material in a RPB device. The centrifugal forces, unleashed by the rotation, shear the liquid film into fine droplets, thereby creating a large surface area for gas-liquid mass transfer. The high gravity forces in the RPB device dramatically shrink the Height Equivalent of a Transfer Unit (HETU), by an order of magnitude, so that the same separation can be accomplished by the RPB device with a smaller footprint relative to a conventional column.
Notwithstanding the strong claims for performance of RPB devices, they have found industry application in only a handful of instances over several decades since their invention. This reluctance may be attributed to power consumption and reliability concerns about rotating equipment. In the limited number of situations where space is a major constraint, investors have chosen to settle for the certainty of gravity flow columns (or spray columns) over the novelty of RPB devices.
Provided herein is an integrated system for onboard scrubbing of a marine exhaust gas on a ship, comprising:
Also provided herein is a process for onboard scrubbing of the marine exhaust gas on the ship, comprising feeding the marine exhaust gas to the integrated systems disclosed herein and discharging to an atmosphere a discharged gas that has been scrubbed onboard the ship.
Additionally, provided herein is a marine ship comprising one or more of the integrated systems for onboard scrubbing of the marine exhaust gas that are described in this disclosure.
The present invention may suitably comprise, consist of, or consist essentially of, the claims and embodiments, as described herein.
The integrated system and processes using the integrated system disclosed herein are carefully crafted to ensure the overall integrated system, besides being compact, is reliable, efficient, and fit-for-purpose for the marine shipping industry. This current disclosure uniquely integrates a RPB device with various unit operations associated with on-board scrubbing of marine exhaust gas (MEG) to meet IMO equivalent specifications. Given the space constraint, the unit operations in the MEG loop are tightly integrated into a compact whole.
Marine exhaust gas leaving an engine on a ship is typically hot, having a temperature greater than 180° C., or ranging in temperature from 200° C. to 390° C. The temperature of the marine exhaust gas can vary depending on whether an Energy Economizer is employed in the gas loop, whether the engine is a two or four-stroke engine, or whether the engine is operating at full or part-load. The integrated system of this disclosure comprises a Venturi quencher that cools the hot marine exhaust gas to a lower temperature, which is needed to more effectively dissolve sulfur oxides into the quench water or the seawater. The Venturi quencher quickly produces the cooled two-phase mixture of the marine exhaust gas and the quench water. In one embodiment, the cooled two-phase mixture has a lower temperature from about 10° C. to about 50° C., or from about 20° C. to 25° C.
In one embodiment, the Venturi quencher is configured to contact the hot marine exhaust gas at high velocity, through a throat of the Venturi quencher, with fine droplets of the quench water. The cooling happens very quickly. In one embodiment, the cooling of the hot marine exhaust gas can occur instantaneously, i.e., within 0.1 to 10.0 seconds, in a throat of the Venturi quencher.
Marine exhaust gas leaving an engine on a ship can comprise contaminants that originate from partial combustion of hydrocarbons or were originally present in the fuel being combusted in the marine engine. These contaminants can include sulfur oxides, nitrogen oxides, soot, ash particulates, and metals. Some of the contaminants can be particulates.
In one embodiment, particulates in the marine exhaust gas are collected in the quench water and removed from the quenched marine exhaust gas. In one embodiment, the Venturi quencher is configured with a liquid inlet that creates one or more sprays of the quench water along an upper converging section of the Venturi quencher. An example of this embodiment is shown in
In one embodiment, the Venturi quencher is a wetted-wall Venturi quencher that operates as a quench unit and can be a compact solution for cooling a hot marine exhaust gas and removing soot and particulates from the hot marine exhaust gas. By removing particulates greater than 3 microns, the quench unit can protect the packing in the RPB device from fouling by soot and particulates and enable effective SO2 scrubbing in the RPB device.
In one embodiment, the quench water used in the Venturi quencher can be fresh seawater, recycled seawater, oxidized seawater, seawater withdrawn from a spent seawater sump of the RPB device, or combinations thereof.
In one embodiment, the spent seawater recycle line recycles a portion of the spent water, as recycled water from the spent seawater sump, to the front of the Venturi quencher for quench cooling. Using recycled water from the spent seawater sump can significantly reduce the volume of fresh seawater needed for quenching and sulfur oxide removal.
In one embodiment, the integrated system maximizes a cascade of the recycled water from the spent seawater sump through the Venturi quencher and minimizes the use of the fresh seawater in the Venturi quencher. In one embodiment, a cascade of the recycled water from the spent seawater sump through the Venturi quencher is maximized and the fresh seawater is used principally for controlling a level of liquid collected in the spent seawater sump. In one embodiment, the Venturi quencher is configured to cause the marine exhaust gas to contact the recycled water before the marine exhaust gas is contacted by the fresh seawater.
In one embodiment, the Venturi quencher is configured to handle large volumetric flows, which are common on many large ships. In one embodiment, the Venturi quencher is rectangular and handles volumetric flows through the Venturi quencher greater than 88,000 actual-cubic-feet-per-minute (ACFM). In one embodiment, the Venturi quencher is configured to handle volumes of marine exhaust gas that vary over a broad range. One configuration that handles varied volumes of marine exhaust gas, also shown in
In one embodiment, the Venturi quencher can comprise a flooded elbow that connects to the RPB device and provides a tangential entry of the cooled two-phase mixture into the circumferential gas distributor. In one embodiment, the flooded elbow is at the bottom of the Venturi quencher and the flooded elbow is fitted with a liquid seal. The liquid seal minimizes erosion that could occur due to impingement by particulates in the Venturi quencher. Further, provision of a small outlet for a bleed stream, from the bottom of the flooded elbow, that removes particulate build-up can be included. In one embodiment, the Venturi quencher has a conical bottom on the flooded elbow with a bottom drain that can be a liquid slurry drain outlet. In one embodiment the integrated system additionally comprises a bottom drain on the Venturi quencher that drains a slipstream of particulates and liquid from a bottom of a flooded elbow of the Venturi quencher.
The Venturi quencher is connected to the RPB device. In one embodiment, the connection between the Venturi quencher and the RPB device utilizes a tangential gas entry. In one embodiment, that tangential gas entry provides a cyclonic action that disengages the quenched marine exhaust gas from the quench water. The tangential gas entry minimizes maldistribution of the quenched marine exhaust gas in the RPB device. Gas maldistribution in RPB devices is described in Llerna-Chavez and Larachi, Chem Eng Sci, 64 (2009), 2113. In one embodiment, the design of the tangential gas entry is such that the gas flow direction is co-current with a rotating direction of a rotation of the RPB device.
The RPB device has a circumferential gas distributor, connected to the Venturi quencher. The circumferential gas distributor is configured to receive a cooled two-phase mixture of the marine exhaust gas and the quench water from the Venturi quencher, disengage a quenched marine exhaust gas from the cooled two-phase mixture, and distribute the quenched marine exhaust gas along an outer circumference of the RPB device. In one embodiment, the circumferential gas distributor is an elongated skirt or blade that causes the quench water to drop out of the cooled two-phase mixture, such as to a spent seawater sump, while the quenched marine exhaust gas is raised from the bottom of the elongated skirt or blade to enter a packed bed in the RPB device.
In one embodiment, the circumferential gas distributor is configured to evenly distribute the quenched marine exhaust gas across the 360-degree circumference of the RPB device. In one embodiment, the circumferential gas distributor is shaped and sized such that it segregates the quench water containing soot and particulates from the packing material in the RPB device, to prevent fouling of the packing material and extend the life of the RPB device. In one embodiment, the circumferential gas distributor drops out the quench water to a spent seawater sump in the RPB device. In some embodiments, the elongated skirt is used as the circumferential gas distributor and all the benefits described in this paragraph are obtained.
In one embodiment, the stationary gas distributor extends along a majority of the outer circumference of the RPB device and is an elongated skirt that causes the quench water to drop out of the cooled two-phase mixture while the quenched marine exhaust gas is raised up and enters a packing in a packed bed in the RPB device.
In one embodiment, the RPB device utilizes the seawater to effectively remove contaminants, including SO2, from the marine exhaust gas, such that a discharged gas meets IMO mandated specifications. The seawater can be fresh seawater, or the seawater may also comprise an alkali. In one embodiment, the seawater is fresh cold seawater. In one embodiment the RPB device removes sulfur oxides, e.g., SO2 and SO3 such that the discharged gas is equivalent to the emissions from burning fuel containing from zero to less than 0.5 wt % sulfur. In one embodiment, the discharged gas comprises less than half of the sulfur, such as from zero to 30% of the sulfur, that was originally present in the marine exhaust gas before entry into the Venturi quencher. Examples of suitable RPB devices are taught in U.S. Provisional Patent Application No. 62/520,660.
In one embodiment, the RPB device comprises a motor drive at one end that rotates a packed bed that is fixed to a rotating shaft within the RPB device. In one embodiment, the motor drive is at the bottom of the RPB device. This embodiment is shown in
In one embodiment, a rotating shaft in the RPB device is supported at opposite ends of the RPB device with roller bearings. In one embodiment, the rotating shaft in the RPB device is supported at both the top and the bottom of the RPB device by roller bearings, with a motor drive at the bottom. However, the motor drive could also be located on the top of the RPB device without compromising the effectiveness of the integrated system.
Unlike spray towers, RPB devices are characterized by a high degree of micro-mixing and very short holdup times of gas and liquid. In the RPB device the chemical reactions to scrub the sulfur oxides from the marine exhaust gas are very fast. However, the bisulfites and sulfites that are formed during the scrubbing in the Venturi quencher or the RPB device can reverse and produce sulfur oxides again. Sulfites are compounds that contain the sulfite ion, SO2−. Bisulfites are compounds that contain the bisulfate ion, HSO3−. These reverse reactions can result in unacceptable sulfur oxide (e.g., sulfur dioxide) emissions from the ship. In one embodiment, these reverse reactions, outside of the RPB device, are forestalled by aerating a liquid effluent from the RPB device and/or the quench water from the Venturi quencher by converting the bisulfites and/or the sulfites into stable sulfates in the liquid effluent.
In one embodiment, the RPB device can additionally comprise a spent seawater sump, at the bottom of the RPB device, that is well-aerated and oxidizes sulfur and sulfur compounds that are collected from either or both of a quench water from the Venturi quencher or a liquid effluent from the RPB device. One example of a spent seawater sump is shown in
In one embodiment, oxidizing the sulfur and sulfur compounds in the spent seawater sump enables the spent seawater to be recycled and more effectively used in the Venturi quencher. When the recycled water from the spent seawater sump is passed through the Venturi quencher, the recycled water is heated, and stable sulfates are retained in the recycled water that is heated rather than being released to the atmosphere.
The aeration in the spent seawater sump can reduce the chemical oxygen demand (COD) upon discharge of a wastewater from the integrated system. In one embodiment the COD of the wastewater after aerating in the spent seawater sump can be reduced to below 1500 mg/l. In one embodiment, carbon dioxide is formed in the liquids collected in the spent seawater sump. The carbon dioxide formed in the spent seawater sump can be passed through the RPB device, along with nitrogen from air, and exit with clean exhaust gas (discharged gas) from the ship to the atmosphere. Atmosphere is defined herein as the ambient mixture of gases that surround the earth and which exist outside of the ship.
In one embodiment, the integrated system additionally comprises a spent seawater sump that is provided with an air supply line through which air is sparged into collected liquids, and the spent seawater sump collects the quench water from the Venturi quencher, an effluent liquid from the rotating packed bed device, or a combination thereof, and the spent seawater sump creates stable sulfates in the collected liquids in the spent seawater sump. There can be insufficient oxygen in flue gas to completely oxidize SO32− to SO42−. Sparging air into the seawater that collects in the spent seawater sump helps to stabilize the sulfur that is present as sulfates prior to discharge of the spent seawater effluent or recycling of the spent seawater to the Venturi quencher. Sparging air also minimizes COD in the spent seawater effluent.
In one embodiment, additional fresh seawater can be blended into a liquid effluent from the RPB device or from the spent seawater sump of the RPB device. The additional seawater can neutralize any residual acid in the liquid effluent and meet a target pH of between 6 and 10, or a target pH of 6.5 or greater.
In one embodiment, the liquid effluent from the RPB device or a blended mixture of the liquid effluent with fresh seawater can be routed to a separator that is connected to the RPB device. In one embodiment, the separator can be a centrifuge or a cyclone separator. The separator can be configured to separate the liquid effluent or the blended mixture into two streams: i) an overhead effluent clean seawater stream that can be discharged to the ocean, and ii) a bottom sludge that can be collected in a holding tank on the ship, for discharge at an upcoming port. In one embodiment, the separator can also have provision for air blown into it via an air sparger, and can also comprise a vent that emits carbon dioxide, or small amounts of other light gases.
The RPB device has a gas outlet for discharging a scrubbed marine exhaust gas. In one embodiment, the gas outlet passes to a fan that disperses the scrubbed marine exhaust gas to the atmosphere. The scrubbed marine exhaust gas can contain entrained moisture. In one embodiment, the integrated system additionally comprises one or more mist eliminators fitted at the gas outlet, e.g., at the top, of the RPB device. In one embodiment, the mist eliminator is a demister pad. The demister pad can be configured to trap and condense entrained water from discharged gas from the RPB device and prevent a visible plume of gas from the ship. In one embodiment, the discharged gas does not have a visible plume. In one embodiment, the demister pad is a vane-type circular demister pad that is fitted onto a circular gas outlet from the RPB device. One exemplary-demister pad (600), a circular demister pad, is shown in
In one embodiment, the mist eliminator comprises steam coils and the steam coils warm the discharged gas and provide buoyancy to the discharged gas. In one embodiment, the integrated system comprises a mist eliminator having a set of circular steam coils. An example of a circular mist eliminator with multiple steam coils is shown in
In one embodiment, the integrated system additionally comprises a Continuous Emissions Monitoring System (CEMS) module that confirms the effective operation of the integrated system of this invention. In one embodiment, when the CEMS module confirms the effective operation of the integrated system, the discharged gas from the integrated system can be vented directly to the atmosphere. For example, the CEMS module can confirm that the discharged gas is a desulfurized flue gas meeting environmental limits on sulfur. In one embodiment, the venting is enabled by an induced draft exhaust fan that can be fluidly connected to the gas outlet on the top of the RPB device.
In one embodiment, as shown in
In one embodiment, the marine exhaust gas, having a temperature greater than 180° C., can be aggregated from multiple engines and a boiler on the ship.
Hydrodynamic studies with RPB devices reported in Yan, Lin & Ruan, I&EC Res, 2012, 51, 10472 have shown that not all of the packing area in a packed bed of a RPB device is equally wetted or equally efficient for mass-transfer. An entry region, a narrow circumferential zone that is close to the center eye of the RPB device, sees more intense gas-liquid contact. The center eye is defined herein as the space in the center of the RPB device without any packing material. If care is not taken, the outer periphery of the packing bed in the RPB device can be a completely dry region and not function to reduce contaminants and perform effective onboard scrubbing of a marine exhaust gas. This feature can be more pronounced as the size of the RPB device increases. Guo, Wen, Zhao, Wang, Zhang, Li & Qian (Eniron. Eng. Sci Technol., 2014, 48, 6844) evaluated the optimum packing thickness at different revolutions per minute and liquid jet velocities and concluded that not all sections of the packing are equally effective for mass transfer. They further noted that the mass-transfer effectiveness drops off towards the outer layers, leading to an optimum packing thickness.
In one embodiment, the RPB device has a ratio of an outer diameter to an inner diameter of a packed bed in the RPB device that provides good counter-current mass-transfer between the quenched marine exhaust gas and seawater across the depth of the packed bed. In one embodiment, the ratio of the outer diameter to the inner diameter of the packed bed in the RPB device is 2.3:1 or less. Surprisingly, the gas-liquid mass transfer rates between the quenched marine exhaust gas and the seawater are very fast and this design limitation is readily achievable and provides for effective onboard scrubbing of a marine exhaust gas on a ship using seawater.
Pan and Chiang (Journal of Cleaner Production, 149 (2017), 540-556) make the point that a RPB is even more effective than wet scrubbers, such as Venturi quenchers, in trapping soot and fine particulates from flue gas. In one embodiment, the Venturi quencher and the RPB device in the integrated system are both configured to remove particulates from gas flows within the integrated system and to produce a discharged gas with minimal to no particulates. In one embodiment, the Venturi quencher traps particulates larger than 3 microns in average diameter; and the RPB device comprises packing material that traps sub-micron particulates up to 0.1 micron in average diameter as well as any particulates between these two ranges. In one embodiment, the outer diameter of the packed bed in the RPB device is sized to provide a large surface area in an outer periphery that provides the trapping of sub-micron particulates for an extended time without causing an excessive pressure-drop in the RPB device.
In one embodiment, a bulk of sulfur oxide contaminants (e.g., sulfur dioxide) mass transfer between the quenched marine exhaust gas and the seawater occurs in the inner areas of the packed bed, closer to the center eye, and a second bulk of the trapping of the sub-micron particulates occurs in the outer areas of the packed bed, farther from the center eye.
In one embodiment, the RPB device comprises a wash inlet that feeds a wash solution to the outer areas of the packed bed. In one embodiment, a wash inlet on the RPB device can periodically spray a wash solution into the RPB device that loosens soot and particulates lodged on an outer periphery of the packing material in the RPB device, which drop into a spent seawater sump in the RPB device. An example of a wash solution that could be used is a solution of ammonium citrate. Other solutions that might be employed include: detergent mixtures, petroleum distillates (alone or in emulsions), xylene emulsions, ethanol, ethylene glycol monobutyl ether, and combinations thereof. In one embodiment, the wash inlet can comprise one or more nozzles or sprayers. In one embodiment, a rotation of the packed bed in the RPB device ensures that all the packed bed surface area on an outer periphery gets sprayed with a wash solution that removes soot or particulates. In one embodiment the RPB device comprises a wash water supply system.
The integrated system includes a stationary liquid distributor with multiple spray nozzles that feed a seawater across an inner circumference of the RPB device. In one embodiment, the seawater is fresh seawater, such as fresh cold seawater. An example of this type of stationary liquid distributor is shown in
In one embodiment, the spray nozzles are equally-sized, equally-spaced across a ring circumference of each of the multiple liquid rings, and the positioning of the spray nozzles is oriented to spray the fresh seawater evenly on the packing material.
In one embodiment, the rings in the liquid distributor have diameters that place them equidistant from the inner surface of the packing material in the RPB device. In one embodiment, the rings all have the same diameter. In one embodiment, the diameters of the rings vary across the length of the liquid distributor.
In one embodiment the liquid distributor is held stationary at the top by a housing for the RPB device, in such a way that the positioning of the liquid distributor does not interfere with the rotation of the rotating shaft or the packed bed in the RPB device.
In one embodiment, fresh seawater is supplied to the stationary liquid distributor by an inlet header pipe that serves as a fresh seawater supply line, at the top of the RPB device, as shown in
Hydrodynamic studies in RPB devices by Yan, Lin & Ruan, I&EC Res. 2012, 51, 10472 have shown that gas-side pressure drop in a RPB device is proportional to the gas flow rate in the RPB device and the revolutions per minute (RPM) of the rotation of the packing material in the RPB device. In one embodiment, the integrated system provides high seawater flowrates and strong inlet pressure to achieve uniform wetting of the packing material and effective scrubbing of the marine exhaust gas over a range of gas flow rates provided by the gas distributor. Since seawater supply is abundant, the flowrates of the seawater in the liquid distributor can be kept high, or even constantly high, regardless of swings in the gas flowrate of the quenched marine exhaust gas. The swings in the gas flowrate of the quenched marine exhaust gas can vary depending on the operation and loads on the engines on the ship, but the effective scrubbing of the marine exhaust gas is maintained. In one embodiment, the flowrates of the seawater in the liquid distributor are kept constant over a range of quenched marine exhaust gas flowrates through the gas distributor.
A key to the descriptions for the numbers used in the drawings is as follows.
One example of the integrated system of this disclosure is shown in
The transitional term “comprising”, which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. The transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. The transitional phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Furthermore, all ranges disclosed herein are inclusive of the endpoints and are independently combinable. Whenever a numerical range with a lower limit and an upper limit are disclosed, any number falling within the range is also specifically disclosed. Unless otherwise specified, all percentages are in weight percent.
Any term, abbreviation or shorthand not defined is understood to have the ordinary meaning used by a person skilled in the art at the time the application is filed. The singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one instance.
All the publications, patents and patent applications cited in this application are herein incorporated by reference in their entirety to the same extent as if the disclosure of each individual publication, patent application or patent was specifically and individually indicated to be incorporated by reference in its entirety.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. Many modifications of the exemplary embodiments of the invention disclosed above will readily occur to those skilled in the art. Accordingly, the invention is to be construed as including all structure and methods that fall within the scope of the appended claims. Unless otherwise specified, the recitation of a genus of elements, materials or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof
The invention illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.
Number | Date | Country | |
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62566622 | Oct 2017 | US |