The invention relates to processing of combustion gasses to remove contaminants such as oxides of sulfur, nitrogen and carbon. The invention has particular application to treating exhaust from combustion engines such as marine diesel engines.
Marine diesel engines power the majority of ships used for marine transportation. These engines typically burn Heavy Fuel Oil (HFO), which contains high concentrations of sulfur and other impurities. The combustion process produces high concentrations of sulfur oxides (SOX), nitrogen oxides (NOX), carbon oxides (COX) such as C02, and other gases that are subject to increasing restrictions with new emerging emissions requirements.
One approach to reducing marine engine emissions is to switch to higher purified fuels, or distillates. These distillates are more expensive than HFO. An alternative is to post-treat, clean, or scrub the combustion exhaust gasses before they are discharged into the atmosphere.
Sea water scrubbers have been developed as a post-treatment solution to clean marine engine exhaust. A commonly used process is to spray aqueous alkaline or ammonia sorbents into the exhaust stream. However, these ‘wet’ sea water scrubbers can require large amounts of water and consequently generate large amounts of waste water, which can include metal salts such as calcium sulfate, soot, oils, and heavy metals. This can produce a toxic sludge that requires complex on board water treatment, and as well as disposal of sludge at designated ports. The resultant system is large, complex, expensive and energy intensive, increasing ship fuel consumption by as much as three percent. Although conventional sea water scrubber systems may be well suited for fixed land based power plants, they are simply too large and complex to operate efficiently in a marine application. As well, such systems may not be well suited to removing C02 from marine engine exhaust.
Treatment of marine exhaust could in principle be accomplished by modifying existing land-based technology to bubble marine exhaust gases through an ionic liquid. However, this approach may not be practical due to the high flow rates of marine exhaust and the resultant large volume of ionic liquid required, in light of the space and weight constraints of a marine vessel. The energy required to compress the exhaust gases to bubble through the ionic liquids could exceed the total energy available from the ship.
A system for scrubbing marine engine exhaust gasses using membrane technology has been proposed in Chinese patent No 200710012371.1.
An object of the present invention is to provide an improved method and system for reducing the concentration of one or more target emission gasses from a source such as a marine diesel engine.
An alternative to the use of a conventional seawater scrubber for removing unwanted compounds from marine engine exhaust gas is to use membrane technology to separate and process one or more Target Emission Gasses (TEG's) such as SOX, NOX and/or COX from the exhaust gas. Advantages to using membranes over traditional solvent-based extraction processes such as sea water-based scrubbers include being potentially smaller, more energy efficient and producing less waste water than a conventional water-based scrubber. Although membrane-based systems have been proposed in the past, the present invention relates to improvements that render such systems highly effective in a variety of applications including use with marine vessels.
According to one aspect, the invention relates to a method for reducing the concentration of a target emission gas (TEG) from a source of engine exhaust gas comprising the steps of:
directing said gas into an enclosed space containing at least one array of hollow fibre ceramic membranes, wherein said exhaust gas contacts an exterior surface of said membranes whereupon TEG within said exhaust gas selectively permeates through said membrane thereby lowering the concentration of said TEG within said exhaust gas;
circulating a carrier liquid capable of retaining said TEG through bores of said hollow fibre ceramic membranes thereby elevating the concentration of said TEG compounds within said carrier liquid;
discharging said exhaust gas containing a reduced TEG concentration from the enclosed space and discharging said liquid from said hollow fibre ceramic membrane array, wherein said discharged liquid contains molecules of TEG dissolved therein.
The liquid can discharged from the membrane assembly into the environment in one of an “open” mode of operation or alternatively a closed loop mode can be used, such as wherein said TEG is separated from said liquid and said liquid is recycled through said membrane array.
The carrier liquid may comprise one of an ionic liquid, sodium hydroxide, fresh water or seawater. The ionic liquid may comprise a task-specific ionic liquid (TSIL) which is specific to said TEG's. If the carrier liquid is an ionic liquid, the method may comprise the further step performed after said liquid enters the discharge conduit, of separating said TEG from said carrier liquid for storage and recycling said carrier liquid through said membranes.
The TEG may comprise one or more of a sulfur oxide, a nitrous oxide or a carbon oxide such as CO2.
The method may include the further steps of determining the concentration of TEG within untreated exhaust gas, determining an optimal rate of liquid flow required to reduce the TEG concentration in said untreated gas to a target level and selectively controlling the rate of liquid flow through said membrane array to match said optimal rate of liquid flow.
The method may include the further step of determining the effectiveness of said membrane array at reducing concentrations of said TEG by determining whether said liquid passing through said array experiences one or both of a pressure drop that exceeds a predetermined level or a pH drop that is less than a predetermined level.
The membrane array may comprise a module housed in a modular housing wherein said liquid is circulated through a selected number of said modules based on a determination of the level of TEG concentration in said exhaust gas and/or the flow rate of said exhaust gas. Selected ones of said modules may be removed and replaced if it these have been determined to be less effective by a predetermined level.
According to another aspect, the invention relates to an apparatus for lowering the concentration of at least one target emission gas (TEG) from a source of engine exhaust gas comprising:
The apparatus may further comprise a carrier recycling subsystem in communication with the primary carrier outlet and inlet, said recycling subsystem comprising a TEG stripping device for removing at least one TEG from said carrier liquid, wherein said carrier is circulated in an essentially closed loop through said apparatus.
The carrier liquid may comprise water which is circulated in an open loop through said apparatus, said apparatus comprising a water inlet and a water outlet for non-recycling circulation of water through said membrane array.
The apparatus may comprise multiple ones of said membrane arrays arranged in parallel or in series for contacting the emission gas, for operation in one of a parallel mode or a sequential mode of circulating the liquid.
The system may further include a carrier recycling subsystem in communication with the carrier liquid outlet and inlet, said recycling subsystem comprising a TEG stripping device for removing at least one TEG from said carrier liquid, wherein said carrier is circulated in an essentially closed loop through said apparatus.
Alternatively, the carrier liquid comprises water which is circulated in an open loop through said apparatus, said apparatus comprising a water inlet and a water outlet for non-recycling circulation of water through said membrane array.
The modules may further comprise one or both of a liquid inlet manifold or liquid outlet manifold in fluid communication with said bores at inlet and outlet ends of said bores respectively.
The system may further comprise at least one of a pH sensor system for determining a pH drop in said liquid carrier from circulating through said membrane array and a pressure sensor system for determining a pressure drop in said liquid carrier from circulating through said membrane array, said sensors being operatively linked to a signal processor for determining whether said pH drop and/or pressure drop is indicative of a reduced level of effectiveness of said membrane array at reducing concentrations of TEG.
The system may further comprise a sensor for measuring TEG concentration within untreated exhaust gas from said source and a control system in operative communication with said sensor and with a pump for controlling the flow rate of said carrier liquid through said system, said control system being configured to determine the flow rate of said carrier liquid through modules required in order to achieve a selected level of TEG concentration reduction and to control said flow rate to provide said flow rate.
An ionic liquid, used in association with an appropriate semipermeable membrane, can separate, capture and store a Target Emission Gas (TEG) such as SOX, NOX and/or COX from the exhaust gas in a closed loop reversible process. This alternative can eliminate or reduce the production of waste water and waste sludge in comparison with certain other solvents.
An ionic liquid (IL) is a solution that contains an organic cation (e.g. imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium), and a polyatomic inorganic anion (e.g. tetrafluoroborate, hexafluorophosphate, chloride) or an organic anion (e.g. trifluoromethylsulfonate, bis[(trifluoromethyl)sulfonyl]imide. The main advantages of ILs are their negligible volatility, non-flammability and good chemical and thermal stability. They are considered as environmental benign carriers as compared to volatile organic solvents, reducing the environmental risks of air pollution. Furthermore, certain properties of ILs (hydrophobicity, viscosity, solubility, acidity and basicity etc.) can be tuned to improve the solubility of one or more TEGs within the IL by selecting a specific combination of cation and anion and varied by altering the substitute group on the cation or the combined anion.
An ionic liquid may be “task specific.” An example of such a Task Specific Ionic Liquid (TSIL) is formed by the reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, following a workup and anion exchange. This yields an ionic liquid active at room temperature, incorporating a cation with an appended amine group. The ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The ionic liquid, which can be repeatedly recycled, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents and yet is nonvolatile and does not require water to function. The unique properties of ionic liquids make them particularly well-suited for physical and chemical absorption processes. They can be easily adjusted by substituting cations and anions in their structure and thereby “tuned” to absorb specific gases by either physical and or chemical absorption over specified processing conditions including temperature and pressure. These task specific ionic liquids provide significant improvements in chemical absorption efficiencies over other solvents
Ionic liquids have application in various liquid chemical separation processes. An example of an IL application is the BASIL (Biphasic Acid Scavenging utilizing Ionic Liquids) process developed by BASF, in which 1-alkylimidazole scavenges an acid from an existing process. IL compounds are also used in chemical synthesis such as the synthesis process for 2,5-dihydrofuran by Eastman and the difasol process, an IL-based process which is a modification to the dimersol process by which short chain alkenes are branched into alkenes of higher molecular weight. A further IL-based process is the Ionikylation process developed by Petrochina for the alkylation of four-carbon olefins with isobutane.
The invention is based on the principle that SOX, NOX, and/or COX can be selectively removed from marine exhaust gases by the use of a liquid carrier circulated through a semi-permeable membrane system such as a ceramic membrane. These impurities are generally considered safe for discharge when dissolved into a liquid but should not be discharged as gasses into the atmosphere. With the use of a membrane to separate such compounds, the TEG can permeate through the membranes while particulates within the marine exhaust including ash, soot, and oils do not. The carriers remain clean and devoid of toxic impurities, and can be safely discharged, re-used, or regenerated.
The system according to the invention can be operated in an operating modes consisting of one of an Open Mode, a Closed Loop or a Zero Discharge mode.
The liquid carrier used in an Open Mode can be the water within which the vessel floats, which can be fresh water or sea water. The membrane separation system comprises an array of porous hollow fiber membrane membranes in which fresh water or sea water circulates within the interiors of the membranes. The fresh water or sea water is drawn into the vessel from surrounding waters and is circulated through the hollow fiber membrane membranes. Flue gases pass over and contact the exterior of the porous hollow fiber membrane membranes and permeate through the membrane. One or more TEG's is absorbed by the water and removed from the exhaust stream. The absorbed gases form acids, which are neutralized by the hardness of the fresh water or salinity of the sea water as precipitates such as sulfides. The fresh water or sea water containing the precipitates is subsequently discharged into the surrounding waters of the ship.
The carrier liquid used in a Closed Loop mode can be a basic solution such as sodium hydroxide, which is circulated through a hollow fiber membrane array. Flue gases contact the porous hollow fiber membrane and permeate through the membrane into the bore within which the carrier circulates. TEG's are absorbed by the solution within the membrane bore and thus removed from the exhaust stream. The absorbed gases form acids which are neutralized by the base. The heat absorbed by the carrier liquid as it passes through the membrane array elevates the carrier temperature and maintains the TEG compounds in solution. The carrier liquid can then be cooled within a desorption vessel, which causes the TEG compounds to precipitate in solid form such as sulfide precipitates. The precipitated solids can then be removed by a mechanical separation process such as filtering. The unsaturated carrier liquid can then be recirculated as a closed circulation loop. Cooling of the carrier liquid within the desorption vessel can be provided by use of a heat exchanged within the vessel in which ocean water is circulated as a cooling fluid.
The liquid carrier used in a Zero Discharge mode is an ionic liquid (IL). The zero discharge mode comprises a closed loop reversible process where little or no chemical precipitates are generated. The membrane separation system comprises an array of porous hollow fiber membrane membranes through which IL circulates and a desorption vessel (DV) for separating the TEG's from saturated IL. The sulfur dioxide, nitrogen oxides and carbon oxides can be separated from the ionic liquids within the DV by the application of one or more of differential pressure, temperature, and/or electric potential. The separated gases are then stored in pure states or as compounds, and the ionic liquid reused. The absorbed gases are stored and be used for commercial applications. The differential temperature required to dissociate the gases is provided by the exhaust gases by means of a heat exchanger.
By means of the invention, exhaust gases permeate through the ceramic porous membranes but toxic particulates within the marine exhaust including ash, soot, and oils are too large to permeate through the membrane pores. The carriers remain clean and void of toxic impurities and can be safely discharged, re-used or regenerated in open loop, closed loop, or zero discharge modes. In contrast, conventional Wet Water Scrubbers may spray carriers directly into the marine exhaust. Toxic particulates become trapped and suspended within the carriers, and must be removed from the carriers using complex, energy intensive, and expensive cleaning systems. The cleaning process produces a sludge byproduct that is expensive to dispose of on land.
In the present patent specification, the following terms shall have the meanings described below, unless otherwise specified or if the context clearly requires otherwise:
“Gas” or “gasses” refer to a compound or mixture of compounds that exists in the gas phase under ambient conditions of temperature and pressure.
“Diesel” refers to an internal combustion engine that of the compression-ignition design. A diesel engine can burn a variety of fuels including without limitation diesel fuel, bunker crude, biodiesel and others. The term “diesel” or “diesel emissions” is not restricted to any particular fuel type but includes any hydrocarbon fuel that may be combusted in a diesel-type engine.
“Target Emission Gas” or “TEG” refers to any gas or gasses that are intended to be removed from an exhaust gas stream generated by a combustive process. TEG's can include but not limited to Sulfur Oxides, Nitrogen Oxides, and Carbon Oxides such as C02. It will be understood that a TEG can exist in either a gas phase or a liquid or solid phase under different conditions such as when dissolved into solution or bound to a liquid phase compound.
“Emissions” refers to total combustion exhaust gasses from an engine or other source of exhaust gasses, including target emission gas as well as other gasses.
“Carrier” refers to either one of a liquid containing a compound that is capable of binding to a TEG or a liquid that can dissolve a TEG into solution so as to be operative in a membrane system to selectively reduce the concentration of the TEG from a gas-rich environment.
“Semi-permeable membrane” may also be termed a selectively permeable membrane, a partially permeable membrane or a differentially permeable membrane, and is a membrane that allows selected molecules or ions to pass through it by diffusion. The rate of passage through the membrane can depends on the pressure, concentration, and temperature of the molecules or solutes on either side, as well as the permeability of the membrane to each solute. The membrane can vary in thickness, depending on the composition of the membrane and other factors.
In order to better understand various exemplary embodiments, reference is made to the accompanying drawings, wherein:
Gas absorption unit 22 comprises a main housing 30, seen in detail in
Multiple modules 26 can be configured within main housing 30 in an array for operation in parallel or in series for removing a selected TEG's from the engine exhaust. Operation of system 20 in parallel refers to a mode of operation wherein carrier is fed to multiple modules 26 in parallel, such that each module receives equally unsaturated carrier liquid. Operation of system 20 in series refers to a mode of operation wherein the carrier liquid is fed in series through multiple modules 26 whereby the liquid becomes increasingly saturated as it passes through the respective modules.
Exhaust gas enters gas absorption unit 22 through an inlet conduit 34 and is discharged after treatment through outlet conduit 38. Unsaturated liquid carrier is fed into gas absorption unit 22 through liquid inlet conduit 40. The saturated liquid carrier exits unit 22 through outlet conduit 42 and is then fed into desorption unit 24 where the TEG is removed from the carrier. As discussed below, the carrier liquid absorbs one or more TEG's from the exhaust gas for transport to a separate location for storage or disposal. The now-unsaturated carrier is then recirculated into inlet conduit 40. As seen in
As shown generally in
Gas treatment system 20 further comprises a pH sensor 54 for measuring the pH of carrier liquid within outlet conduit 42. System 20 further comprises a first pressure sensor 56 for measuring the carrier liquid pressure within inlet conduit 40 and a second pressure sensor 58 for measuring carrier pressure within outlet conduit 42. One or more first TEG sensors 60 are provided for detecting the level(s) of selected TEG's within the untreated exhaust entering system 20 within engine exhaust conduit 34. One or more second TEG sensors 62 are provided for detecting the levels of the selected TEG's within the treated exhaust in discharge conduit 38. The respective sensors 60 and 62 are in operative communication with a control system 200 whereby the values detected thereby are transmitted in realtime to control system 200 for efficient operation of the system, as described in more detail below.
As seen in more detail in
Module housing 64 can be modular in configuration to permit convenient assembly of multiple modules 26 in the form of a single unit for installation in a vessel or elsewhere. As discussed below, multiple modules 26 can be linked in parallel or series depending on the application. In one example, housing 64 is rectangular and has dimensions of 50 cm×50 cm×100 cm. Housing 64 may be fabricated from metal sheeting such as a heavy gauge stainless steel sheet. Multiple modules 26 can be secured in a rack for access and easy replacement.
Housing 64 is fabricated from sheet metal and comprises opposing side walls 74a and 74b and opposing end walls 76a and 76b. For purposes of description, an elongate axis “a” can be considered to extend between end walls 76a and b. The interior of housing 64 is divided into two essentially equal spaces by a central divider wall 78 which is parallel to end walls 76. Divider wall 78 supports hollow membrane membranes 80 within housing 64, as described below. External bracing members 82 may be provided for additional structural integrity of housing 64. Housing 64 is open above and below to allow gas to flow freely through the housing.
Housing 64 retains within its interior first and second perforated walls 84a and 84b (seen in
End walls 76a and 76b have recessed central portions 88a and 88b respectively that open to the interior of housing 64. Recesses 88a and b are covered by respective perforated walls 84a and b, which are sealed and secured to end walls 76 by mounting strips 85 and gaskets 87. Recesses 88a and b each define an enclosed manifold, recess 88b defines an inlet manifold and recess 88a defines an outlet manifold.
Perforated walls 84 may be secured to end walls 76 by bolts or other fasteners.
Housing 64 houses within its interior one or more membrane assemblies 66. Each assembly 66 consists of an array of porous ceramic hollow fiber membranes 80 that span the interior of housing 64, extending axially between end walls 76a and b. Membranes 80, one of which is shown in detail in
Suitable ceramic hollow fiber membranes include commercially available aluminum oxide (AI2O3) hollow fibre membranes, such as the Membralox® membrane. A description of this membrane is available at: http://www.pall.com/main/food-and-beverage/product.page?id=41052. Representative dimensions of a suitable membrane 80 is: pore size: 100 A; ID: 4 mm; length: 1020 mm.
Opposing ends of membranes 80 are secured within openings 86 in walls 84a and b. Membrane bore 92 communicates with a respective opening 86 at either end of membrane 80. The intersection between membrane 140 and each corresponding opening 86 is sealed against fluid (gas and or liquid) leakage. For example, membranes 80 may be secured to walls 84 at openings 86 by a soldering or gluing process. Membranes 80 pass through openings 94 within divider wall 78, which supports membranes 80 at their midpoint. It will thus be seen that fluid entering into inlet manifold 88b is distributed across membrane array 96 wherein the fluid enters into bores 92 of membranes 80. The carrier then flows through bores 92 and is discharged into outlet manifold 88a. All liquid-filled spaces within housing 64 are sealed against leakage.
Unsaturated carrier liquid enters inlet manifold 88b through liquid inlet 98 (seen in
Untreated exhaust gas enters housing 64 through inlet plenum 32, which discharges untreated (raw) exhaust gas from an engine or other source of contaminated gasses that contains a TEG. The gas flows through the interior of housing 64, contacting membrane array 96 as the gas travels to outlet plenum 36. Membrane array 96 essentially fills the interior of housing 64 whereby a large portion of the gas contacts at least one membrane wall 90 as the gas flows through the housing. The amount of contact between exhaust gas and the membrane surfaces will be determined by several factors including the configuration of array 96, the size and spacing of membranes 80 and the speed of gas flow through housing 64. Increased contact may be obtained by closer spacing of membranes and a larger number thereof, although this has to be balanced against a possible increase of backpressure and other factors. As a result, the configuration of membrane array 96 including the number of tubular membranes that can be included within a housing of a given size, will depend to some extent on the parameters of the engine that provides the expected source of emissions and such factors as the backpressure that can be imposed by device 3 without causing significant decrease in engine performance.
The respective gas and carrier flowpaths through the housing 64, wherein the gas and liquid streams contact opposing surfaces of membranes 80, are shown schematically in
The exterior of membranes 80 thus consists of a high partial pressure side of membrane wall 90, in which the partial pressure of TEG's within the exhaust gas is relatively high in comparison with the partial pressure of the carrier circulating within bore 92. The difference in partial pressure drives the TEG's from the exterior to the interior of membrane 80. Carrier 72 flows through the interiors of membranes 80 to maintain a consistently low gas partial pressure of the TEG's.
TEG molecules 68 diffuse through the membrane according to Fick's law of diffusion and exit the membrane material at the low pressure side, where they dissolve into the permeate liquid 72 or otherwise combine with liquid 72. The stripped exhaust gas, which is rich in non-TEG molecules 3 and low in TEG molecules 68, then exits housing 64 for discharge into the atmosphere.
Carrier liquid 72, carrying TEG's 68 in dissolved or bound form (depending on the carrier), then exits housing 64 and is circulated to gas desorption vessel 24. Desorption vessel 24 is depicted schematically in
Carrier liquid 72 may comprise a task specific ionic liquid (TSIL) which binds with the TEGs molecules and increases diffusion efficiency through the phenomenon commonly referred to as the facilitated transport.
Examples of TSILs that may be used in the present invention, either alone or in combination, include:
Alternatively, carrier 150 may comprise sodium hydroxide, which can be used to absorb sulfur oxides from the emission stream and neutralize sulfur acids.
One embodiment of system 20, seen in
In the embodiment of
The multiple modules can be the same or different. In the case of different modules, the membrane assemblies therein can be configured with different pore sizes and/or membrane wall thicknesses to absorb different TEG's.
Furthermore, although
An embodiment depicted in
A further alternative embodiment of a TEG desorption system is shown in
The carrier used in the “zero discharge mode” embodiments may be a Task Specific Ionic Liquid “TSIL”. The TSIL comprises a reversible carrier. This permits the TEG+TSIL solution 7 (IL with TEG dissolved therein) to be separated in the desorption vessels 28a-c by the application of differential pressure, temperature and/or or electric potential.
Treatment system 20 is normally able to operate at engine pressure. In some cases, system 20 can generate excessive back pressure, depending on the engine design or manufacturer-imposed requirements and the number of other systems that contribute to back pressure such as turbo units, heat exchangers, pipe bends etc. If the back pressure exceeds a predetermined maximum, a booster fan 10 can be provided to boost the exhaust pressure upstream of system 20 to reduce back pressure imposed by system 20.
In one embodiment, heat from the engine exhaust is extracted with a heat exchanger prior to entering housing 64. This provides two benefits. The first is that temperature of the marine exhaust is lowered to within the lower operating temperatures of certain polymer membranes and TSILs. The second benefit is to apply the captured heat energy to provide the differential temperature to dissociate the TEGs+TSILs. The overall thermal efficiency of the system is improved, reducing the energy to operate the system.
The desorption vessel 24 is operated at near vacuum pressure to improve the dissociation rate of the TEGs and TSILs. An electric potential may also be applied to improve the dissociation of the TEGs and TSILs.
The TEGs are freed as a gas within the desorption vessels 24a-c, and collected and stored in a pressurized vessels 28a-c, or combined as a compound for storage as a solid. The TSILs remains as a liquid within the desorption vessels 24a-c. The TSIL is then pumped back to the gas absorption unit 22.
A supplemental amount of TSIL may be added periodically from a storage vessel to replace any TSIL lost through evaporation or chemical decomposition.
As shown schematically in
The control system 200 for operation of gas treatment system 20 is described below. The operation of system 20 is configure to optimize the mass transfer or absorption exhaust gas to ensure that the exhaust gas sufficiently contacts the membrane exterior surface to permit it to be absorbed through the membrane, utilizing principles of mass transfer, or Henry's Law. Control system 200 comprises in general terms a computer processor that includes a random access memory (RAM), a data storage module such as a hard drive and a user interface 330 comprising display and a data entry terminal. Control system 200 is in operative communication via wireless or wired data communication links with the sensors and detectors described herein and the various controllable components described herein including the adjustable valves, pumps, compressors and other adjustable components described herein that permit operation of gas treatment system 20.
As seen in
TEGc=Target Emission Gas Concentration as measured with sensor 62 at the funnel (exhaust outlet) after passing through the absorption unit 22.
TEGa=Target Emission Gas allowable limit, for example 25 ppm for SOX.
X=index for the counter, which tracks the numbers of gas absorption modules 26 that are in operation and non-operative.
N=total number of modules 26 available for use in system 20, for example N=20 modules for 8 MW engine.
Control system 200 operates initializes operation of the system and monitors the performance of absorption modules 20 according to the following steps:
1. At step 400, power-on control system 200 from standby mode. This step may be taken either before or after the vessel engine is powered on.
2. At step 402, enter into control system 200 form the user interface the total number of gas absorption modules 26 available in the system. This step may be pre-programmed into the control system. If not previously performed, the normal operating pressure of modules 26 may also be entered.
3. At step 404, measure the TEGc with gas sensor 62 and compare this value to the TEGa at step 406. Step 406 further comprises a determination of the number of modules of system 20 that should be actuated for system 20 to operate at an optimal efficiency level. For example, the system may contain 20 modules, and control system 200 may determine that only 15 modules are required to provide the target TEG reduction.
4. If the untreated engine exhaust contains a low level of TEG's below a selected value (TEGc is less than TEGa), the system will not turn on and the system returns to standby mode at step 408. If the TEGc levels exceed the TECa value, the system is put into operation at 410.
5. If the system is put into operation, liquid flow valve 332a for a first module 26a is actuated at 412 and the liquid pump 44 is actuated at step 414 to run at 1/N speed. This provides variable speed control. For example, if the system contains 20 modules, and control system 200 determines that only 15 modules are required to provide the target TEG reduction, then pump 44 is run at 15/20 of full operational speed, thereby reducing the power requirements for operating the system. The system then performs tests on the selected number of modules according to the steps described below. Pumps 312 are controlled by pump controller 314 which is a unit that is either responsive to controller 200 or incorporated therein.
6. The pH of the liquid solution is measured at the exit of the first absorption module 26a by pH sensor 54 at step 416. This value is indicated as pHx in
7. If pH X fails to reach pHt, indicative of fouling of membrane assembly 66a, then valve 332a is turned off at step 420, shutting off the unit, and the SERVICE REQUIRED indicator 426 is actuated at step 422. This sends a signal to service the affected module. Optionally, the signal may be sent to both an on-board monitor and also a wirelessly transmitted signal to an on-shore operator who can then arrange for a replacement module at the next port of call of the vessel. If the pH detected at step 416 remains less than pHt, then the system proceeds to step 424.
8. At step 424, carrier pressure is measured at the membrane outlet side (Px) within carrier discharge conduit. At step 425, this pressure is compared with the input pressure detected by pressure sensor 56 to determine a pressure drop. A pressure drop that exceeds a predetermined level (pressure tolerance level, Pt) is indicative of a leak, for example caused by a broken tube or seal.
9. If there is a leak, or broken tube, the control system will close the valve at step 428 and sound an alarm at step 430. This can send a satellite signal to the next port of call to schedule service to the system.
10. If no excessive pressure drop is detected, the above steps are repeated for subsequent modules 26b, c etc. (X=X+i) at steps 432 and 434 to determine whether any of these modules are fouled or leaking. Once the above steps have been performed for the optimal number of modules required for operation at the target efficiency, as determined at step 406, controller 200 continues to run the system, as shown at step 408, with this number of modules and at the corresponding pump speed for optimum efficiency.
Tests have been performed to show operational results obtained with the present system. The results of such tests are summarized in the graphs described below.
When running the apparatus as discussed above, there may be wicking of the carrier liquids to the outside of the ceramic membranes. This is undesirable, as it decreases the efficiency of the removal of the TEG's from the exhaust gas, and the wicking liquid may drip and form puddles underneath the ceramic membranes. The wicking liquid may also be corrosive, damaging the scrubber equipment.
This wicking may be eliminated through the application of negative pressure on the outlet side of the ceramic membranes, typically through the use of a suction pump. Such suction pumps are illustrated as pump 312 in
It is believed that the wicking effect may be ameliorated with low levels of negative pressure. In practice, the inventive apparatus has been run with negative pressures ranging from −25 PSI to −7 PSI, with elimination of the wicking problem observed.
In theory, the ceramic membranes may be primed through the application of a powerful enough suction pump. In practice, it has been found to be useful to use one or more priming pumps to fill the ceramic membranes. Such priming pumps are illustrated as pump 46 in
Similarly, the negative pressure may be created by one or more suction pumps located at the outlet of the ceramic membrane(s). In one preferred embodiment, the ceramic membranes are primed through the use of one priming pump, and there is a suction pump for each module. For reliability, it is preferable to have more than one suction pump. If one suction pump fails, the other suction pumps can compensate.
In operation, humidity in the exhaust stream may result in condensation on the ceramic membranes and more generally within the scrubber modules. This is undesirable as this will reduce the efficiency of the ceramic membranes for TEG's transfer. This may also result in the creation of sulphuric acid or the pooling of water and/or sulphuric acid in the scrubber modules, and lead to heavier maintenance requirements.
To address this concern, a molecular sieve (or other device to remove moisture from a gas) may be used to dehumidify the exhaust gas before it enters the scrubber modules or encounters the ceramic membranes. For example, an Enviro-Tronics™ molecular sieve BLD 4123/01-03 can be used for this purpose; however a much larger capacity molecular sieve would have to be used in a commercial application on a ship. An example of the latter is a SupasivNanomol™ from Ashton Industrial.
As discussed above, specific carrier liquids called Task-Specific Ionic Liquids or TSIL's may be selected for superior performance in extracting specific TEGs from the exhaust gas of a marine engine. A ship necessarily is a closed system in respect of carrier liquids (apart from open-loop implementations where the carrier liquid is sea water). Use of a non-resuable and non-regenerative carrier liquid requires the ship to carry enough carrier liquid to last throughout the entire voyage, and to have sufficient capacity to store the carrier liquid before use and the carrier liquid after use. The need to carry the weight of carrier liquid as well as the space requirements to store the carrier liquid both before and after use is very costly to the shipping company. Use of a regenerative carrier liquid addresses both of these concerns, by reducing the weight of carrier liquid onboard and reducing the space requirements for storing the carrier liquid, allowing the ship to carry more revenue-generating cargo.
An example of a regenerative TSIL is the use of a phosphoric acid regeneration system to remove SO2. The beginning or clean carrier liquid H3PO4+NaOH will inter react to create Na2HPO4+2H2O (in the aqueous phase), i.e.:
H3PO4+NaOHNa2HPO4+2H2O (I)
When the mixture of H3PO4, NaOH, Na2HPO4 and 2H2O encounters SO2 in the ceramic membrane, new aqueous products are formed:
Na2HPO4+SO2+H2ONaSO3+NaH2PO4 (II)
The SO2 may be recovered from the liquid carrier by using two heat exchangers. The first heats the SO2-bearing carrier liquid to separate gaseous H2O and SO2 from a liquid NA2HPO4. The second heat exchanger condenses the H2O, leaving gaseous SO2 of a high purity. The Na2HPO4 and H2O are mixed, thus recreating the original carrier liquid.
H3PO4+NaOHNa2HPO4+2H2O (I)
Turning to
The system as illustrated first passes the untreated exhaust gas 500 through a molecular sieve 502 before cooling in cooling element 504, and this is generally the preferred embodiment. However, the exhaust gas could be cooled before being dehumidified, and any combination of apparatus that results in a dry, cooled exhaust gas 506 may be used. Furthermore, the system will work without either dehumidification or cooling of the exhaust gas.
The use of a cooling element 504 is not necessary. However, the removal of SO2 from the gaseous to the liquid phase in ceramic membrane scrubber 508 increases in efficiency as the temperature difference between dry, cooled exhaust gas 506 and carrier liquid 501 is decreased. This gain in efficiency is desirable. Generally, it is more efficient to cool the exhaust gas 500 than to heat carrier liquid 501 to gain this efficiency.
Returning to
H3PO4+NaOHNa2HPO4+2H2O (I)
The carrier liquid 501 is passed through the ceramic membrane scrubber 508 where it encounters gaseous SO2 entering the ceramic membranes from dry, cooled exhaust gas 506. Upon encountering the SO2, a chemical reaction occurs so that the carrier liquid upon exiting the ceramic membrane scrubber 508 comprises exit liquid 503:
H3PO4+NaOHNa2HPO4+2H2O (I)
and
Na2HPO4+SO2+H2ONaSO3+NaH2PO4 (II)
The SO2 is now in liquid form. Exit exhaust gas 507 has a lower concentration of SO2 than dry, cooled exhaust gas 506.
The liquid 503 is taken to siphon-type evaporator 510, which is heated by steam 512 or another suitable source of heat. Evaporator 510 separates the liquid 503 into a gaseous phase 514 containing SO2+H2O and a liquid phase 516 containing Na2HPO4. Generally, several types of evaporators may be used for this step. The gaseous phase 514 is condensed in condenser 516 to produce gaseous SO2 518 and liquid H2O 520.
Gaseous SO2 518 can then be dealt with as desired. Typically, the captured gaseous SO2 518 is taken to a sulphur recovery unit; more generally, it can be stored or treated and released or converted to a useful form. The gaseous SO2 518 may, for example, be converted to sulphuric acid.
Liquid H2O 520 is mixed with liquid Na2HPO4 516 in tank 522. Since the liquid Na2HPO4 516 contains heat provided by siphon-type evaporator 510 and the liquid H2O 520 contains heat from condenser 516, the liquid Na2HPO4 516 and liquid H2O 520 will react to regenerate liquid carrier liquid 501:
H3PO4+NaOHNa2HPO4+2H2O (I)
For greater efficiency, the contents of tank 522 may be mixed or agitated.
In order for heat exchanger 510 to create gaseous SO2 and H20, the carrier liquid will have to be heated to between 100 and 250 degrees Celsius. To condense the water, gaseous stream 514 should be cooled below 100 degrees Celsius. Such a system should be able to produce an SO2 stream of approximately 90-95% purity.
As noted above, the system illustrated in
In one specific example, using the setup illustrated in
The invention is not intended to be limited to the embodiments described herein, but rather the invention is intended to be applied widely within the scope of the inventive concept as defined in the specification as a whole including the appended claims.
This application is a continuation-in-part of co-pending U.S. application Ser. No. 14/745,079, filed on Jun. 19, 2015, which is a continuation of co-pending PCT application No. PCT/CA2014/050359 filed on Apr. 8, 2014, which claims priority to U.S. Provisional Application No. 61/835,288, filed on Jun. 14, 2013, the entire disclosures of which are incorporated herein by reference.
Number | Date | Country | |
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61835288 | Jun 2013 | US |
Number | Date | Country | |
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Parent | PCT/CA2014/050359 | Apr 2014 | US |
Child | 14745079 | US |
Number | Date | Country | |
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Parent | 14745079 | Jun 2015 | US |
Child | 14793446 | US |