Patent Grant
6905534
1. Field of the Invention
The invention relates generally to the removal of vapor phase contaminants from a gas stream. More specifically, the invention is directed to the removal of vapor phase mercury from the flue gas of a combustion system.
2. Description of Related Art
The emission of trace metals from utility power plants is an important issue in light of the 1990 Clean Air Act Amendment (CAAA), Title III. In particular, special attention has been given to mercury (Hg) in terms of its environmental release and impacts, and the Environmental Protection Agency (EPA) is closely scrutinizing sources that emit mercury. Mercury is present in flue gas from a fossil-fuel-fired combustion system in very low concentrations (<1 ppm) and forms a number of volatile compounds that are difficult to remove. Specially designed and costly emissions-control systems are required to effectively capture these trace amounts of mercury.
Several approaches have previously been adopted for removing mercury from gas streams. These techniques include passing the gas stream through a fixed or fluidized sorbent bed or structure or using a wet scrubbing system. Approaches using fixed bed technologies normally pass the mercury containing gas through a bed consisting of sorbent particles or through various structures such as honeycombs, screens, or fibers that are coated with a sorbent. Common sorbents include activated carbon and noble metals such as gold and silver. In many cases where noble metals are used, the structure is coated with the noble metal sorbent while the support underneath is made of ceramic or metallic materials. The sorbents in these fixed structures can be periodically regenerated by heating the structure and driving off the adsorbed mercury (see, for example, U.S. Pat. Nos. 5,409,522 and 5,419,884, which are incorporated herein by reference in their entireties). The mercury driven off can then be recovered or removed separately.
However, in regenerating the sorbent in such fixed bed systems, the bed must be taken off-line periodically. This necessitates that a second bed be used and remain on-line while the first one is regenerating. In addition, the beds need to be located downstream of a primary particulate collection device to remove all of the solid suspended particles in the gas stream and to avoid pluggage. These fixed bed systems also require significant space and are very difficult to retrofit into existing systems, such as into the ductwork of power plants, without major modifications and high pressure drop penalties (e.g., 10-30 inches of water).
U.S. Pat. Nos. 5,948,143 and 6,136,072, which are incorporated herein by reference in their entireties, describe concepts that addressed some of these problems through the use of porous tubes and plates that can be regenerated and cleaned while in the presence of flue gas containing particles. These porous tubes and plates are cleaned by a series of back pulses across their walls. However, the fabrication of porous tubes and plates is complex and relatively expensive. The tubes and plates are also heavy and difficult to install and heat due to the thick wall requirements.
Therefore, a need remains for a cost-effective method of removing trace contaminants, in particular mercury, from the flue gas of a combustion system. Specifically, there is a need for a fixed bed process for removing such contaminants that can be easily retrofitted into an existing combustion process, easily cleaned to avoid plugging, and easily regenerated.
The present invention provides a method and apparatus for removing trace contaminants from a gas stream or flue gas. In one embodiment, the present invention an apparatus for removing a trace contaminant from a gas stream, comprising a gas duct configured to receive a gas stream comprising a trace contaminant; a plurality of substrates disposed within the gas duct; a trace contaminant sorbent disposed on at least a portion of each of the substrates; an isolation device for separating the portion of each of the substrates from the gas stream; and a regenerator for regenerating the trace contaminant sorbent.
In another embodiment, the present invention comprises a method for removing a trace contaminant from a gas stream, comprising passing a gas stream comprising a trace contaminant through a gas duct; contacting the trace contaminant with a trace contaminant sorbent disposed on at least a portion of a substrate within the gas duct; adsorbing the trace contaminant with the trace contaminant sorbent; isolating the portion of the substrate from the gas stream; cleaning the substrate in-situ and concurrently with the passing of the gas stream through the gas duct; and regenerating the trace contaminant sorbent in-situ and concurrently with the passing of the gas stream through the gas duct.
In another embodiment, the present invention comprises one or more substrates having a trace contaminant sorbent thereon positioned inside of an electrostatic precipitator or downstream of an electrostatic precipitator, where, for example, a substrate having a trace contaminant sorbent thereon may be used in place of an electrically-charged plate typically used in the ESP. In another embodiment, the present invention comprises one or more substrates having a trace contaminant sorbent thereon positioned inside of a baghouse, where, for example, the substrate may be used in place of a filter bag cage or the filter cloth, or positioned near the outlet of each filter bag, or placed to cover all or a portion of the outlet of a plurality of filter bags. In another embodiment, the present invention comprises one or more substrates having a trace contaminant sorbent thereon positioned downstream of a baghouse, for example, near the outlet of the baghouse.
In another embodiment, the present invention comprises one or more substrates having a trace contaminant sorbent thereon positioned in the mist eliminator section of a wet scrubber, wherein the substrates also act as a mist eliminator. In another embodiment, the present invention comprises one or more substrates having a trace contaminant sorbent thereon positioned upstream or downstream of a mist eliminator in a wet scrubber.
In another embodiment, the present invention comprises a substrate that is disposed within the gas duct, wherein the substrate is itself constructed of a sorbent material.
The present invention provides a cost-effective method of removing trace contaminants, in particular mercury, from the flue gas of a combustion system. Specifically, the present invention provides a fixed bed process for removing such contaminants that can be easily retrofitted into an existing combustion process, easily cleaned to avoid plugging, and easily regenerated.
These and other features of the present invention will appear from the following description from which the preferred embodiments are set forth in detail in conjunction with the accompanying drawings.
In accordance with one embodiment of the present invention, a substrate having a trace contaminant sorbent disposed on at least a portion of the surface of the substrate is placed within a gas duct of a process, such as the one described in connection with
It should be appreciated that, in general, the substrate may be located anywhere in the gas duct of a given process where it is desirable to remove a particular trace contaminant from a flue gas. It should be also appreciated that any number of substrates may be used in either the same general location or in different locations and each of these substrates may have the same, similar, or different shapes and sizes. Moreover, each of these substrates may utilize the same, different, or a mixture of trace contaminant sorbents. The remainder of this description, however, will be presented in the context of the process described in
Referring back to
The size and shape of the substrate is determined, in part, upon the size and shape of the gas duct into which it is placed. It should be appreciated that the present invention may easily be used as a retrofit in existing processes such as the one described in connection with FIG. 1. In such a retrofit, it would be desirable to utilize existing ductwork for the substrates of the present invention rather than replacing existing ductwork to accommodate a pre-designed substrate or substrates. Therefore, the size and shape of the substrates would be determined based upon the size of the existing ductwork.
The size and shape of the substrate would also be determined, in part, on maximizing contact between the flue gas and the substrate, avoiding or minimizing deposition of particulate and ash in the flue gas on the substrate, and minimizing gas flow pressure drop across the substrate. For example, in connection with the process of
As noted, the size and shape of the substrate would be selected to effect the most contact between the gas and the surface of the substrate while minimizing particle deposition and fouling of the plate as well as gas flow resistance or pressure drop. For example, if a plurality of substrates of the present invention were sized to be used in an existing duct that was relatively small, the length of the substrates could be extended to provide the necessary surface area to achieve the desired trace contaminant removal. Preferably, the substrate has a high surface area, such as approximately 1-100 ft2 of surface area per ft3/s of gas flow, more preferably approximately 1-50 ft2/ft3/s, and most preferably approximately 10 ft2/ft3/s.
Lastly, it should be appreciated that the substrate may be placed within a gas duct in any orientation. One of skill in the art will appreciate that the orientation of the substrate will be dependent upon many factors, including, for example, the size, shape, and number of substrates, the size and shape of the gas duct itself, the desired contact between the substrate and the flue gas, and the pressure drop across the substrate. One of skill in the art will appreciate how to optimize these and other factors to determine such placement and orientation of the substrate within the gas duct.
In a preferred embodiment, the substrate is a flat, thin plate coated with a trace contaminant sorbent. A typical plate size may be 1-20 feet in length, a height substantially the same as the height of the gas duct into which it is placed, and a thickness of 0.1-1 inch. Such a plate may be made from any appropriate material sufficient to retain a trace contaminant sorbent on its surface and capable of withstanding the flue gas environment into which it is placed. Preferably, such a plate or other substrate may, for example, be made of any metal, including steel, or ceramic.
It should be appreciated that any sorbent may be disposed on the substrate; however, the choice of sorbent will be dependent upon the trace contaminant to be removed, including its physical properties and characteristics. For example, gold is a preferred sorbent for use in the removal of mercury from the flue gas since it readily forms an amalgam with mercury. Other metals that form amalgams with mercury, such as silver and zinc, are also preferred. The sorbent may consist of a single layer of the selected trace contaminant sorbent or of multiple layers of either the same or different sorbents, such as gold plated over silver or zinc. A preferred embodiment comprises gold as the trace contaminant sorbent on a metal substrate or metal or plate. Another preferred embodiment comprises gold as the trace contaminant sorbent coated over layers of silver or zinc coated on a metal substrate. By coating the gold over silver or zinc, less gold is necessary since absorbed mercury will also form an amalgam with the underlying silver or zinc; however, the gold may act to protect the silver or zinc from corrosion. In this embodiment, the gold layer may be on the order of 1 or a few microns in thickness. One of skill in the art will appreciate that the application of the sorbent to the substrate can be performed by various methods known in the art, depending upon the particular sorbent and the particular substrate used, such as electroplating or metal vapor deposition. In a preferred embodiment, the substrate is either a metal or ceramic flat plate, as described above, that is coated with 0.1-100 μm thick layer of trace contaminant sorbent, such as gold or other trace contaminant sorbents, such as silver, zinc, activated carbon, or any other sorbent selected for removal of a specific trace contaminant.
While the substrate has been discussed as being made of a metal or ceramic, it should be recognized that the substrate may be made of any material on which a trace contaminant sorbent may be disposed. Also, the material used to construct the substrate must be able to withstand the flue gas conditions to which it will be exposed. In another embodiment, however, the substrate may be made from the trace contaminant sorbent material itself, which avoids the step of disposing a trace contaminant material onto the substrate. For example, the substrate may be made from an activated carbon or carbon fiber material. When the substrate is made from the trace contaminant material itself, the substrate needs to have sufficient integrity to remain intact during operation. One of skill in the art will recognize how to make a substrate with sufficient integrity from a material such as a trace contaminant sorbent using methods known in the art. It should be appreciated that the above as well as the following embodiments are described in terms of a substrate having trace contaminant sorbent disposed thereon; however, any of these embodiments may utilize a substrate made from the trace contaminant sorbent itself. Therefore, the discussion of each embodiment should not be construed as limited to the use of a substrate having a trace contaminant sorbent disposed thereon and may alternatively, or in combination, be used with a substrate made from a trace contaminant sorbent material itself.
In operation, when the isolation device 404 is in the open position, the isolation door 410 is oriented substantially parallel to the gas flow 406 and thereby allows the gas flow 406 to travel within the corresponding channel. In other words, the gas flow 406 passes between and in contact with two sides of adjacent substrates 402 that form a channel corresponding to the isolation door 410 that is in the open position. More specifically, the gas flow 406 is free to pass between two corresponding sides of two substrates 402, or, in the case where the substrate 402 is located next to the gas duct wall 403, along one corresponding side of a substrate 402 and the gas duct wall 403. When the isolation device 404 is in the closed position, the isolation door 410 prevents the passage of the gas flow 406 through that corresponding channel, thereby isolating one particular side of a substrate 402 and one particular side of an adjacent substrate 402, or, in the case where the substrate 402 is located next to the gas duct wall 403, isolating only that corresponding side of the substrate 402.
This feature is particularly useful for cleaning the substrate or regenerating the trace contaminant sorbent without having to stop the flow of gas through the duct or without having to stop or divert the gas flow through the entire structure of substrates, as will be further described below. In particular, this feature allows the isolated sides of the substrates 402 to be cleaned in-situ, that is without removing them from the gas duct, and the trace contaminant sorbent on those isolated sides can be regenerated in-situ, again without removing the trace contaminant sorbent or substrate from the gas duct. Moreover, this cleaning and regeneration can be performed concurrently with the gas flow 406 moving past the sides of the substrates 402 that have not been isolated.
It should be appreciated, however, that the isolation device 404 and the damper valves 408 may be controlled and activated by any known control system known in the art. Further, more than one isolation device may be activated at the same time or they may be activated in a predetermined, controlled sequence based upon a predetermined set of parameters or measurements. It should also be appreciated, as noted, that one or more isolation devices 404 may be activated and put into the closed position, while the remaining isolation devices 404 remain in the open position, thereby allowing the gas flow 406 to flow concurrently while certain isolation devices 404 are in the closed position and others are in the open position.
It should be appreciated that a cleaning mechanism may be added to clean any type of substrate or substrates used in the present invention. Further, the cleaning mechanism and the method used to clean the substrate or substrates of the present invention may be any cleaning mechanism or method known in the art; however, it should be appreciated that the cleaning mechanism is an optional part of the present invention. For example, a mechanical rapping device or a high pressure air jet may be used to dislodge accumulated particulate matter on the substrate. Furthermore, such cleaning mechanism may be activated and used in conjunction with the operation of the isolation device. That is, upon activating the isolation device, the corresponding side of the substrate that has been isolated may be cleaned using the cleaning mechanism. Moreover, such cleaning may be performed in-situ and concurrent with the flow of flue gas past the other non-isolated substrates.
It should also be appreciated that the present invention may further comprise a regenerator for regenerating the trace contaminant sorbent on the substrate. Such a regenerator may comprise any device capable of desorbing the sorbed trace contaminant from the trace contaminant sorbent. For example, a regenerator may comprise an electrical resistance heater attached to each substrate for heating the substrate to a given temperature at which any trace contaminant is desorbed from the trace contaminant sorbent. Another example of a regenerator is a device capable of providing a hot gas stream that is passed by the substrate and desorbs the trace contaminant from the trace contaminant sorbent based upon the gas stream's temperature. It should be appreciated that the regenerator may be used separately or in combination with the cleaning mechanism. Moreover, such regeneration may be utilized in conjunction with the operation of the isolation device. That is, upon activating the isolation device, the trace contaminant sorbent on the corresponding side of the substrate that has been isolated may be regenerated. Moreover, such regeneration may be performed in-situ and concurrent with the flow of flue gas past the other non-isolated substrates.
As noted, one example of a regenerator comprises a heater for heating the substrate, such as an electrical resistance heating device attached to each substrate. In operation, the substrate would be heated upon activation of the electrical heater to a temperature at which any adsorbed trace contaminant would be desorbed from the trace contaminant sorbent. This regeneration could be performed in-situ, that is without removing the substrate from the gas duct. This regeneration could also be performed while the flue gas was not flowing through the gas duct or in conjunction with the isolation device whereby only those isolated substrates, or only those particular isolated sides of certain substrates, are heated to desorb any adsorbed trace contaminant. The desorbed trace contaminant can then be collected by a gas stream that is passed by the isolated sides of those substrates being regenerated. This gas stream can then be routed to a secondary recovery system where the desorbed trace contaminant is collected, concentrated, and disposed of by methods well known in the art. Once the trace contaminant sorbent has been regenerated it is capable of being placed back in service.
As the regeneration gas 416 passes beside and contacts the isolated side 402a of the substrate 402, any adsorbed trace contaminant is desorbed from the trace contaminant sorbent and carried with the regeneration gas 416 through the outlet regeneration gas duct 422. As noted above, after exiting the isolated channel 412, the regeneration gas 416 may be sent to a separate secondary recovery system where the trace contaminant is removed, concentrated, and disposed of by any known method in the art. It should be appreciated that the regenerator and its operation described in connection with
In general operation of the present invention, a trace contaminant would be removed upon contacting the flue gas and, therefore, the trace contaminant, with the trace contaminant sorbent disposed on the substrate, such as a plate. Upon such contact, the trace contaminant would adsorb onto the sorbent. With respect to the removal of mercury, for example, upon contact between the trace contaminant mercury and the trace contaminant sorbent selected to remove mercury, for example, gold, the mercury would be adsorbed on the trace contaminant sorbent on the substrate surface as the flue gas passes over the substrate. In the case of gold, it should be appreciated that the adsorbed mercury reacts with the gold to form an amalgam.
As the substrate surface gets fouled with dust particles from the gas stream, it can be cleaned, preferably in-situ (i.e., without having to remove the substrate from the duct) and during continued operation of the main process (i.e. without stopping the flow of the flue gas, that is, concurrently with the flow of gas through the gas duct). This allows process operation to continue uninterrupted while the substrates or plates, or at least a portion of them, are cleaned. Cleaning may be conducted by mechanically rapping, by directing a high pressure air jet toward the substrate surface to knock the dust or particulate matter off of the surface, or by any other method known in the art. It should be appreciated that such cleaning may be performed at any time or at a particular, predetermined time, for example, at a point where a given amount of particulate matter has attached to the substrate such that contact between the trace contaminant and the trace contaminant sorbent has been significantly adversely affected or reduced.
When the surface of the trace contaminant sorbent becomes saturated with the trace contaminant, the sorbent may be regenerated. In one embodiment, this regeneration may be accomplished by heating the sorbent using electric heaters, steam or the flue gas itself, to desorb the trace contaminant followed by collection of the desorbed contaminant in a secondary recovery system. For example, with respect to removal of mercury, metal plates may be used as the substrate with gold as the trace contaminant sorbent. In this case the plates and the gold sorbent can be regenerated by heating the plates so that the mercury desorbs since the formation of an amalgam is a relatively easily reversible reaction. It should further be appreciated that mercury can be easily desorbed from activated carbon upon heating as well. Any mercury desorbed from the plates can be recovered in a secondary system for later containment through condensation or other storage mechanism or process.
In a preferred embodiment, such regeneration may be conducted in-situ and concurrent with the flow of flue gas through the gas duct. For example, the regeneration can take place within the gas stream by isolating some or all of the substrates via the use of an isolation device, such as a system of damper valves as described in connection with
Further, it should be appreciated that gas flow vanes (not shown) may also be used in an upstream portion of the ESP. In this case, one or more of these gas flow vanes may also be replaced, in addition to replacing one or more of the ESP plates, with a substrate having a trace contaminant sorbent thereon, or made from a trace contaminant sorbent, according to the present invention. Alternatively, rather than replacing any of the ESP plates, it is possible to just replace one or more of the gas flow vanes with a substrate having a trace contaminant sorbent thereon or made from such a sorbent.
It should be appreciated that either the substrate in the ESP or used as gas low vanes may also be configured to be cleaned and/or regenerated as described previously, such as by using a cleaner mechanism and/or regenerator may be sued. For example, the substrates in the ESP may be cleaned as ordinary electrically-charged plates in an ESP are cleaned. Also, the substrates may be isolated to regenerate the sorbent in-situ using an isolation device as described above.
In operation, the flue gas 1102 exits the ESP 1106 and passes by the substrates or plates 1110 resulting in adsorption of trace contaminants present in the flue gas 1102. It should be appreciated that in this embodiment the gas flow velocity in the outlet damper valve chamber is relatively slower. Therefore, the substrate or plates may be construed to be relatively shorter than if plates were used in a section of ductwork where the gas velocity was relatively higher. Because the gas velocity is relatively slower, the same contact time between the gas and the trace contaminant sorbent may be achieved with relatively shorter plates.
A substrate having a trace contaminant sorbent thereon may be used in conjunction with the bags 1202 and cages 1204 in a variety of ways, which are separately shown in FIG. 12. In one embodiment, the substrate may be in the shape of a cylindrical rod 1208 that extends from the top to the bottom of the bag or cage. Such a rod 1208 may be used in conjunction with a cage (not shown) or alone such that the rods act to support a bag. In operation, the gas passes from the outside of the bag into its interior and flows past the rods having trace contaminant sorbent, which allows trace contaminants to be adsorbed by the sorbent.
In another embodiment, instead of using a substrate such as rods, a wire mesh material 1210, such as chicken wire, that is rolled in the shape of a tube may be used. In this embodiment, the wire mesh 1210 may completely replace the bag 1202 and its cage 1204. In operation, as gas is passed into the baghouse 1200, it will flow past the wire mesh allowing trace contaminants to be adsorbed onto the trace contaminant sorbent. Similarly, a substrate 1212 such as this wire mesh may be used in conjunction with a cage 1214 and/or a bag 1202 as well. In this configuration, the substrate 1212 may be removed without having to remove the cage 1214. It should be appreciated that in any of the embodiments described above in connection with
It should be appreciated that the substrate used to replace one or more of the mist eliminator vanes may be any substrate according to the present invention. The shape of this substrate may also be any shape, recognizing that it must allow gas flow to pass by it and also must fit between any remaining mist eliminator vanes in the case where only a few vanes are replaced. Alternatively, each of the mist eliminator vanes may be replaced, in which case, the substrates will need to be shaped to provide mist elimination. For example, the substrates may be shaped the same as the mist eliminator vanes. One specific example of such a substrate is a gold plated mesh that has sufficient rigidity to be shaped similarly to a mist eliminator vane.
Further, it should be appreciated that the position of the array of substrates 1702 may be positioned downstream of the mist eliminator. Also, it should be appreciated that the array of substrates may be used in a horizontal position, where the gas duct is oriented such that the gas flow is in a horizontal direction. One advantage of using a combination of an array of substrates and a separate mist eliminator allows for removal of one or the other without having to lose the functionality provided by the other. For example, if portions of the array of substrates need to be removed for cleaning or regeneration, the mist eliminator section would still be operational to remove entrained mist. Conversely, if the mist eliminator served to provide both trace contaminant removal and mist elimination, removal of the mist eliminator section for cleaning, for example, would result in the loss of trace contaminant removal by those vanes comprising a sorbent.
The invention having been described, the following Examples are presented to illustrate, rather than to limit, the scope of the invention.
Tests have been conducted in the laboratory and at 7 power plants burning lignite, PRB and bituminous coals to determine real-time mercury removal across gold-coated plates and mercury removal following several weeks of exposure to flue gas at each plant. Tests were conducted downstream of ESPs, scrubbers, spray dryers, and baghouses.
Field tests have been conducted using gold as the sorbent surface downstream of both a wet and dry sulfur dioxide scrubber. Using lignite coal, 70-90% mercury removal was obtained downstream of a spray dryer baghouse configuration at a gas velocity of 30-40 ft/s. The gold plates were 10 ft long and spaced 0.5 inches apart resulting in a pressure drop of approximately 2 inches of water. Tests also showed that the gold-coated plates may be thermally regenerated without degradation of the adsorption capacity. Tests using gold plates 1-3 ft in length with 0.25 inch spacing downstream of a wet scrubber with 8-17 scfm flue gas flow showed 63-95% mercury removal. The gold plates were continuously wetted with wash water from a full-scale mist eliminator.
Various embodiments of the invention have been described above. The descriptions are intended to be illustrative of the present invention and are not intended to be limiting. It will be apparent to one of skill in the art that modifications may be made to the invention as described without departing from the scope of the claims set out below. For example, it is to be understood that although the invention has been described using as an example mercury, any trace contaminant may be removed by the present invention. It should be also be appreciated that the present invention is adaptable to existing flue gas ducts or for use in new gas ductwork. Furthermore, it is to be understood that although the invention has been described for use in connection with flue gas streams from combustion processes, is contemplated that the invention may be used in connection with any gas stream containing a trace contaminant. It should also be appreciated that in any of the embodiments described that the substrate may either have a sorbent material coated thereon or be constructed from a sorbent material. Also, while the sorbent structure in some embodiments has been described as a rectangular flat plate, it should be appreciated that other shapes for the sorbent structure are contemplated by the present invention.
This application is a continuation-in-part of U.S. patent application Ser. No. 10/124,000 filed Apr. 16, 2002, now U.S. Pat. No. 6,695,894, which claims the benefit of U.S. Provisional Application No. 60/284,588 filed Apr. 16, 2001. Both of these applications are incorporated herein by reference in their entirety.
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| Number | Date | Country | |
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| Number | Date | Country | |
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| Parent | 10124000 | Apr 2002 | US |
| Child | 10431553 | US |
