CN110755997A

CN110755997A - Emissions control system with ability to clean and/or regenerate carbon-based sorbents and method of use

Info

Publication number: CN110755997A
Application number: CN201910668183.7A
Authority: CN
Inventors: H·斯图勒; L·斯图勒; V·T·沃尔沃思; S·德拉蒙德
Original assignee: Chemical And Metal Technology Co Ltd
Current assignee: Chemical And Metal Technology Co Ltd
Priority date: 2018-07-23
Filing date: 2019-07-23
Publication date: 2020-02-07
Also published as: JP7281355B2; JP2020040060A

Abstract

A system and method for cleaning, conditioning and/or regenerating carbon-based sorbents is disclosed wherein contaminants are separated from the sorbents using a chemical cleaning process. The contaminants can be disposed of or recycled for industrial use. The cleaned and/or regenerated carbon-based adsorbent is recycled back to the fluidized bed apparatus in the shape of a reverse venturi for later use. The spent carbon-based adsorbent may be directed to appropriate disposal. Carbon-based adsorbents include, but are not limited to, activated carbon adsorbents and biochar adsorbents. Optionally, the sorbent may be treated by the system prior to exposure of the sorbent to contaminated emissions to enhance and increase the porosity of the outer surface of the sorbent.

Description

Emissions control system with ability to clean and/or regenerate carbon-based sorbents and method of use

Cross Reference to Related Applications

This application is a partial continuation of U.S. patent application No. 15/606,704 filed on 26/5/2017, which is a partial continuation of U.S. patent application No. 14/808,563 filed on 24/7/2015, which claims the benefit of U.S. provisional application No. 62/029,044 filed on 25/7/2014 and U.S. provisional application No. 62/133,791 filed on 16/3/2015. The entire contents of the above application are incorporated herein by reference. Cross Reference to Related Applications

The present disclosure relates generally to industrial emission control systems and methods, devices used in such systems, and methods of removing pollutants from gaseous and non-gaseous emissions.

Background

This section provides background information related to the present disclosure that is not necessarily prior art.

Many industries in many economic sectors have such emissions or emissions of that kind. Such emissions can be divided into two basic groups, one being gaseous and the other non-gaseous. Emissions in the gaseous group and emissions in the non-gaseous group often contain harmful pollutants. The emissions in the gaseous group may be in the form of exhaust gas produced by a coal-fired plant or from a natural gas combustion facility. The emissions in the non-gaseous group may be in the form of liquid, sludge or pulp-like material. When the level of harmful pollutants in the effluent reaches and/or exceeds allowable limits, the pollutants must be neutralized, captured, collected, removed, disposed of, and/or properly sequestered by one or other methods.

Many industries rely on burning fuels as a means of accomplishing some aspects of their respective processes. For example, in a first example, a steel mill burns and/or smelts metal in the process of making metal shapes, extrusions, and other metal castings. The processes used in the metal industry include operations where particles are emitted as metal vapor and ionized metal. Pollutants harmful to the environment, plants, animals and/or humans are released into the air via metal vapors. To some extent, it is necessary to properly collect and dispose of the hazardous contaminants in the metal vapor and/or metal vapor compounds. In a second example, industries that mine precious metals such as gold, silver, and platinum include metal and metal vapor emissions containing heavy metal contaminants and particulates that are considered harmful if not captured, collected, and properly disposed of. In a third example, emissions from natural gas burning industries often contain higher levels of pollutants that are considered harmful if not captured, collected and properly disposed of. In a fourth example, energy producers using coal as a combustible consumable to produce steam in boilers for rotating electrical generators have considerable emissions containing metal vapors and metal compounds that are considered harmful to the environment, plants, animals, and humans. Among other harmful contaminants, metal vapor emissions typically contain mercury (Hg).

Due to the pattern of global air jets, airborne metal vapor emissions can be carried from one country and deposited in another. For example, many mercury emissions produced in china and/or india may actually end up in the united states and/or the seawater in between. In a similar manner, many mercury-containing emissions produced in the united states may actually be deposited in europe and/or the seawater in between. To complete this cycle, many of the mercury-containing emissions produced in europe may actually be deposited in china and/or india. Therefore, the sequestration of mercury and other harmful pollutants in emissions produced by industrial processes is a global problem with global applications that require global efforts to address.

National and international regulations, provisions, expenses, monitoring, and a series of evolving and increasingly stringent laws are proposed and/or enforced for those industrial processes that produce such emissions. For example, one of the most serious and regulated pollutants in metal vapor emissions is mercury. The human industrial process has greatly increased the accumulation of mercury and/or mercury deposits at concentrations well above naturally occurring levels. It is estimated that the total amount of mercury released by human activity worldwide is up to 1,960 metric tons per year. The number is calculated from the data analyzed in 2010. The largest contributors to this particular type of emissions worldwide are coal (24%) and gold mining (37%) activities. In the united states, the proportion of coal emissions is higher than in gold mining activities.

A major problem with animal and human exposure to mercury is that it is a bioaccumulating substance. Thus, any amount of mercury ingested by the fish or other animal will remain in the animal (i.e., accumulate) and be transferred to the human or other animal when ingested by the human or other animal. In addition, mercury is not emitted from the body of the ingested subject. In the food chain, larger predators who have the longest survival time and/or eat large numbers of other animals have the greatest risk of accumulating excess mercury. Animals, especially fish, that eat too much mercury in humans experience a variety of well-known medical problems, including neurological diseases and/or reproductive problems.

There are three main types of mercury emissions: man-made emissions, re-emissions, and naturally occurring emissions. Man-made emissions are primarily a result of industrial activities. Sources of artificial emissions include industrial coal-fired plants, natural gas combustion facilities, cement production plants, oil refining facilities, chlor-alkali industry, vinyl chloride industry, mining operations, and smelting operations. Re-emissions occur when mercury deposited in the soil is re-distributed via flooding or forest fires. Mercury absorbed in and/or deposited in the soil may be released back into the water via storm water runoff and/or flooding. Therefore, soil erosion contributes to this problem. Forest fires, whether they are natural disasters, fires or intentional burning of felled forests, re-emit mercury back into the air and/or water supply and can only be re-deposited elsewhere. Naturally occurring emissions include volcanic eruptions and geothermal vents. It is estimated that about half of all mercury released into the atmosphere comes from naturally occurring events such as volcanic eruptions and thermal vents.

As mentioned above, coal-fired plants release large quantities of mercury and other pollutants into the environment each year. Accordingly, many efforts are underway to reduce the amount of harmful pollutants in the flue gas emissions produced by coal-fired plants. Many coal-fired plants in the united states are equipped with emission control systems that capture, sequester, and/or recover harmful elements, such as mercury. In coal-fired plants, coal is burned to boil water, turning it into operationSteam of the generator. The flue gas emissions from the combustion of coal are typically conveyed through a duct system to a fluid gas desulfurization unit and/or a spray drying system to remove some of the emissions and some of the toxic fumes, such as sulfur dioxide (SO), from the flue gas₂) And hydrogen chloride (HCl). Typical duct systems then direct the flue gas stream to a wet or dry scrubber where more sulfur dioxide, hydrogen chloride and fly ash are removed. The flow of flue gases is directed through a bag house where particles are separated from the flow of flue gases, similar to the way a household vacuum cleaner bag works. The smoke passes through a bag like filter having holes that allow airflow but not the larger particles flowing in the airflow. The surface of the filter bag is shaken and/or cleaned to collect the captured particles so that they can be disposed of. Often, these deposits are themselves harmful emissions and must be disposed of. The remaining flue gases passing through this type of emission control system are then allowed to escape through the high stack and released into the atmosphere.

A problem with this type of emission control system is that it is almost ineffective to capture and/or collect heavy metals such as mercury contained in the form of metal vapors and metal compound vapors. Because coal-fired combustion systems combust coal at relatively high temperatures approaching 1500 degrees fahrenheit, mercury is converted into nano-sized vapor particles that can pass through even the most capable filtration systems. As a result, large emissions of airborne mercury and other harmful pollutants are released into the atmosphere.

To capture and collect mercury from coal burning systems and/or other mercury emission sources, several known systems have been developed to address this problem, and these generally fall into one of three categories.

The first type is a group of methods and/or systems for capturing mercury by injecting a sorbent into a flue gas stream. The most commonly used adsorbent materials, in addition to the precious metals, are activated carbon and/or biochar. Activated carbon is typically halogenated with bromine. Biochar is a form of charcoal that is rich in carbon. Injecting the sorbent into the flue gas helps to capture pollutants in one and/or any combination of the following typical emission control devices: an electrostatic precipitator, a fluidized gas desulfurization system, a scrubber system, or a fabric filter system. There are several variations of these systems that require the injection of activated carbon at various points in the emissions control system after the coal is combusted. Some exemplary methods and/or systems of the first category are disclosed in U.S. Pat. nos. 7,578,869, 7,575,629, 7,494,632, 7,306,774, 7,850,764, 7,704,920, 7,141,091, 6,905,534, 6,712,878, 6,695,894, 6,558,454, 6,451,094, 6,136,072, 7,618,603, 7,494,632, 8,747,676, 8,241,398, 8,728,974, 8,728,217, 8,721,777, 8,685,351 and 8,029,600.

The second is a group of methods and/or systems that pretreat the coal prior to combustion in an effort to reduce the mercury levels in the coal. Some exemplary methods and/or systems of the second category are described in U.S. patent nos. 7,540,384, 7,275,644, 8,651,282, 8,523,963, 8,579,999, 8,062,410, and 7,987,613. All of the methods and/or systems set forth in these exemplary patents produce large quantities of unusable coal, which is also considered hazardous waste. Thus, the methods and/or systems of the second class of known solutions are inefficient and expensive to operate. In addition, coal pretreatment typically requires a large amount of capital and physical space, and thus retrofitting many existing emission control systems with the necessary equipment is impractical.

The third category is a group of methods and/or systems that inject catalyst into the emission control device upstream of the activated carbon injection system. The catalysts in these processes and/or systems ionize mercury, making it easier to collect and remove from flue gases. However, these methods and/or systems are inefficient and costly to operate, such that the methods and/or systems of the third class of known solutions are not cost-effective. Examples of the third category are described in U.S. patent nos. 8,480,791, 8,241,398, 7,753,992 and 7,731,781. In addition to these examples, U.S. patent No. 7,214,254 discloses a method and apparatus for regenerating expensive sorbent materials by using microwave and fluidized bed reactors. The method selectively vaporizes mercury in the sorbent, where the mercury can be captured in a specialized filter or condensed and collected. The use of microwave generation makes this process impractical for large scale commercial applications and therefore only for the regeneration of expensive adsorbents. Another example is found in U.S. patent application publication No. 2006/0120935, which discloses a method of: any of several matrix materials are used to create a chemical attraction for mercury as the flue gas passes through the emission control device, thereby removing mercury from the flue gas. This method is also impractical for large-scale commercial use. Thus, current emission control systems and methods typically operate by transferring harmful pollutants from gaseous emissions to non-gaseous emissions, which creates another set of emission control problems.

While many laws and regulations focus on metal vapor emissions, other forms of emissions containing hazardous pollutants, such as mud and/or sludge-like emissions, sludge and/or sludge-like emissions, liquid and/or liquid-like emissions, and other emissions variants, should not be ignored. All of the emissions types listed may also require disposal, wherein the hazardous contaminants they contain may be neutralized, captured, collected, removed, disposed of, and/or properly sequestered by such or other means. Historically, the most cost-effective and most widely used processes for removing harmful pollutants have utilized activated carbon (in one form or another) through which the emissions are passed. Thus, the demand for activated carbon in the united states is expected to increase annually by 2017, requiring over 10 billion pounds per year and an industrial cost of over $ 1 to $ 1.50 per pound per year. This amounts to about 10 billion dollars per year. The increased demand for activated carbon is expected to be due in large part to the implementation of EPA-issued regulations that require utility and industrial manufacturers to upgrade coal fired power plants to meet increasingly stringent requirements.

In addition to stricter gas emission regulations, The EPA has also imposed stricter regulations on non-gaseous emissions by The Clean water act, which must be fully followed by 2016. The combination of increasing legislation on all types of emissions can affect the various types of emissions produced by various different industries. Some industries, such as power producers that burn fuel to generate electricity, produce primary gaseous emissions containing harmful pollutants. According to industry standards, these gaseous emissions are exposed to activated carbon materials in an effort to capture a sufficient amount of harmful pollutants so that the gaseous emissions are at or below the allowable limits for the pollutants. The process of removing harmful pollutants from the gaseous emissions produced by burning these fuels results in and/or produces secondary non-gaseous emissions in the form of liquid or slurry substances containing the harmful pollutants. The harmful pollutants in the secondary non-gaseous emissions must also be properly captured and/or sequestered to prevent their emission into the environment. Both primary gaseous emissions and secondary non-gaseous emissions require means to properly capture and/or recover and/or limit enough hazardous contaminants to comply with environmental regulations. The industrial costs associated with known available processes capable of accomplishing the removal of harmful pollutants from secondary non-gaseous emissions are almost cost prohibitive, such that some industries are forced to shut down the facility if they cannot pass the costs on to the consumer.

According to some practices, non-gaseous emissions are considered hazardous because they contain higher levels of pollutants that are discarded and sequestered for long term storage in ponds, heaps, or dry beds. While this practice isolates the hazardous contaminants, they are expensive and consume land area without neutralizing the hazardous contaminants themselves, which can lead to environmental hazards in the area of the contaminants. One example of a non-gaseous emission is fly ash, which is a natural product from the combustion of coal. The fly ash has substantially the same composition as volcanic ash. Fly ash contains trace concentrations (i.e., amounts) of many heavy metals and other known harmful and toxic contaminants, including mercury, beryllium, cadmium, barium, chromium, copper, lead, molybdenum, nickel, radium, selenium, thorium, uranium, vanadium, and zinc. Some evaluations have shown that as much as 10% of coal burned in the united states is composed of non-combustible materials that can become ash. As a result, the concentration of harmful trace elements in the coal ash was 10 times higher than the concentration of these elements in the raw coal.

Fly ash is considered to be a pozzolanic material and has a long history of use in the production of concrete because it forms a cementitious material when mixed with calcium hydroxide, which aggregates with water and other compounds to form a concrete mixture that is well suited for roads, airport runways and bridges. Fly ash produced in coal-fired plants is flue ash, which consists of particles that are very fine and rise with the flue gas. Ash that does not rise is commonly referred to as bottom ash. In the early days of coal-fired plants, the fly ash was simply released into the atmosphere. Environmental regulations have required the installation of emission control devices to prevent the release of fly ash into the atmosphere for recent decades. In many plants, electrostatic precipitators are used to capture fly ash before it can reach a stack and be discharged to the atmosphere. Typically, the bottom ash is mixed with the captured fly ash to form so-called coal ash. Typically, fly ash contains higher levels of harmful pollutants than bottom ash, which is why mixing bottom ash with fly ash allows the proportion levels of harmful pollutants to meet most non-gaseous emission standards. However, future standards may reclassify fly ash as a hazardous material. If the fly ash is reclassified as a hazardous material, it will prevent its use in the production of cement, asphalt, and many other widely used applications. It is estimated by some studies that the cost of concrete increases in the united states alone will exceed 50 billion dollars per year due to the banning of fly ash in concrete production. The increase in cost is a direct result of using more expensive alternative materials instead of fly ash. Furthermore, no other known material is suitable as a direct replacement for fly ash in cement due to its unique physical properties.

Reports have shown that more than 450 coal fired power plants produce more than 1.3 million tons of fly ash per year in the united states. Some reports estimate that only 40% of this fly ash is reused, indicating that up to 5200 ten thousand tons of fly ash can be reused each year, leaving up to 7800 ten thousand tons of fly ash stored in bulk in slurry ponds and heaps each year. Fly ash is typically stored in wet ponds to reduce the likelihood of escaping particles becoming airborne, which can cause large amounts of stored contaminants to be transported to the atmosphere and surrounding environment. In addition to the air-borne transport of bulk stored fly ash, the containment systems required for long-term containment of fly ash present a threat of damage and/or failure. A well-known failure case occurred in tennessee in 2008, where a dam of a wet storage fly ash pond collapsed, causing 540 million cubic yards of fly ash to leak. The leakage damages several houses and pollutes the nearby river. The cleaning costs are still continuous at the time of this application and may exceed $ 12 billion.

In another example, non-gaseous emissions may be a byproduct in a typical wastewater generation system of a coal burning facility. In a typical wastewater generation system, a large amount of water comes from boiler discharge and cooling water processes. These large volumes of wastewater contain relatively low levels of contaminants and are used to dilute other waste streams containing higher levels of contaminants. The contaminated wastewater stream, typically discharged from a scrubber system, is diluted with large volumes of wastewater from boiler discharge and/or cooling water processes, then treated in large continuous mixing tanks containing lime to form gypsum, which is then pumped to settling ponds. In the process, certain amounts of mercury and other heavy metals are entrained in the gypsum and stabilized for use in wallboard and cement. This gypsum is generally considered non-leaching and is not considered a pollution hazard. However, water from settling ponds is typically discharged into waterways. Current regulations allow for such continuous emissions, but imminent regulations suggest that certain contaminants and/or the levels of such contaminants be mandated as hazardous contaminants.

With respect to the removal of mercury and heavy metals from non-gaseous industrial wastewater streams, carbonates, phosphates or sulfides are commonly used in an effort to reduce harmful contaminants to low residual levels. One known method for removing mercury and other harmful contaminants from industrial wastewater streams is a chemical precipitation reaction. Another known method utilizes ion exchange. One of the major problems with chemical precipitation reactions and ion exchange processes is that these processes are not sufficient to fully comply with the more stringent EPA regulations for non-gaseous emissions when the contaminants are high, such as when treating fly ash slurry emissions.

Another source of contaminated non-gaseous emissions is marine vessel waste discharge and/or ballast discharge. Commercial vessels such as cargo ships and tankers have both waste discharge and ballast discharge. The recreational cruise ship also has effluent water to be treated at the port site. In addition, military and defense vessels have a large volume of discharged sewage.

Offshore drilling operations produce another significant effluent. On-site treatment of sewage waste on an offshore drilling platform is much cheaper than transporting the waste to land for disposal. Therefore, it is necessary to effectively filter the marine waste before it is discharged to the ocean to maintain proper and acceptable ecological requirements. Almost all contaminated emissions applications vary in the type of pollutant and/or the specific concentration in the emissions. Therefore, a one-knife approach to a suitable sorbent optimized for all possible pollutant emission applications is not possible. There is a need to provide application specific sorbent schemes for optimizing effective emission control based on the specific pollutants in the emissions. There is also a need to be able to adjust the sorbent application during use to correspond to variations in the level and/or type of contaminants remaining in the effluent.

There are also various known commercial emissions control methods and systems sold under different trade names for treating secondary non-gaseous emissions. One known treatment method, under the trade name Blue PRO, is a reactive filtration process that uses co-precipitation and absorption to remove mercury from secondary non-gaseous emissions. Another known treatment method, under the trade name MERSORB-LW, uses a granular coal-based sorbent to remove mercury from secondary non-gaseous emissions by co-precipitation and absorption. Another treatment known as chlor-alkali Electrolysis Wastewater (Chloralkali Electrolysis Wastewater) is the removal of mercury from secondary non-gaseous emissions during the electrolytic production of chlorine. Another treatment method uses absorption kinetics and activated carbon from fertilizer waste to remove mercury from secondary non-gaseous emissions. Another treatment method uses porous cellulose supports modified with polyethyleneimine as an absorbent to remove mercury from secondary non-gaseous emissions. Another treatment method uses microorganisms in enzymatic reduction to remove mercury from secondary non-gaseous emissions. Another known treatment method, under the trade name MerCURxE, uses a chemical precipitation reaction to treat contaminated liquid-like non-gaseous emissions.

A common treatment for some emission control systems is to dilute the pollutants rather than remove them from the emissions. Thus, if the PPM level of the pollutants in the emissions exceeds the allowable level, rather than removing the pollutants to reduce the level, an additional uncontaminated volume is added to the emissions such that the resulting PPM level is reduced to the allowable level, although the actual amount of pollution allowed remains unchanged. There is a pressing need to overcome this dilution practice by providing an effective emissions control method that not only reduces the PPM level of the pollutants, but also removes the pollutants from the emissions.

Disclosure of Invention

This section provides a general summary of the disclosure, and does not fully disclose its full scope or all of its features.

In accordance with one aspect of the present disclosure, an apparatus for removing pollutants from emissions is disclosed. The device includes a housing in the shape of an inverted venturi tube. The housing includes an inlet portion for receiving the emissions at a predetermined inlet flow rate, an outlet portion for discharging the emissions at a predetermined outlet flow rate, and an enlarged portion disposed between the inlet portion and the outlet portion of the housing for capturing contaminants in the emissions. The inlet portion, the outlet portion, and the enlarged portion of the housing are disposed in fluid communication with one another. In addition, the inlet portion of the housing has an inlet portion cross-sectional area, the outlet portion of the housing has an outlet portion cross-sectional area, and the enlarged portion of the housing has an enlarged portion cross-sectional area. The enlarged portion cross-sectional area is greater than the inlet portion cross-sectional area and the outlet portion cross-sectional area, depending on the reverse venturi shape of the housing. Due to this geometry of the housing, emissions entering the enlarged portion of the housing slow and pass through the enlarged portion of the housing at a lower velocity relative to the velocity of emissions passing through the inlet and outlet portions of the housing. Because the flow of the emissions is slowed in the enlarged portion of the housing, the residence time of the emissions in the enlarged portion of the housing is increased.

The device also includes a quantity of reactive material including one or more carbon-based sorbents disposed within the enlarged portion of the housing. The mass of reactive material has a reactive outer surface disposed to contact the emissions. Furthermore, a substantial amount of the reactive material comprises an amalgam-forming metal at the reactive outer surface. The amalgam-forming metal in the mass of reactive material chemically bonds with at least some of the contaminants in the emissions passing through the enlarged portion of the housing to the reactive outer surface of the mass of reactive material. One or more sorbent processing subsystems are disposed in fluid communication with the housing. Each sorbent processing subsystem receives carbon-based sorbent from the housing via a sorbent discharge port and returns cleaned carbon-based sorbent to the housing via a sorbent return port. The adsorbent treatment subsystem includes a solvent for separating contaminants from the carbon-based adsorbent in a cleaning and conditioning process before the cleaned carbon-based adsorbent is returned to the housing of the fluidized bed apparatus.

In accordance with another aspect of the present disclosure, an emissions control method for removing pollutants from emissions is disclosed. The method comprises the following steps: the method includes directing the effluent through one or more prefilters containing a prefiltering sorbent, and directing the effluent out of the prefilters and into a treatment system. The treatment system has a fluidized bed apparatus in the shape of a reverse venturi that contains reactive material that chemically bonds with the contaminants carried in the effluent. The reactive material in the reverse venturi-shaped fluidized bed unit is selected from the group of carbon-based adsorbents. For example, but not limiting of, the carbon-based adsorbent in the counter-venturi shaped fluidized bed apparatus may be activated carbon and/or biochar. The method further comprises the following steps: traps contaminants in the reactive material contained in the counter-venturi shaped fluidized bed apparatus and directs the carbon-based adsorbent through one or more adsorbent handling subsystems. The adsorbent treatment subsystem contains a solvent that cleans and conditions the carbon-based adsorbent prior to directing it back into the fluidized bed apparatus in the shape of the counter-venturi.

It is important to maintain optimum process conditions for the carbon-based adsorbent for removing the polluting emissions from the fluidized bed apparatus in the shape of a reverse venturi. Thus, the carbon-based adsorbent is directed from the counter-venturi shaped fluidized bed apparatus and into the adsorbent handling subsystem. The adsorbent treatment subsystem is designed to clean, condition and/or regenerate the carbon-based adsorbent to optimal conditions prior to returning the carbon-based adsorbent to the counter-venturi shaped fluidized bed apparatus. The sorbent treatment subsystem is further designed to separate and direct spent and depleted sorbent from the remainder of the carbon-based sorbent that can be cleaned and/or regenerated for disposal of the spent and depleted sorbent. The adsorbent treatment subsystem is also designed to separate the captured contaminants from the carbon-based adsorbent for recycle for use in various industries or for proper treatment if there are no viable recycle options. The sorbent processing subsystem is further designed to supplement and/or replace carbon-based sorbent that has been separated for processing and/or that has been consumed during normal operation to remove pollutants from the pollutant emissions. The sorbent treatment subsystem is also designed to condition the carbon-based sorbent prior to exposure to the contaminated emissions. In accordance with this aspect of the disclosure, the solvent in the sorbent processing subsystem increases the porosity of the outer surface of the carbon-based sorbent to increase its ability to combine with contaminants in the effluent passing through the fluidized bed apparatus in the shape of the inverted venturi.

In addition to the significant savings advantages, the subject apparatus and methods are more effective in removing harmful pollutants from gaseous and non-gaseous emissions as compared to known emission control systems and methods. It is estimated that these improvements are sufficient to enable the industry to meet and/or exceed anticipated regulatory requirements, which are not economically feasible with current technology. Thus, even if regulations require reclassification of fly ash as a hazardous material, the subject apparatus and method have the potential to allow continued use of fly ash, thereby avoiding significant increases in the cost of the construction industry, utility power generation industry, and other industries producing non-gaseous, ash-type by-products.

The fluidized bed apparatus in the shape of a reverse venturi may have a specific size with a length to diameter ratio to provide an optimal limiting residence time as the effluent passes through the specialized adsorbent contained in the apparatus. By testing and experimentation, it has been determined that the optimum length to diameter ratio of the housing of the fluidized bed apparatus is 2.9: 1 to 9.8: 1, exemplary preferably 4.4: 1. thus, in one exemplary preferred embodiment, the diameter is 4.5 feet and the length is 19.8 feet, which results in a length to diameter ratio of 4.4: 1.

another feature of the exemplary reverse venturi-shaped fluidized bed apparatus is that it has a predominantly rounded, outwardly projecting convex end when viewed from either end of the vessel exterior. Testing of an exemplary example of a system having a fluidized bed apparatus configured in this manner has demonstrated that residence time (time of effluent contact with adsorbent) is maximized because the flow of effluent randomly turns back on itself, minimizing cavitation turbulence, thereby increasing maximized intimate contact. The predominantly rounded, outwardly projecting convex end provides a relatively smooth return flow at both ends of the fluidized bed apparatus with minimal cavitation turbulence of the effluent. Cavitation turbulence through the filter is known to impede and/or disrupt flow. There is a need to extend the residence time in and through a fluidized bed apparatus to optimize contaminant capture and removal from the effluent; however, if the flow is cavitated turbulent, the extended residence time is not optimized. Various baffles and/or other application specific flow restricting barriers may be incorporated into the housing of the fluidized bed apparatus.

According to another aspect of the present disclosure, an example contaminant removal system is provided with a reconfigurable segmented component. Each system component may be isolated, bypassed, merged, and/or reconfigured to meet the requirements of a particular application. The exemplary emissions control system may also include one or more pre-filters and/or post-filters containing a quantity of reactive sorbent. The pre-filter and post-filter may be connected in parallel or in series with the fluidized bed apparatus, depending on the specific requirements of the application.

Emission pollutants from industrial applications include: hg (mercury), As (arsenic), Ba (barium), Cd (cadmium), Cr (chromium), Cu (copper), Pb (lead), Sn (tin), P (phosphorus), NO₂(Nitrogen dioxide), NO₃(nitrate), NH₃(Ammonia). The long list of pollutants precludes the ability to have a knife-cut emissions control scheme. Furthermore, an emission control scheme that may work with one pollutant in a gaseous emission may not be effective for the same pollutant in a non-gaseous emission, and vice versa.

International standards and regulations, federal standards and regulations, state standards and regulations, and local standards and regulations all set various levels of allowable Parts Per Million (PPM) of each pollutant in gaseous and/or non-gaseous emissions. Many of these standards and regulations set different allowable levels for pollutants depending on whether the pollutants remain in the gaseous emissions as compared to the non-gaseous emissions.

The test pollutant emissions may be spot checked and/or a continuous online monitoring device used to determine the type and level of pollutants present in the emissions. Depending on the test results, a particular pre-filter and/or post-filter may be selected to direct the pollutant emissions. Each pre-filter and/or post-filter contains a specific mass of reactive sorbent as a broad spectrum treatment option for specific pollutants present in the emissions.

During emission of the emissions, the type and/or level of pollutants present in the emissions may vary and/or fluctuate. Frequent monitoring of pollutants and/or continuous online monitoring provides the ability to adjust the selection of a particular pre-filter and/or post-filter to best correspond to a particular pollutant present in the emissions at any given time during the flow of the emissions.

The present disclosure provides a broad spectrum table that matches the specific types of pollutants present in gaseous and non-gaseous emissions with specific reactive sorbents that are effective in capturing and removing the corresponding pollutants. The table also matches the ability to separate a particular reactive sorbent from a particular captured pollutant so that the pollutant can be recycled or treated, and whether the sorbent can be regenerated and reused in an emissions control system.

In addition to permanently installed systems for specific applications, the system of the present subject matter may also be configured as a transportable system. Examples of transportable systems include, but are not limited to, truck mounted systems, barge mounted systems, trailer mounted systems, and rail car systems. By providing a temporary bypass for the emissions, it is useful for the transportable system application to provide a bypass for the field built system so that maintenance, inspection and/or repair can be performed on the permanent field built system. The transportable system can also be used to provide additional filtration capability to the permanent field construction plant when the flow rate of the polluting emissions exceeds the capacity of the permanent field construction system.

The particular adsorbents described herein in connection with the disclosed apparatus and methods also have a number of advantages. Generally, carbon-based sorbents improve the ability of the disclosed emissions equipment to better capture, sequester, and/or recycle mercury and other hazardous materials with efficiencies not previously possible using known emissions control systems and methods. Another significant benefit of the carbon-based adsorbent disclosed herein is that the carbon-based adsorbent can be used to treat both gaseous and non-gaseous emissions, thereby overcoming many of the disadvantages of known methods for treating contaminated non-gaseous emissions, including secondary emissions generated by primary emission control processes for treating gaseous emissions. In addition, the carbon-based sorbents described herein provide improved ability to treat gaseous emissions sufficiently effectively to prevent the need for secondary treatment of non-gaseous emissions produced as a byproduct of the primary gaseous emission treatment process. The carbon-based adsorbent disclosed herein is also beneficial because it is reusable. Through the regeneration process, the solvent in the adsorbent treatment subsystem separates (i.e., removes) the harmful contaminants that form metal chemical bonds with the amalgam in the carbon-based adsorbent, thereby restoring the ability of the carbon-based adsorbent to remove contaminants from gaseous and/or non-gaseous emissions.

Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

Drawings

The drawings described herein are for illustrative purposes only of selected embodiments and not all possible embodiments, and are not intended to limit the scope of the present disclosure.

Other advantages of the present invention will be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:

FIG. 1 is a schematic diagram showing a known layout of a coal fired power plant;

FIG. 2 is a schematic diagram showing a known layout of an emissions control system for removing pollutants from emissions produced by a coal fired power plant of the type shown in FIG. 1;

FIG. 3 is a schematic illustration of the emissions control system shown in FIG. 2, wherein the emissions control system has been modified by the addition of an exemplary reverse venturi apparatus constructed in accordance with the present disclosure;

FIG. 4A is a side cross-sectional view of an exemplary reverse venturi apparatus constructed in accordance with the present disclosure, the exemplary reverse venturi apparatus including a housing having an inlet portion, an enlarged portion, and an outlet portion;

FIG. 4B is a front cross-sectional view of an inlet portion of the housing of the exemplary reverse venturi apparatus shown in FIG. 4A;

FIG. 4C is a front cross-sectional view of an enlarged portion of the housing of the exemplary reverse venturi apparatus shown in FIG. 4A;

FIG. 4D is a front cross-sectional view of an outlet portion of the housing of the exemplary reverse venturi apparatus shown in FIG. 4A;

FIG. 5 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the present disclosure, with a series of staggered baffles disposed in an enlarged portion of the housing creating a serpentine flow path for the exhaust;

FIG. 6A is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the present disclosure, with a helical baffle disposed in an enlarged portion of the housing creating a helical flow path for the exhaust;

FIG. 6B is a front perspective view of the helical baffle shown in the exemplary reverse venturi apparatus shown in FIG. 6A;

FIG. 7A is a side cross-sectional view of another exemplary reverse venturi apparatus constructed according to the present disclosure, with a plurality of spaced baffles disposed in an enlarged portion of the housing;

FIG. 7B is an elevational cross-sectional view of the exemplary reverse venturi apparatus shown in FIG. 7A taken along section line A-A, illustrating an orifice in one baffle;

FIG. 8 is a cross-sectional side view of another exemplary reverse venturi apparatus constructed according to the present disclosure, with a plurality of segments disposed in an enlarged portion of the housing;

FIG. 9 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the present disclosure, with a plurality of entanglement lines disposed in an enlarged portion of the housing, forming a wool-like material therein;

FIG. 10 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed according to the present disclosure, with a filter element disposed in an enlarged portion of a housing;

FIG. 11 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed according to the present disclosure, wherein the enlarged portion of the housing includes a plurality of baffles and a plurality of differently sized segments disposed between adjacent baffles;

FIG. 12A is a front view illustrating one exemplary size of a segment contained in an enlarged portion of a housing of the exemplary reverse venturi apparatus shown in FIG. 11;

FIG. 12B is a front view illustrating another exemplary size of a segment contained in an enlarged portion of a housing of the exemplary reverse venturi apparatus shown in FIG. 11;

FIG. 12C is a front view illustrating another exemplary size of a segment contained in an enlarged portion of a housing of the exemplary reverse venturi apparatus shown in FIG. 11;

FIG. 12D is a front view illustrating another exemplary size of a segment contained in an enlarged portion of a housing of the exemplary reverse venturi apparatus shown in FIG. 11;

FIG. 13A is a front view showing one exemplary sheet of loose material having an asterisk-like shape that, in combination with other sheets, may be used in place of the segments shown in the exemplary reverse venturi apparatus shown in FIGS. 8 and 11;

fig. 13B is a front view illustrating an exemplary crystal slice that, in combination with other crystal slices, may be used to replace the segments shown in the exemplary reverse venturi apparatus shown in fig. 8 and 11.

FIG. 13C is a front view illustrating an exemplary coil that may be used in combination with other coils to replace the segment shown in the exemplary reverse venturi apparatus shown in FIGS. 8 and 11;

FIG. 14 is a side cross-sectional view illustrating another exemplary reverse venturi apparatus constructed according to the present disclosure, including two separate enlarged portions connected in series;

FIG. 15 is a side cross-sectional view illustrating another exemplary reverse venturi apparatus constructed according to the present disclosure, including two separate enlarged portions connected together in parallel;

FIG. 16 is a side cross-sectional view illustrating another example reverse venturi apparatus constructed according to the present disclosure.

FIG. 17 is a block flow diagram illustrating a known method for removing pollutants from gaseous emissions;

FIG. 18A is a block diagram illustrating a method for removing pollutants from the gaseous emissions shown in FIG. 17, wherein the method is improved by adding the step of injecting a sorbent into the gaseous emissions at a first introduction point and then passing the gaseous emissions through a reversing venturi device;

FIG. 18B is a block diagram illustrating a method for removing pollutants from the gaseous emissions shown in FIG. 17, wherein the method is improved by adding the step of injecting a sorbent into the gaseous emissions at a second point of introduction and then passing the gaseous emissions through a reversing venturi device;

FIG. 19 is a block diagram illustrating a known method for removing pollutants from non-gaseous emissions that requires deposition of the non-gaseous emissions in a settling tank;

FIG. 20 is a block diagram showing a method for removing pollutants from the non-gaseous emissions shown in FIG. 19, wherein the method is improved by adding the step of treating a portion of the non-gaseous emissions extracted from the settling tank with a sorbent;

FIG. 21 is a graph illustrating the percentage of pollutants removed from emissions by known emissions control systems and the percentage of pollutants removed from emissions by the apparatus and methods disclosed herein;

FIG. 22 is a block flow diagram illustrating an exemplary method of removing pollutants from gaseous emissions and cleaning reactive materials that separate the pollutants from the gaseous emissions using a fluidized bed apparatus in the shape of a reverse venturi;

FIG. 23 is a block flow diagram illustrating an exemplary method of removing pollutants from non-gaseous emissions and cleaning reactive materials that separate the pollutants from the non-gaseous emissions using a fluidized bed apparatus in the shape of a reverse venturi;

FIG. 24 is a flow chart illustrating exemplary method steps for cleaning and recycling sorbent that separates contaminants from an effluent through an extended non-turbulent effluent stream of an exemplary reverse venturi shaped fluidized bed apparatus;

FIG. 25 is a block flow diagram illustrating an exemplary method of using a reverse venturi-shaped fluidized bed apparatus having a tilting mechanism mounted to a transportable platform plate, wherein the housing of the reverse venturi-shaped fluidized bed apparatus is oriented relatively parallel to the platform plate for removing contaminants from a gaseous effluent;

FIG. 26 is a block flow diagram illustrating an exemplary method of using a reverse venturi-shaped fluidized bed apparatus having a tilt mechanism mounted to a transportable platform plate, wherein the housing of the reverse venturi-shaped fluidized bed apparatus is oriented transversely with respect to the platform plate for removing contaminants from a non-gaseous effluent;

FIG. 27 is a table showing the specific types of contaminants that are matched to the effectiveness of the disclosed CZTS alloy adsorbents, as compared to activated carbon and zeolite adsorbents for gaseous and non-gaseous emissions;

FIG. 28 is a schematic diagram showing a particular CZTS alloy sorbent in comparison to other particular types of sorbents for gaseous and non-gaseous emissions;

FIG. 29 is a table showing prior art sorbents and their ability to separate and reuse contaminants in gaseous and non-gaseous emissions;

FIG. 30 is a table showing the disclosed broad spectrum CZTS alloy sorbents and their ability to separate and reuse contaminants in gaseous and non-gaseous emissions.

FIG. 31 is a block diagram illustrating a method of directing contaminated gaseous emissions through various filters containing specific effective sorbents matched to the type and/or level of contaminants in the gaseous emissions;

FIG. 32 is a block diagram illustrating a method of directing contaminated non-gaseous emissions through various filters containing specific effective sorbents matched to the type and/or level of contaminants in the non-gaseous emissions;

FIG. 33 is a flow diagram illustrating an extended non-turbulent exhaust stream through an exemplary counter-venturi shaped fluidized bed apparatus, and exemplary method steps for cleaning and recycling sorbent that separates contaminants from the exhaust by using a series of sorbent recycling subsystems for CZTS sorbent, CZTS alloy sorbent, and/or carbon-based sorbent; and

fig. 34 is a block diagram illustrating a method of directing a contaminated carbon-based adsorbent through a sorbent processing subsystem that separates contaminants from the carbon-based adsorbent so that the carbon-based adsorbent and waste/contaminated byproducts can be appropriately treated, recycled, reused, and/or replaced.

Detailed Description

Referring to the drawings, wherein like reference numbers represent corresponding parts throughout the several views, there is shown an apparatus and method for removing contaminants from industrial emissions.

Example embodiments will now be described more fully with reference to the accompanying drawings. The exemplary embodiments are provided so that this disclosure will be thorough and will fully convey the scope of the disclosure to those skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that should not be construed as limiting the scope of the disclosure. In some exemplary embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises," "comprising," "including," and "having" are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also understood that additional or alternative steps may be employed.

When an element or layer is referred to as being "on," "engaged to," "connected to" or "coupled to" another element or layer, it may be directly on, engaged, connected or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly engaged to," "directly connected to" or "directly coupled to" another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between … …" and "directly between … …", "adjacent" and "directly adjacent", etc.). As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as "first," "second," and other numerical terms used herein do not refer to a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.

Spatially relative terms, such as "inner," "outer," "below," "lower," "upper," and the like, may be used herein for ease of description to describe one element or feature's relationship to another element or feature as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the example term "below" may include both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

As used herein, the term "conduit" is intended to encompass all references to conduits commonly used for conveying liquid and/or liquid-like emissions and gaseous and/or gaseous-like emissions. The actual method of transport of the emissions, regardless of the type of emissions, gives no or no preference. The term "ambient temperature" as used herein refers to the temperature of the surrounding environment (e.g., standard temperature and pressure "STP"). Additionally, it should be understood that the terms "contaminant" and "contaminant" are used interchangeably in this disclosure.

Referring to FIG. 1, a schematic diagram of a typical coal fired power plant 100 is shown. The coal fired power plant 100 includes an industrial facility fluidized bed reactor 1 that combusts one or more types of coal 2 to produce electricity 7. The power 7 may then be distributed to the grid via a power line 8. Flow ofCombustion in the fluidized bed reactor 1 is driven by air 3, flame 4 and coal 2. The combustion process is used to heat water and produce steam 5. The steam is then used to turn the generator 6, and the generator 6 produces electricity 7. Gaseous emissions 10 from the combustion process are released into the environment through a stack 9. When the coal fired power plant 100 is not equipped with any emission control system (FIG. 1), the emissions 10 include many harmful pollutants, such as fly ash, mercury (Hg), metal vapors, sulfur dioxide (SO), and the like₂) Hydrogen chloride (HCl) and other toxic fumes.

Referring to FIG. 2, a schematic diagram of a retrofit coal fired power plant 200 is shown that includes an exemplary emissions control system 202. The emissions control system 202 facilitates the capture and collection of some harmful pollutants in the gaseous emissions 10. The emissions control system 202 transports the gaseous emissions 10 from the fluidized bed reactor 1 where combustion occurs to a wet or dry scrubber 11, which wet or dry scrubber 11 removes some sulfur dioxide and fly ash contaminants from the gaseous emissions 10. Instead of, or in addition to, conveying the gaseous emissions 10 to the wet or dry scrubber 11, the emissions control system 202 may convey the gaseous emissions 10 into the spray dryer 12 where some sulfur dioxide, toxic fumes, and other pollutants are captured and collected. The effluent may also be directed through a fabric filter unit 13 (i.e., a baghouse), which fabric filter unit 13 uses filter bags to remove particulates from the flow of the gaseous effluent 10. The system collects and removes many pollutants from the gaseous emissions 10 before the gaseous emissions 10 are released to the surrounding atmosphere (i.e., the environment) through the stack 9. A problem with the typical emissions control system 202 shown in fig. 2 is that nano-sized contaminants, such as mercury, contained in the metal vapor emissions are readily passed through the wet or dry scrubber 11, spray dryer 12 and fabric filter unit 13 of the emissions control system 202.

Referring to FIG. 3, a schematic diagram of an improved coal fired power plant 300 is shown that includes sorbent injectors 14 and a reverse venturi apparatus 15 in addition to the emission control system 202 shown in FIG. 2. The sorbent injector 14 operates to add sorbent to the gaseous effluent 10 and may optionally be disposed upstream of the reverse venturi device 15. More specifically, in the example shown in fig. 3, the sorbent injectors are located between the spray dryer 12 and the fabric filter unit 13. In fig. 3, the reverse venturi device is located between the fabric filter unit 13 and the chimney 9, although alternative locations for the reverse venturi device 15 are possible. One major advantage of this location is that Existing installations can install the reverse venturi device 15 and simply apply for a "modify to Existing Permit", saving time and money compared to applying for a new Permit for a completely new emission control system. In operation, gaseous effluent 10 is directed from fabric filter unit 13 to reverse venturi apparatus 15. As will be explained in more detail below, the reverse venturi apparatus 15 is configured with internal features that are adapted to collect and capture large quantities of mercury, heavy metals, nano-sized particles, and other contaminants. Thus, the resulting gaseous emissions 10 leaving the stack 9 are stripped of almost all harmful pollutants.

Referring to fig. 4A-D, the reverse venturi apparatus 15 includes a housing 16 in the shape of a reverse venturi. It will be appreciated that a venturi may be generally described as a conduit that first narrows down from a larger cross-section to a smaller cross-section, and then expands from the smaller cross-section back to the larger cross-section. Thus, the term "reverse venturi" as used herein describes the reverse conduit which first expands from a smaller cross-section to a larger cross-section and then narrows from the larger cross-section down to the smaller cross-section. Specifically, the housing 16 of the disclosed reverse venturi apparatus 15 extends along a central axis 17 and has an inlet portion 18, an enlarged portion 19 and an outlet portion 20. The inlet portion 18 of the housing 16 is sized to receive the gaseous emissions 10 at a predetermined inlet flow rate, characterized by an inlet velocity V₁And pressure P₁. The outlet portion 20 of the housing 16 is sized to discharge the gaseous emissions 10 at a predetermined outlet flow rate, characterized by an outlet velocity V₃And pressure P₃. An enlarged portion 19 is disposed between the inlet portion 18 and the outlet portion 20 of the housing 16 and defines an enlarged chamber 21 therein for trapping gaseous emissions 10A contaminant. The enlarged portion 19 of the housing 16 has an inner surface 68, the inner surface 68 facing generally toward the central axis 17. The inlet portion 18, the enlarged portion 19, and the outlet portion 20 of the housing 16 are sequentially arranged along the central axis 17 such that the inlet portion 18, the enlarged portion 19, and the outlet portion 20 of the housing 16 are in fluid communication with one another. In other words, the inlet portion 18, the enlarged portion 19, and the outlet portion 20 of the housing 16 cooperate to form a conduit extending along the central axis 17.

The inlet portion 18 of the housing 16 has an inlet portion cross-sectional area A transverse to the central axis 17₁And the outlet portion 20 of the housing 16 has an outlet portion cross-sectional area A transverse to the central axis 17₃. Inlet section cross-sectional area A₁May be equal to the cross-sectional area A of the outlet portion₃(i.e. may be cross-sectional area A with the outlet section)₃Same) such that the predetermined inlet flow rate is equal to the predetermined outlet portion flow rate (i.e., the same as the predetermined outlet portion flow rate). Alternatively, the inlet section cross-sectional area A₁Can be cross-sectional area A of the outlet part₃Different (i.e., may be larger or smaller) such that the predetermined inlet flow rate is different (i.e., smaller or larger) than the predetermined outlet flow rate. It should be understood that, as used herein, the term "flow rate" refers to the volumetric flow rate of the effluent.

The enlarged portion 19 of the housing 16 has an enlarged cross-sectional area A₂Transverse to the central axis 17 and larger than the inlet section cross-sectional area a₁And outlet portion cross-sectional area A₃. Thus, the size of the enlarged portion 19 is such that the flow velocity V of the gaseous emissions 10 within the enlarged portion 19 of the housing 16₂Less than the flow velocity V of the gaseous emissions 10 in the inlet portion 18 of the housing 16₁And is less than the flow velocity V of the gaseous emissions 10 in the outlet portion 20 of the housing 16₃. This reduced flow rate, in turn, increases the residence time of the gaseous emissions 10 within the enlarged portion 19 of the housing 16. It should be understood that, as used herein, the term "residence time" refers to the average amount of time required for molecules in the gaseous emissions 10 to travel through the enlarged portion 19 of the housing 16. In other words, the "residence time" of the enlarged portion 19 of the housing 16 is equal to all rows in the enlarged chamber 21The amount of time it takes for the deposit update. It should also be understood that, as used herein, the term "cross-sectional area" refers to the internal cross-sectional area (i.e., the space within the housing 16) that remains constant regardless of variations in the thickness of the housing 16. Accordingly, enlarged portion cross-sectional area a2 reflects the size of enlarged cavity 21 and is bounded by inner surface 68.

Due to the geometry of the housing 16, the internal pressure P of the gaseous exhaust 10 passing through the inlet portion 18 of the housing 16₁And the internal pressure P of the gaseous exhaust 10 through the outlet portion 20 of the housing 16₃Greater than the internal pressure P of the gaseous emissions 10 through the enlarged portion 19 of the housing 16₂. The pressure differential and the flow velocity V of the gaseous emissions 10 within the enlarged portion 19 of the housing 16₂Less than the flow velocity V of the gaseous emissions 10 in the inlet portion 18 of the housing 16₁And is less than the flow velocity V of the gaseous emissions 10 in the outlet portion 20 of the housing 16₃Combined with the fact that the gaseous emissions 10 are caused to reside in the enlarged portion 19 of the housing 16. Due to the pressure and velocity differences noted above and because the gaseous emissions 10 will naturally expand to occupy the entire volume of the enlarged chamber 21, an expansion force is therefore exerted on the gaseous emissions 10 in the enlarged portion 19 of the housing 16. This, in combination with the effects of laminar flow, aerodynamic dynamics, and physics of gas behavior, the resulting increase in residence time enhances the ability of the reverse venturi apparatus 15 to effectively capture and thereby remove pollutants from the gaseous effluent 10.

The housing 16 may have a variety of different shapes and configurations. For example, and without limitation, the inlet portion 18, enlarged portion 19, and outlet portion 20 of the housing 16 shown in FIGS. 4A-D all have a circular cross-sectional area A₁、A₂、A₃. Alternatively, the cross-sectional area A of one or more of the inlet portion 18, the enlarged portion 19, and the outlet portion 20 of the housing 16₁、A₂、A₃May have a non-circular shape, wherein various combinations of circular and non-circular cross-sectional areas are possible and are considered to be within the scope of the present disclosure. In some configurations, the enlarged portion 19 of the housing 16 may have a diverging end 22 and a converging end 23. According to these configurations, the enlarged portion 19 of the housing 16Tapering outwardly from the inlet portion cross-sectional area A1 to an enlarged portion cross-sectional area A at the diverging end 22₂. In other words, the cross-section of the enlarged portion 19 of the housing 16 increases at the diverging end 22 in a direction moving away from the inlet portion 18 of the housing 16. Conversely, the enlarged portion 19 of the housing 16 has a cross-sectional area A from the enlarged portion at the converging end 23₂Tapering inwardly to an outlet portion cross-sectional area A₃. In other words, the cross-section of the enlarged portion 19 of the housing 16 decreases at the converging end 23 in a direction toward the outlet portion 20 of the housing 16. Thus, it should be appreciated that the gaseous emissions 10 in the enlarged portion 19 of the housing 16 generally flow from the diverging end 22 to the converging end 23. The inlet portion 18, the enlarged portion 19 and the outlet portion 20 of the housing 16 all have a circular cross-sectional area A₁、A₂、A₃In embodiments, the diverging end 22 and the converging end 23 of the housing 16 may have a generally conical shape. Nevertheless, alternative shapes for the diverging end 22 and the converging end 23 of the enlarged portion 19 of the housing 16 are possible. By way of example and not limitation, the diverging end 22 and the converging end 23 may have a polygonal shape to improve ease of manufacture while avoiding any significant adverse effect on the flow of the gaseous emissions 10 through the housing 16 of the reversing venturi apparatus 15. In another alternative configuration, the enlarged portion 19 of the housing 16 may have a sausage-like shape with relatively abrupt transitions between the inlet portion 18 and the diverging end 22 and between the converging end 23 and the outlet portion 20. It is speculated that a smooth transition is preferable to an abrupt transition because laminar flow behavior of the gaseous emissions 10 may be preferred. However, slight disturbances to the laminar flow of the gaseous emissions 10 at the abrupt transition are not considered to be an overwhelming loss, and instead may provide enhanced flow in areas where increased residence time is not required.

With continuing reference to fig. 4A-D and with additional reference to fig. 5-11, a quantity of reactive material 24 is disposed within the enlarged portion 19 of the housing 16. The quantity of reactive material 24 has a reactive outer surface 25 that is disposed in contact with the gaseous emissions 10. Further, the quantity of reactive material 24 includes an amalgam-forming metal at the reactive outer surface 25 that chemically bonds with at least some of the pollutants in the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16 to the reactive outer surface 25 of the quantity of reactive material 24. In this manner, contaminants bound to the reactive outer surface 25 of the mass of reactive material 24 remain trapped in the enlarged portion 19 of the housing 16 and are thus removed from the flow of gaseous emissions 10 exiting the enlarged portion 19 of the housing 16 and entering the outlet portion 20 of the housing 16. It should be understood that, as used herein, the term "amalgam-forming metal" describes a material selected from a group of metals that is capable of forming a compound with one or more pollutants in the gaseous emissions 10. By way of non-limiting example, the amalgam-forming metal may be zinc and the contaminant in the gaseous emission 10 may be mercury, such that an amalgam of zinc and mercury is formed when the gaseous emission 10 is in contact with the reactive outer surface 25 of the quantity of reactive material 24.

It should be appreciated that the enlarged portion 19 of the housing 16 must be sized to accommodate the predetermined inlet flow rate of the gaseous emissions 10 while providing a residence time long enough for the amalgam-forming metal in the bulk of the reactive material 24 to chemically bond with the pollutants in the gaseous emissions 10. Thus, to achieve this balance, the enlarged cross-sectional area a2 may be in the range of 3 square feet to 330 square feet to achieve a residence time of 1 second to 2.5 seconds. A specific residence time is necessary to allow sufficient time for the contaminants in the gaseous emissions 10 to chemically bond to the amalgam-forming metal in the mass of reactive material 24. Thus, the range of expanded partial cross-sectional areas A2 is calculated to achieve a residence time for the coal fired power plant 100 ranging in output from 1 Megawatt (MW) to 6,000 Megawatts (MW). The amalgam-forming metal may be a variety of different materials, as is known in the chemical art. As a non-limiting example, the amalgam-forming metal may be selected from the group consisting of zinc, iron, and aluminum. It should also be understood that the housing 16 is made of a different material than the quantity of reactive material 24. By way of non-limiting example, the housing 16 may be made of steel, plastic, or fiberglass.

The quantity of reactive material 24 may be provided in a variety of different non-limiting configurations. Referring to fig. 4A, a quantity of reactive material 24 is shown coated on an inner surface 68 of the housing 16. Alternatively, referring to fig. 5-11, the quantity of reactive material 24 may form one or more blocking elements 26a-j disposed within the enlarged portion 19 of the housing 16. In this way, the blocking elements 26a-j create a tortuous flow path 27 for the gaseous emissions 10 through the enlarged portion 19 of the housing 16. Thus, the blocking elements 26a-j increase the residence time of the gaseous emissions 10 through the enlarged portion 19 of the housing 16. Several embodiments discussed below completely disrupt the flow of the gaseous emissions 10 through the enlarged portion 19 of the housing 16 such that the resulting tortuous flow path 27 is completely random, which greatly enhances the opportunity for chemical reactions between the pollutants in the gaseous emissions 10 and the amalgam-forming metal in the bulk of the reactive material 24.

In each of the configurations shown in fig. 5-11, the barrier elements 26a-j present a large surface area such that the reactive outer surface 25 of the mass of reactive material 24 is large. This is advantageous because the chemical reaction between the amalgam-forming metal in the reactive outer surface 25 of the mass of reactive material 24 and the contaminants in the gaseous contaminants 10 allows the enlarged portion 19 of the housing 16 to trap, capture and/or collect the contaminants, thereby removing/eliminating them from the gaseous emissions 10. Thus, the amount of pollutants that the enlarged portion 19 of the housing 16 may remove from the gaseous emissions 10 passing through the enlarged chamber 21 is proportional to the size of the reactive outer surface 25 of the mass of reactive material 24 in the enlarged portion 19 of the housing 16. In addition, the complex surface shape and/or texture of the barriers 26a-j may provide additional surface area to facilitate physical capture of contaminants, whether or not capture is a result of a chemical reaction between the contaminants and the amalgam-forming metal.

Referring again to fig. 3, the sorbent added to the emissions by the sorbent injector 14 comprises an amalgam-forming metal. In this way, the amalgam-forming metal in the sorbent chemically bonds with at least some of the pollutants in the gaseous emissions 10 before the gaseous emissions 10 enter the enlarged portion 19 of the housing 16. Although the adsorbent may have many different compositions, the adsorbent may be, for example, zinc (Zn) powder or Copper Zinc Tin Sulfide (CZTS) compounds. Because the sorbent chemically bonds with at least some of the pollutants in the gaseous emissions 10 before the gaseous emissions 10 enter the enlarged portion 19 of the housing 16, the sorbent aids in the removal of the pollutants from the gaseous emissions 10 by the mass of reactive material 24.

Referring to FIG. 5, the blocking elements 26a-j are provided in the form of a series of alternating baffles 26a, the baffles 26a extending from an inner surface 68 of the enlarged portion 19 of the housing 16. A series of alternating baffles 26a are transverse to the central axis 17 and impart a serpentine shape to the tortuous flow path 27. The serpentine shape of the tortuous flow path 27 increases the residence time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16, which in turn increases the capture and removal of pollutants in the gaseous emissions 10 by the mass of reactive material 24 forming the series of interleaved baffles 26 a. In one variation, the series of alternating baffles 26a are made of zinc. In another variation, the series of alternating baffles 26a are made of a non-zinc material coated with zinc. It should be understood that the placement of the interleaved baffles 26a need not be equally or symmetrically oriented along the length of the central axis 17, as some applications may benefit from a larger space between adjacent baffles 26a, while other applications may benefit from a smaller space between adjacent baffles 26 a. It should also be appreciated that if the series of interleaved baffles 26a become saturated during operation of the reversing venturi apparatus 15, the series of interleaved baffles 26a may be replaced and/or cleaned as desired.

Referring to fig. 6A-B, alternatively, at least one of the blocking elements 26A-j is in the form of a helical baffle 26B. A helical baffle 26b extends helically within the enlarged portion 19 of the shell 16 along the central axis 17 and about the central axis 17. Thus, the helical baffle 26b makes the tortuous flow path 27 take a helical shape. The helical shape of the tortuous flow path 27 increases the residence time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16, which in turn increases the capture and removal of pollutants in the gaseous emissions 10 by the mass of reactive material 24 forming the helical baffle 26 b. In one variation, the helical baffles 26b are made of zinc. In another variation, the helical baffles 26b are made of a non-zinc material coated with zinc. In yet another variation, the helical baffle 26b is mechanically driven such that the helical baffle 26b rotates about the central axis 17 within the enlarged portion 19 of the casing 16. The rotation of the helical baffle 26b may artificially accelerate or artificially decelerate the flow of the gaseous emissions 10 through the enlarged portion 19 of the housing 16, depending on the direction of rotation of the helical baffle. It will be appreciated that if the helical baffle 26b becomes saturated during operation of the reversing venturi apparatus 15, the helical baffle 26b may be replaced and/or cleaned as required.

Referring to fig. 7A-B, the at least one blocking element 26a-j is a plurality of baffles 26 c. Each baffle 26c extends transversely from the inner surface 68 of the enlarged portion 19 of the housing 16 through the enlarged portion 19 of the housing 16. The baffles 26c are spaced apart from one another along the central axis 17, and each baffle 26c includes an aperture 28 that allows the gaseous emissions 10 to flow through the baffle 26 c. Of course, it should be understood that any number of baffles 26c are possible, including configurations that include only a single baffle 26 c. It should also be understood that the size, shape and number of apertures 28 in each baffle 26c can vary. For example, the baffles 26c may be provided in the form of screens, wherein apertures 28 are formed between intersecting lines of the screens. The apertures 28 in the baffle 26c restrict the flow of the gaseous emissions 10 in the enlarged portion 19 of the casing 16, thereby increasing the residence time of the gaseous emissions 10 in the enlarged portion 19 of the casing 16. This improves the capture and removal of pollutants from the gaseous effluent 10 by the mass of reactive material 24 forming the baffle 26 c. In one variation, the baffles 26c are made of zinc. In another variation, the baffles 26c are made of a non-zinc material coated with zinc. It will be appreciated that if the baffle 26c becomes saturated during operation of the reversing venturi apparatus 15, the baffle 26c may be replaced and/or cleaned as desired. In yet another variation, the size of the apertures 28 in one of the baffles 26c is different than the size of the apertures 28 in an adjacent one of the baffles 26 c. By using different sized apertures 28 in different baffles 26c, the flow of the gaseous emissions 10 may be accelerated and/or restricted to enhance the capture and removal of pollutants in the gaseous emissions 10 by the large amount of reactive material in the baffles 26 c. In a similar manner, the baffles 26c need not be equally spaced apart in the enlarged chamber 21, nor need the apertures 28 in one of the baffles 26c be the same size, shape or location as the apertures 28 in an adjacent baffle 26 c. By utilizing different sizes, shapes, and locations of the apertures 28 from one baffle 26c to another baffle 26, and by utilizing different spacing of the baffles 26c, the residence time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16 may be increased to promote increased contact along the physical and chemical capture and collection locations of the reactive material 24 in large quantities.

In other alternative configurations shown in fig. 8-11, the at least one blocking element 26a-j may not be fixed to the housing 16 itself, but may be freely positioned within the enlarged portion 19 of the housing 16. In such a configuration, at least one of the barrier elements 26a-j may include various forms of barrier media 26 d-j. Similar to barrier elements 26a-c, barrier dielectrics 26d-j can be made of zinc or a non-zinc material coated with zinc. Zinc readily melts, allowing complex shapes to be cast using conventional molding methods, dewaxing processes, centrifugal processes, and the like. Other methods of construction readily include machining, extrusion, sintering, stamping, hot forging and forming, laser cutting, and the like. Alternatively, steel may be used to form the base shape, which is then coated or galvanized as a surface covering. The barrier media 26d-j may be used to completely fill the entire enlarged chamber 21, partially fill the enlarged chamber 21, or fill between the baffles 26c previously described in connection with fig. 7A-B.

Fig. 8 illustrates a configuration in which at least one of the blocking elements 26a-j is a plurality of fragments 26d contained in the enlarged portion 19 of the housing 16. According to this configuration, as the gaseous emissions 10 travel from the inlet portion 18 through the enlarged portion 19 of the housing 16 to the outlet portion 20 of the housing 16, the gaseous emissions 10 pass through the spaces between adjacent fragments 26 d. To this end, the plurality of chips 26d may be provided with an irregular shape such that the chips 26d are loosely packed with each other in the enlarged portion 19 of the housing 16. In one non-limiting example, the plurality of fragments 26d may be made of sponge zinc. Sponge zinc is a popcorn shaped zinc structure made by immersing molten zinc in a cooling liquid such as water. The molten zinc droplets thus produced solidify into relatively small spherical structures having extremely high surface area to volume ratios. In addition, the surface area of the resulting structure has a sponge-like surface texture. These structures can be produced in a range of sizes for specific applications. Some steel processes can produce steel plates similar to the complex spherical structure of sponge zinc, which can be coated with zinc.

The loose-fill nature of the plurality of fragments 26d in FIG. 8 gives the random shape of the tortuous flow path 27, which increases the residence time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16. This in turn enhances the capture and removal of pollutants from the gaseous emissions 10 by the mass of reactive material 24 forming the plurality of fragments 26 d. If the plurality of debris 26d in FIG. 8 becomes saturated during operation of the reverse venturi apparatus 15, they may be replaced and/or cleaned as needed.

In another alternative configuration shown in fig. 9, the at least one blocking element 26a-j is a plurality of twine lines 26e disposed in the enlarged portion 19 of the housing 16. Thus, the plurality of twine threads 26e form a fleece material in the enlarged portion 19 of the housing 16. According to one possible configuration, the plurality of twine lines 26e are folded like steel wool and crumpled to form a mass with a very large surface area. The twine 26e may itself be of the same composition, thickness and length, or alternatively may be a mixture of different compositions, thicknesses and/or lengths. In one variation, the plurality of intertwined lines 26e are made of zinc wire and are randomly intertwined to form a zinc wool. Zinc wool can be produced with different density levels and/or filament sizes to provide a particular flow restriction capability. In another variation, the plurality of intertwined lines 26e are made of steel wire and randomly intertwined to form steel wool. The steel wool may be coated with zinc. The relatively loose packed nature of the plurality of intertwined lines 26e in fig. 9 gives the random shape of the tortuous flow path 27, which increases the residence time of the gaseous emissions 10 through the enlarged portion 19 of the housing 16. This in turn enhances the capture and removal of pollutants from the gaseous emissions 10 by the large amount of reactive material 24 forming the plurality of entanglement lines 26 e. It should be understood that if the plurality of entanglement lines 26e become saturated during operation of the reverse venturi apparatus 15, the plurality of entanglement lines 26e may be replaced and/or cleaned as desired.

Referring to FIG. 10, another alternative configuration is shown wherein at least one of the blocking elements 26a-j is a filter element 26 f. The filter element 26f extends transversely with respect to the central axis 17 through the enlarged portion 19 of the housing 16. The filter element 26f is porous such that the pores in the filter element 26f allow the gaseous emissions 10 to pass through the filter element 26f as the gaseous emissions 10 flow through the enlarged portion 19 of the housing 16 from the inlet portion 18 to the outlet portion 20 of the housing 16. The arrangement of the filter element 26f, which may be made of sintered metal, causes the tortuous flow path 27 to have a random shape, which increases the residence time of the gaseous emissions 10 through the enlarged portion 19 of the housing 16. This in turn enhances the capture and removal of pollutants from the gaseous emissions 10 by the large amount of reactive material 24 forming the filter element 26 f. The sintered metal of the filter element 26f is preferably made of zinc or a non-zinc material coated with zinc. It will be appreciated that if the filter element 26f becomes saturated during operation of the reverse venturi apparatus 15, the filter element 26f may be replaced and/or cleaned as required.

Referring to FIG. 11, at least one blocking element 26a-j is shown as a combination of the plurality of baffles 26c shown in FIGS. 7A-B and a plurality of fragments 26g-j having different sizes and similar to the plurality of fragments 26d shown in FIG. 8. According to this alternative configuration, a plurality of baffles 26c and a plurality of debris 26g-j are disposed in the enlarged portion 19 of the housing 16. 7A-B, a plurality of baffles 26c, shown in FIG. 11, extend laterally from the inner surface 68 of the enlarged portion 19 of the housing 16 across the enlarged portion 19 of the housing 16. In addition, the plurality of baffles 26c are spaced relative to each other along the central axis 17 such that the baffles 26c divide the enlarged chamber 21 into a plurality of sections. An aperture 28 in each baffle 26c allows the gaseous emissions 10 to flow through the baffle 26 c. A plurality of fragments 26g-j are disposed between adjacent baffles 26c (i.e., in portions of the enlarged chamber 21).

As shown in fig. 11 and 12A-D, a plurality of fragments 26g-j form a mass of reactive material 24. The plurality of fragments 26g-j may be provided in different sizes, with the plurality of fragments 26g-j being grouped in similar sizes (i.e., fragments 26g, 26h, 26i, and 26j are in different groups) and separated from another size of fragment by baffle 26 c. For example, the set of debris 26g-j may be arranged such that the size of the debris 26g-j decreases moving away from the inlet portion 18 of the housing 16 and toward the outlet portion 20 of the housing 16. In other words, the size of the fragments 26g-j in each group may be gradual and may decrease as the gaseous emissions 10 move in the general flow direction in the enlarged portion 19 of the housing 16. In one variation, the chips 26g-j are made of zinc. For example, the chips 26g-j may be formed into a popcorn-like structure having a particularly large surface area and a random sponge-like surface texture by dropping molten zinc into a cooling liquid. It should be understood that in another variation, different sized pieces 26g-j may be mixed together and therefore not grouped based on size.

As shown in fig. 13A-C, several alternatively shaped blocking elements 26k-m are shown in loose material form, which may be used in addition to or in place of the plurality of fragments 26d and 26g-j shown in fig. 8 and 11. Fig. 13A shows an example where the barriers 26k form a mass of reactive material 24 and have a star-like shape similar to that of a children's toy called "Jacks". Fig. 13B shows another example where the alternatively shaped blocking element 26k-m is a plurality of crystal lamellae 26l (one shown) that form a mass of reactive material 24 and can be located in the enlarged portion 19 of the housing 16 like the fragments 26d and 26g-j shown in fig. 8 and 11. The crystal flakes 26l have a snowflake-like shape. Fig. 13C shows another example where the alternatively shaped blocking element 26k-m is a plurality of coils 26m (one shown) that form a mass of reactive material 24 and may be located in the enlarged portion 19 of the housing 16 like the fragments 26d and 26g-j shown in fig. 8 and 11. It should be understood that the barrier 26k and the plurality of crystalline lamellae 26l can be made of zinc or a non-zinc material coated with zinc using various processes, including but not limited to dewaxed forging and 3D printing. The plurality of coils 26m can be fabricated, for example, by twisting a zinc wire onto a mandrel that is spring-like in shape, except that after being twisted around the mandrel, the entire twisted coil is slit along the length of the mandrel such that a single coil is produced. It should also be understood that the alternatively shaped blocking element 26k-m may or may not completely fill the enlarged cavity 21.

It should be understood that the various types of blocking elements 26a-k described above may be mixed and matched to produce various combinations. Examples of mixing and matching include combining one or more baffles 26A-c shown in fig. 5, 6A-B, and 7A-B with a plurality of fragments 26d and 26g-j shown in fig. 8 and 11. Other examples of mixing and matching include combining the plurality of entanglement lines 26e shown in fig. 9 with the plurality of patches 26d and 26g-j shown in fig. 8 and 11. Other alternative configurations are possible that combine the various types of barrier elements 26a-k described above with other filter materials such as activated carbon. Activated carbon can resemble a sponge and collect contaminants by surface contact. Thus, a limited amount of activated carbon may be introduced into the enlarged portion 19 of the housing 16 to act in conjunction with the various types of blocking elements 26a-k described above. Advantageously, the blocking elements 26a-k retain the activated carbon in the enlarged portion 19 of the housing 16 such that the activated carbon is relatively statically disposed throughout the enlarged chamber 21. This situation is in contrast to typical emission control systems that release activated carbon into a stream 10 of gaseous emissions. Because activated carbon does not flow freely with gaseous emissions, activated carbon can be used more efficiently. Those skilled in the art will readily appreciate that the disclosed variations of the reverse venturi apparatus 15 are merely exemplary and that many combinations well beyond the several examples disclosed herein are possible and desirable to address a particular application.

Referring to FIG. 14, another exemplary reverse venturi apparatus 15 'is shown, which includes two enlarged portions 19, 19' connected together in series by a conduit 38. One enlarged portion 19 of the housing 16 extends between the inlet portion 18 of the housing 16 and the conduit 38, while another enlarged portion 19' extends between the conduit 38 and the outlet portion 20 of the housing 16. Thus, the tortuous flow path 27 for the gaseous emissions 10 is elongated. According to this configuration, the gaseous emissions 10 are directed from the enlarged portion 19, through the conduit 38, and to the enlarged portion 19', where additional pollutants are collected and/or captured. It should also be understood that the present disclosure is not limited to the use of only one or two enlarged portions 19, 19' in series, as some applications with significant emissions and/or heavy pollution levels may require multiple enlarged portions connected together in series.

Referring to FIG. 15, another exemplary reverse venturi device 15 "is shown that includes two

enlarged portions

19, 19" connected together in parallel. The three-way inlet valve 39 controls the flow of the gaseous effluent 10, directing the gaseous effluent 10 into and through a conduit 41 or a conduit 42. The three-way outlet valve 40 directs the gaseous effluent 10 to exit from conduit 41 or conduit 42 without flowing back into conduit 42 directly from conduit 41, and vice versa. As the gaseous emissions 10 are directed through the conduit 41, the gaseous emissions 10 enter the enlarged portion 19 through the inlet portion 18 and exit through the outlet portion 20. As the gaseous emissions 10 are directed through the conduit 42, the gaseous emissions 10 enter the enlarged portion 19 "through the inlet portion 18" and exit through the outlet portion 20 ". One advantage of the reverse venturi apparatus 15 "shown in figure 15 is that when one of the

enlarged portions

19, 19" requires maintenance, repair or cleaning, it can be isolated and taken off-line without shutting down the entire system, as the other of the

enlarged portions

19, 19 "can continue to be serviced.

Over time, chemical reactions and/or physical capture of contaminants that occur on the reactive outer surface 25 of the mass of reactive material 24 may result in a saturation point of the mass of reactive material 24, wherein the efficiency of the reverse venturi apparatus 15 is reduced. Thus, the arrangement shown in FIG. 15 allows for the removal, replacement, and/or cleaning of large amounts of reactive material 24 in the

enlarged portions

19, 19 "of the housing 16 to restore the reverse venturi device to pre-saturation efficiency performance without requiring a complete shut down.

The process of removing contaminants from the saturated mass of reactive material will depend inter alia on the type of contaminant and the type of amalgam-forming metal used. The access to the enlarged chambers 21, 21 "provided in the

enlarged portions

19, 19" of the housing 16 will be commensurate with the type of barrier used. When using relatively small loose barriers, channels of the dump and/or drain type are required. If the barrier is a relatively large block, plate, baffle or assembly, appropriate lifting and handling methods and passages are required.

Still referring to FIG. 15, the reverse venturi apparatus 15 may include one or more nozzles 81, the nozzles 81 being disposed in fluid communication with the enlarged portions 19, 19' of the housing 16. The nozzles 81 are positioned to spray the deoxygenated acid onto the mass of reactive material 24 in the

enlarged portions

19, 19 "of the housing 16. In operation, the deoxidizer brushes the bulk of the reactive material 24 of the contaminant to regenerate the bulk of the reactive material 24. Alternatively, the drain 82 may be placed in fluid communication with the

enlarged portions

19, 19 "of the housing 16 to transport the solution of used deoxygenated acid and contaminants away from the

enlarged portions

19, 19" of the housing 16. Advantageously, the saturated zinc can be recycled and recovered, whether as a coating on steel or as a solid zinc structure. Thus, the materials used in the barrier may be reused and recycled. In addition, many of the captured contaminants, particularly heavy metals such as mercury, can be reused and recovered in lighting and chlorine gas production.

Referring to FIG. 16, another exemplary reverse venturi apparatus 15 is shown in which the expanding chamber 45 has a significantly larger volume compared to the volume of the inlet and

outlet conduits

43, 44. The enlarged portion 46 may be circular, square, triangular, oval, or any of a number of shapes (rectangular shapes are shown) that may be nearly as desirable in order to achieve an enlarged tortuous flow path 77 for the gaseous emissions to flow through the enlarged portion 46.

Referring to FIG. 17, a block diagram of a typical gaseous emission control system is shown. The gaseous effluent is directed from the furnace 47 to an electrostatic precipitator (ESP)48, then to a Fluidized Gas Desulfurization (FGD) unit 49, then through a Fabric Filter (FF) unit 50, and then released into the atmosphere through a stack 51. A first concentrate 52 of the contaminants is removed from the gaseous effluent at ESP 48. In a similar manner, the second concentrate of pollutants 53 is removed from the gaseous effluent at the FGD unit 49. The second concentrate 53, which is usually containing mercury and other heavy metals, produced by the FGD unit 49 is typically transferred to wastewater. A third concentrate 54 of pollutants is removed from the gaseous effluent at FF unit 50.

Referring to fig. 18A-B, the block diagram of fig. 17 has been modified with the introduction point option of sorbent injection and adds an additional step in which the gaseous effluent passes through the reverse venturi apparatus 15 described above. In fig. 18A, a first sorbent introduction point 55 is shown between furnace 47 and ESP 48. Alternatively, in fig. 18B, the second sorbent introduction point 56 is shown located between the FGD unit 49 and the FF unit 50. Which option is considered the most suitable adsorbent will depend on the existing configuration and conditions of the plant. There are many other introduction points and/or combinations of introduction points where the sorbent can be introduced instead of the two options depicted in fig. 18A-B, and thus these two options are shown for illustrative purposes. The counter-venturi apparatus 15 in fig. 18A-B is located after the FF unit 50 and before the stack 51. The reverse venturi apparatus 15 may be configured in accordance with any of the foregoing examples described above, as may be suitable for various applications. Finally, the resulting gaseous emissions released to the atmosphere through the stack 51 after exiting the reverse venturi apparatus 15 will be able to meet and exceed current and future EPA emissions regulations and requirements.

The method shown in fig. 18A-B includes the steps of: combusting the fuel in the furnace 47 to produce a gaseous emission containing pollutants, directing the gaseous emission from the furnace 47 to the ESP48, and using the ESP48 to remove a first portion of the particulate pollutants in the gaseous emission. According to the step of removing the first portion of particulate pollutants in the gaseous emission using the ESP48, a first concentrate 52 is formed that contains the first portion of particulate pollutants that have been removed from the gaseous emission by the ESP 48. It should be appreciated that, in operation, ESP48 utilizes induced electrostatic charges to remove fine pollutant particles from gaseous emissions. The method further comprises the following steps: the gaseous effluent from the ESP48 is directed to the FGD unit 49 and the FGD unit 49 is used to remove sulfur dioxide contaminants from the gaseous effluent. According to the step of removing the sulphur dioxide contaminant from the gaseous effluent using the FGD unit 49, a second concentrate 53 is formed, comprising the sulphur dioxide contaminant that has been removed from the gaseous effluent by the FGD unit 49. The method further comprises the following steps: the gaseous effluent from the FGD unit 49 is directed to an FF unit 50 (i.e., baghouse), and a second portion of the particulate pollutants in the gaseous effluent is removed using the FF unit 50. According to the step of removing a second portion of particulate pollutants in the gaseous emission using the FF unit 50, a third concentrate 54 is formed that contains the second portion of particulate pollutants that have been removed from the gaseous emission by the FF unit 50. It should be appreciated that, in operation, pollutant particles are removed from the gaseous emissions as the gaseous emissions pass through one or more fabric filters (not shown) of the FF unit 50.

According to the present disclosure, the method further comprises the steps of: the gaseous emissions from the FF unit 50 are directed to the reversing venturi device 15 and the reversing venturi device 15 is used to remove heavy metal contaminants from the gaseous emissions. According to the step of removing heavy metal contaminants from the gaseous effluent using the reverse venturi apparatus 15, the gaseous effluent passes through (i.e., flows over) a mass of reactive material disposed in the reverse venturi apparatus 15. The amalgam-forming metal in the bulk of the reactive material chemically bonds with the heavy metal contaminants in the gaseous emissions. Thus, when heavy metal contaminants bind to the amalgam-forming metal in the mass of reactive material, the mass of reactive material traps the heavy metal contaminants in the reverse venturi apparatus 15. The method may then continue to direct the gaseous emissions from the reverse venturi apparatus 15 to a stack 51, which stack 51 discharges the gaseous emissions into the surrounding atmosphere. It will also be appreciated that the reverse venturi apparatus 15 advantageously has a relatively small footprint of equipment, allowing it to be easily installed as a retrofit in the line between the

emission control devices

48, 49, 50 of existing systems and the stack 51 to atmosphere.

Optionally, the method may include the step of injecting a sorbent into the gaseous effluent. According to this step and as shown in fig. 18A, sorbent may be injected into the gaseous effluent at a first sorbent introduction point 55 disposed between the furnace 47 and the ESP 48. Alternatively, as shown in fig. 18B, the sorbent may be injected into the gaseous effluent at a second sorbent introduction point 56 disposed between the FGD unit 49 and the FF unit 50. The sorbent contains an amalgam-forming metal such that the sorbent combines with at least some of the heavy metal contaminants in the gaseous effluent before the gaseous effluent enters the reverse venturi device 15. By injecting sorbent into the gaseous emissions at either the first sorbent introduction point 55 or the second sorbent introduction point 56, more mercury, heavy metals, and acid gases can be collected in the FF unit 50 at levels not previously possible. As mentioned above, the amalgam-forming metal may be selected from the group comprising zinc, iron and aluminium, and the adsorbent may be, for example, a CZTS compound. The adsorbent can be regenerated and rejuvenated so that hazardous contaminants can be collected and recycled.

Referring to FIG. 19, a block diagram of a typical non-gaseous emission control system is shown. The liquid and/or liquid-like effluent may be directed from the Fluidized Gas Desulfurization (FGD) unit 59 and/or from the wet scrubber unit 58 into the lime treatment unit 60 and then to the settling tank 61. After a suitable period of time, the non-gaseous effluent will be directed from the settling tank 61 to either the process system 64 for drying process preparation or to the dewatering system 62. The non-gaseous emissions directed through the process 64 for drying treatment are ready for treatment in a landfill 65. The non-gaseous emissions directed through the dewatering system 62 (which may sometimes include a recirculation system) are ready for a second industrial process 63, which may involve, for example, the manufacture of gypsum and/or cement. Non-gaseous emissions not directed from the settling pond 61 into the dewatering system 62 or to the process 64 for drying treatment are directed to discharge into a flume 66. The resulting non-gaseous emissions released into the water way 66 are not regulated as much as the next few years. Proposed EPA water emissions regulations and requirements will have extremely strict limits compared to the emissions currently allowed into waterways. Industries that require contaminated liquid discharge into waterways have current discharge control technologies that are nearly impossible to meet and/or comply with upcoming EPA regulations.

Referring to fig. 20, the block diagram of fig. 19 has been modified with one or more treatment tanks 67 containing the above-described adsorbent. The treatment tank 67 is located after the non-gaseous effluent is directed out of the settling tank 61 and before they are discharged into the flume 66. The method shown in fig. 20 comprises the following steps: collecting the non-gaseous emissions containing the contaminants, passing the non-gaseous emissions through the FGD unit 59 and/or the wet scrubber 58 to remove some of the contaminants in the non-gaseous emissions, directing the non-gaseous emissions from the FGD unit 59 and/or the wet scrubber 58 to the discharge of the lime treatment unit 60, and passing the non-gaseous emissions through the lime treatment unit 60 to soften the non-gaseous emissions by the Clark process. It should be appreciated that, in operation, the lime treatment unit 60 removes certain ions (e.g., calcium (Ca) and magnesium (Mg)) from the non-gaseous emissions by precipitation. The method further comprises the following steps: directing the non-gaseous emissions from the lime treatment unit 60 to a settling tank 61, wherein some contaminants in the non-gaseous emissions are removed by sedimentation; dehydrating a first portion of the non-gaseous effluent in a settling tank 61 and using the dehydrated by-product in a secondary industrial process 63; and removing a second portion of the non-gaseous emissions from the settling tank 61 and subjecting the second portion of the non-gaseous emissions to a drying process 64. The dewatering process may include recycling of the first portion of the non-gaseous emissions, and the secondary industrial process 63 may involve, for example, the manufacture of gypsum or the manufacture of cement, according to the steps of dewatering the first portion of the non-gaseous emissions in the settling tank 61 and using the dewatering by-products in the secondary industrial process 63. The drying process 64 may include depositing the second portion of the non-gaseous emissions in the landfill 65 according to the steps of removing the second portion of the non-gaseous emissions from the settling tank 61 and subjecting the second portion of the non-gaseous emissions to the drying process 64.

According to the present disclosure, the method further comprises the steps of: a third portion of the non-gaseous effluent in the settling tank 61 is directed to a treatment tank 67 containing the disclosed adsorbent. The sorbent contains an amalgam-forming metal that binds with heavy metal contaminants in the third portion of the non-gaseous emissions. Thus, when the heavy metal contaminants are bound to the adsorbent and settle/precipitate out of the non-gaseous effluent, the adsorbent then traps the heavy metal contaminants in the treatment tank 67. The method may then continue to direct the non-gaseous emissions from the treatment tank 67 to the water channel 66 for discharge. It should be understood that the design of the treatment tank 67 may allow for the continuous passage of non-gaseous emissions (i.e., a waste stream) through the treatment tank 67.

With respect to the adsorbents of the present disclosure, several exemplary embodiments are disclosed. These exemplary embodiments are merely a few examples and do not represent an exhaustive list of potential variations on the subject matter.

As noted above, one exemplary sorbent is elemental zinc powder. The zinc powder is made of elemental zinc. The zinc may be present in powder form or in particulate form. One method that can be used to extend the useful life of zinc dust and/or particles at elevated temperatures for certain gas emissions applications and to reduce and/or prevent premature oxidation is to mix or coat the particles and/or powder with a solid acid such as sulfamic acid, citric acid, or other organic acids. The powder/acid mixture may be injected into the gaseous effluent (e.g., flue gas stream) and/or placed in a suitable exemplary embodiment of the reverse venturi apparatus 15.

The optimum particle size range of the zinc powder is 0.5 nm to 7,500 μm. Furthermore, it has been found that a powder mixture having a range of particles of different sizes is beneficial, especially if the particle size ranges from 0.5 nm to 7,500 μm. Similarly, the optimum particle size range for the zinc particles is 7,500 microns to 3.0 inches. Furthermore, it has been found that a particle mixture having a range of different sized particles is beneficial, particularly if the particle size ranges from 7,500 microns to 7,500 inches.

In another exemplary embodiment, the adsorbent is CZTS, which has the elemental formula Cu₂ZnSnS₄. The CZTS may also include other phases of copper, zinc, tin, and sulfur, which may also be beneficial. The CZTS and/or the associated phases of copper, zinc, tin and sulfur may be blended in stoichiometric proportions and then may be subjected to mechanochemical compounding in a mill. In addition, the CZTS may be mixed with any one of several clays such as bentonite or zeolite and calcium hydroxide (CaOH) in equal proportions. The optimum particle size range for the CZTS powder is from 0.5 nm to 7,500 microns. In testing and development, it has been found that a CZTS powder mixture having a range of different sized particles is beneficial, particularly if the particle size ranges from 0.5 nanometers to 7,500 microns. In applications where specialized CZTS particles are preferred, an optimum particle size of 7,5 has been found00 microns to 3.0 inches. Furthermore, it has been found that a mixture of CZTS particles having a range of different sized particles is beneficial, particularly if the particle size ranges from 7,500 microns to 3.0 inches.

For most contaminants, CZTS is most effective at the minimum particle size within the above range and when the highest amount of CZTS in the metal phase is present. It should be understood that during the manufacture of CZTS, complete conversion of the mixture of copper, zinc, tin and sulfur to CZTS does not occur, but rather a mixture of phases (e.g., danbai (CuZn)₂) And tin sulfur (SnS)).

In one exemplary method of manufacture of CZTS, copper, zinc, tin, and sulfur are added to the mill in no particular order. Milling is accomplished using a ball mill, or some type of disc mill, or a combination of milling equipment that achieve the desired particle size in a sequential combination. An exemplary starting particle size range is 325 standard mesh to 100 standard mesh, with 1 standard mesh equaling 7,500 microns. Mixing the received particles in a predetermined copper: zinc: tin: sulfur ═ 1.7: 1.2: 1.0: the molar ratio of 4.0 was further weighed. After the mesh size and molar ratio are confirmed, the particles are mechanochemical compounded into CZTS and its other phases by milling. The grinding time is controlled to achieve optimum performance for a particular application. It should also be understood that the wet milling process may be used to accomplish milling by adding a suitable solvent such as a glycol ether, glycol, ammonia, or other alcohol, or by dry milling in an inert gas atmosphere.

During milling, intermittent sampling was performed to determine particle size using a particle size analyzer and percent phase transformation using SEM, XRD, or raman. The grinding ball size is important and it has been shown in tests that the optimum ball to powder weight ratio (batch ratio) is at least 5: 1. the grinding balls are preferably made of steel, ceramic, zirconia, or any other material that achieves a size and/or phase change without contaminating the final product. When wet milling is used, the CZTS is dried. The CZTS is then further blended using a ribbon blender, a V-blender, or any other suitable blender, to blend equal portions of bentonite or zeolite and calcium hydroxide.

In accordance with the above method, the sorbent may be introduced into the gaseous effluent, wherein the gaseous effluent has a temperature of about 750 degrees Fahrenheit or less. The sorbent may be introduced into the gaseous effluent by any of several methods, such as, but not limited to, injection, fluidized bed, coated filter, and trapping. The introduction method may be selected based on the existing emissions control system in the plant to facilitate retrofitting. One convenient method may be to inject CZTS into the gaseous effluent instead of activated carbon, where the same injection equipment may be used with or without modification.

In some applications, the treatment of gaseous emissions may be optimized when CZTS is blended with bentonite to effectively remove pollutants. Alternatively, when CZTS is blended with zeolites, the treatment for non-gaseous emission applications may be optimized. In addition to the specific materials blended with CZTS, the proportions of the blend may be application specific to provide optimized contaminant removal capabilities.

As shown in fig. 18A-B, where CZTS is used to treat gaseous emissions, the fabric filter unit 50 should be placed downstream of the CZTS introduction points 55,56 so that the fabric filter unit 50 captures adsorbent particles and increases the contact time of the gaseous emissions with the adsorbent. The deposition of the sorbent on the fabric filters (i.e., the bags) of the fabric filter unit 50 allows for additional contact time between the gaseous effluent and the sorbent and allows for collection of the sorbent for subsequent recovery. The small particle size of the sorbent allows the sorbent, such as dust carried by wind, to be entrained in the flow of the stream of gaseous emissions. During the period of time that the sorbent is entrained in the flow of gaseous emissions, the sorbent comes into contact with the pollutants that are also traveling in the flow of gaseous emissions, and thus can chemically react with and bind to the sorbent. Upon reaching the fabric filter unit 50, the gaseous effluent continues to pass through the filters in the fabric filter unit 50 while the combined sorbent and pollutant have a particle size that is too large to pass through the filters. When the CZTS particles are less than 10 microns, it may be desirable to pre-coat the filter with larger sized CZTS particles, activated carbon, talc, lime, or other suitable substances in the fabric filter unit 50 so that the smaller CZTS particles do not pass through the filter. Alternatively, a lower micron size nominal filter may be used in the fabric filter unit 50.

In other applications of non-gaseous emissions, the CZTS may be introduced into the treatment tank 67 shown in fig. 20. In this configuration, the CZTS is optimally introduced into the treatment tank 67 for a period of time with appropriate agitation, and then the non-gaseous effluent (e.g., wastewater) undergoes pH adjustment, flocculation, and filtration prior to discharge. Thereafter, the CZTS in the treatment tank 67 may be subjected to a recovery process, wherein contaminants are collected from the CZTS. Used CZTS can be recovered by leaching mercury from the CZTS or by vacuum distillation. The collected contaminants can then be reused in other industries. CZTS also has the benefit of being able to reduce nitrate and nitride levels in non-gaseous emissions.

The EPA enacts drainage regulations in force in 2016 to be much stricter than air regulations. The current EPA water regulatory levels listed in nanograms per liter (ng/L), micrograms per liter (μ g/L) and/or g/L are: mercury @119 ng/L; arsenic (As) @8 μ g/L; selenium (Se) @10 μ g/L; nitrogen dioxide (NO)₂) And Nitrate (NO)₃) @0.13 g/L. Other heavy metals such as lead (Pb) and cadmium (Cd) also present EPA limitation levels. In many existing plants, water having a level of contamination above permitted discharge regulations is directed to one or the other of a holding tank and/or other type of sludge holding storage tank. CZTS can treat the solids in the holding tank by the same methods as disclosed herein for treating non-gaseous emissions. Depending on the ionic form of the heavy metals, the sludge composition and/or the pH, the contact time of CZTS in the holding tank may be suitably adjusted. Proper pH adjustment, flocculation and subsequent filtration will allow normal discharge, handling and/or use in other industries, all of which were not previously possible.

It should be understood that the adsorbents disclosed herein do not contain any loose carbon, including activated carbon currently used in the art. Thus, the metal sulfides produced as a by-product of the disclosed process are non-leachable. Thus, these by-products have valuable industrial uses in gypsum wallboard and cement applications. Leaching tests of metal sulfides by EPA are well known and the use in these products has been well documented.

In one configuration, activated carbon may be embedded in the filter of the fabric filter unit 50. The activated carbon is not free to escape into the stream of gaseous emissions. Another limited use of activated carbon is possible, where activated carbon coats CZTS in its crystalline form, resulting in CZTS with a thin layer of carbon having a thickness of about 1.0 nanometer or less. This helps to encourage the capture of very small metal vapor mercury particles. In a similar manner, the CZTS crystal form may be coated with a nano-like thin layer of zeolite or other coating to specifically target specific harmful contaminants for a particular application. In another configuration shown in fig. 33, the counter-venturi fluidized bed apparatus includes an arrangement for cleaning and recycling the adsorbent in the form of a series of adsorbent treatment subsystems for CZTS adsorbent, CZTS alloy adsorbent and/or carbon-based adsorbent.

Referring to FIG. 21, a graph illustrates the percentage of pollutants removed from the emissions as a result of the prior emissions control system and the reverse venturi apparatus and method disclosed herein. Currently, the EPA establishes a 90% pollutant removal level 78 for gaseous emissions. Existing emission control systems 79 are effective at removing 88% -90% of the harmful pollutants. However, the EPA has been increasing the minimum percentage of pollutant removal required for many years, such that many existing emission control systems are no longer able to meet the requirements, and many other existing emission control systems are only able to meet the requirements at their maximum removal capabilities available under current technology.

Still referring to FIG. 21, the exemplary emissions control system 80 may be a new emissions control system based on the reverse venturi apparatus, sorbents and/or methods disclosed herein, or it may be an existing emissions control system that has been modified and expanded to include the reverse venturi apparatus, sorbents and methods disclosed herein. Tests have demonstrated that the exemplary emission control system 80 is effective and capable of removing at least 98% of harmful pollutants, which is well above current EPA regulated levels.

Referring to fig. 22 and 24, an exemplary method of emissions control is shown wherein a contaminated gaseous source 150 is introduced into a system 154 through one or more pre-fluidized bed filters 151, through a fluidized bed 152, through one or more post-fluidized bed filters 153, and discharged through the system, which releases gaseous emissions with environmentally controlled release through a stack 155. It should be understood that it is not always necessary to first pass the contaminated gaseous source 150 through one or more pre-fluidized bed filters 151; however, application specific requirements may require one or more pre-fluidized bed filters 151.

The fluidized bed 152 has a counter-venturi shape with a specific size ratio of length L to diameter D, which is at a minimum of 2.9: 1 and maximum 9.8: 1. This ratio is optimized for extended residence flow time of the contaminated gaseous source 150 in the fluidized bed 152, which fluidized bed 152 is filled with a specialized adsorbent, such as a reactive material 164. The reactive material 164 is an adsorbent comprising Copper Zinc Tin Sulfide (CZTS) compounds and/or alloys thereof. A preferred exemplary length L to diameter D ratio of the fluidized bed 152 is 4.4: 1, which has been determined by trial and error testing.

Preferably, the fluidized bed 152 has a predominantly circular cross-section. Although not shown in fig. 24, one or more of the various baffles and/or other application-specific flow restricting barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 also has predominantly outwardly extending

convex ends

168 and 169 to promote extended residence flow time while minimizing turbulent flow through the reactive material 164. When the contaminated gaseous source 150 stream enters the fluidized bed 152 at the inlet 165, intimate contact with the reactive material 164 is initiated, creating random non-turbulent flow 166. Due to the predominantly outwardly extending

convex ends

168 and 169, the random non-turbulence 166 turns back on itself, resulting in an extended residence time in the fluidized bed 152 before the non-turbulence 166 exits from the fluidized bed 152 through the outlet 167. The reactive material 164 promotes random non-turbulence 166, which is a random, tortuous flow path for the contaminated gaseous source 150. It should be understood that the length L of the fluidized bed 152 does not include the convex ends 168 and 169.

The fluidized bed 152 has a side outlet 170 leading to the sorbent cleaning station 156. The sorbent cleaning station 156 has the option of removing the depleted sorbent 157 from the system for disposal. Additionally, captured contaminant elements 158 captured from the contaminated gaseous source 150 by the reactive material 164 and separated from the reactive material 164 in the sorbent cleaning station 156 may be processed and/or recycled. The sorbent cleaning station 156 returns cleaned reactive material 164 to the fluidized bed 152 through a sorbent return port 159. The bulk refill sorbent vessel 168 provides a supplemental volume of reactive material 164 as needed to replace the removed spent sorbent 157. The system exhaust 154 provides gaseous emissions through ambient controlled release from the exhaust stack 155. Additional discharge of captured waste 160 may also be provided by additional sorbent processing subsystems (fig. 33).

Referring to fig. 23 and 24, an exemplary method of emissions control is shown wherein a non-gaseous source of pollution 161 is introduced into the system through one or more pre-fluidized bed filters 151, through fluidized bed 152, through one or more post-fluidized bed filters 153, and through system exhaust 154, which releases gaseous emissions with environmentally controlled release 162. It should be understood that it is not always necessary to first pass the contaminated non-gaseous source 161 through one or more pre-fluidized bed filters 151; however, application specific requirements may require that one or more pre-fluidized bed filters 151 be required.

The fluidized bed 152 has a counter-venturi shape with a specific size ratio of length L to diameter D, which is at a minimum of 2.9: 1 and maximum 9.8: 1, which is optimized for extended residence flow time of the contaminated non-gaseous source 161 in the fluidized bed 152, the fluidized bed 152 is filled with a specialized adsorbent, such as a reactive material 164. The reactive material 164 is an adsorbent comprising Copper Zinc Tin Sulfide (CZTS) compounds and/or alloys thereof. A preferred exemplary length L to diameter D ratio of the fluidized bed 152 is 4.4: 1, which has been determined by trial and error testing.

Preferably, the fluidized bed 152 also has predominantly outwardly extending

convex ends

168 and 169 to promote extended residence flow time while minimizing turbulent flow through the reactive material 164. When the contaminated non-gaseous source 161 stream enters the fluidized bed 152 at the inlet 165, intimate contact with the reactive material 164 is initiated, creating random non-turbulent flow 166. The random non-turbulence 166 turns itself due to the predominantly outwardly extending

convex ends

168 and 169, resulting in an extended residence time in the fluidized bed 152 before exiting through the outlet 167 from the fluidized bed 152. The reactive material 164 promotes random non-turbulence 166, which is a random tortuous flow path for the contaminated non-gaseous source 161. It should be understood that the length L of the fluidized bed 152 does not include the convex ends 168 and 169.

Preferably, the fluidized bed 152 has a predominantly circular cross-section. Although not shown in fig. 24, one or more of the various baffles and/or other application-specific flow restricting barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 has a side outlet 170 leading to the sorbent cleaning station 156. The sorbent cleaning station 156 has the option of removing the depleted sorbent 157 from the system for disposal. Additionally, captured contaminant elements 158 captured from the contaminated non-gaseous source 161 by the reactive material 164 and separated from the reactive material 164 in the sorbent cleaning station 156 may be processed and/or recycled. The sorbent cleaning station 156 provides for the return of cleaned reactive material 164 to the fluidized bed 152 through a sorbent return port 159. The bulk refill sorbent vessel 168 provides a supplemental volume of reactive material 164 as needed to replace the removed spent sorbent 157. The system exhaust 154 provides non-gaseous emissions through an ambient controlled release 162. Additional drainage of captured waste 163 is also provided.

Referring to fig. 25, an exemplary method is shown: the contaminated gaseous emissions 250 are passed through one or more pre-filters 251, through a fluidized bed 253, through one or more post-filters 255, through a system exhaust 256, and ultimately released as a controlled release gaseous emissions through an exhaust stack 257 and/or through a waste treatment process 262. The fluidized bed 253 is bisected by the longitudinal plane 290. The inlet P3 and the outlet P4 are configured to receive and discharge gaseous emissions when the fluidized bed 253 is positioned with the longitudinal plane 290. Barriers (not shown) inside the fluidized bed 253 provide a preferred tortuous flow path that is particularly suited for gaseous emissions as they are introduced through the inlet P3 and discharged through the outlet P4. The inlet P3 and the outlet P4 are located above the longitudinal plane 290 of the fluidized bed 253.

As shown in fig. 25, the fluid bed 253 may be mounted on a truck 254 and configured to tilt the fluid bed 253 about a pivot point 252. When a gaseous effluent is to be treated in the fluidized bed 253, the longitudinal plane 290 of the fluidized bed 253 is substantially horizontal. The adsorbent cleaning station 258 is disposed in fluid communication with the outlet P5 of the fluidized bed 253, wherein contaminant particles captured by the adsorbent are removed. The removed contaminants may be recycled or disposed of through station 261. Spent sorbent is treated by station 259 and cleaned sorbent is recycled from sorbent return 260 back to fluidized bed 253 through return P6.

Referring to fig. 26, an exemplary method is shown: the contaminated non-gaseous effluent 295 is passed through one or more pre-filters 251, through the fluidized bed 253, through one or more post-filters 255, through the system exhaust 256, and ultimately released as controlled ambient non-gaseous emissions 273 and/or through the waste treatment process 274. The inlet P2 and the outlet P1 are configured to receive and discharge non-gaseous emissions. Barriers (not shown) inside the fluidized bed 253 provide a preferred tortuous flow path that is particularly suited for non-gaseous emissions as they are introduced through the inlet P2 and discharged through the outlet P1. The inlet P2 and the outlet P1 are bisected by the longitudinal plane 290 of the fluidized bed 253 (i.e., aligned with the longitudinal plane 290 of the fluidized bed 253).

When non-gaseous emissions are to be treated in the fluidized bed 253, the longitudinal plane 290 of the fluidized bed 253 is substantially vertical. The adsorbent cleaning station 258 is disposed in fluid communication with the outlet P5 of the fluidized bed 253, wherein contaminant particles captured by the adsorbent are removed. The removed contaminants may be recycled or disposed of through station 261. Spent sorbent is treated by station 259 and cleaned sorbent is recycled from sorbent return 260 back to fluidized bed 253 through return P6.

Referring to fig. 27, a table is shown in which a preferred reactive CZTS alloy adsorbent 341 is disclosed as compared to other adsorbents, including activated carbon 342 and zeolite 343. The main types listed for contaminants 367 include nitrogen species 368, phosphate salts 369, heavy metals 370, sulfur species 371, mercury 372, and selenate 373. The pollutant 367 is further listed for each sorbent listed for

gaseous emissions

344, 346, and 348 as compared to

non-gaseous emissions

345, 347, and 349.

The test proves that: the reactive CZTS alloy sorbent 341 is effective in capturing and removing pollutants 367 in the gaseous emissions 344 and/or non-gaseous emissions 345. In contrast, the activated carbon 342 is ineffective at capturing or removing the pollutants 367 in the gaseous emissions 346 and/or the non-gaseous emissions 347. Similarly, zeolite 343 is ineffective at capturing or removing contaminants 367 in gaseous emissions 348 and/or non-gaseous emissions 349.

Referring to fig. 28, an expanded adsorbent list is shown, including reactive CZTS alloy adsorbent 351 of the present disclosure and other adsorbents, including caustic 350, iron oxide 355, and zeolite 356. The reactive CZTS alloy sorbent 351 includes a sulfur (S) CZTS alloy 352, a selenate (S) CZTS alloy 353, and an iron oxide CZTS alloy 354. CZTS alloy adsorbent 351 is effectively co-reactive with the following group of contaminants: selenate 357, Total Ionized sulfur (Total Ionized sulfur) 358, Total Ionized nitrogen 359(Total Ionized nitrogen) and Total Ionized phosphate (Total Ionized phosphosalts) 360. The reactive CZTS alloy adsorbent 351 is capable of capturing and removing these pollutants from gaseous and non-gaseous emissions.

In contrast, etchant 350 is only effective for total ionized sulfur 358. Iron oxide 355 is only effective against selenate 357 and has very slow reaction characteristics (only effective against non-gaseous emissions) with Total nitrogen species (Total nitrosgens) 359 and Total ionized phosphates (Total ionized phosphatates) 360. Zeolite 356 is only effective for total ionized nitrogen species 359 and total ionized phosphate 360. As a result, known adsorbents such as caustic 350, iron oxide 355, and zeolite 356 have limited effective characteristics compared to the broad spectrum characteristics of reactive CZTS alloy adsorbent 351 disclosed herein. Even though known sorbents have some degree of effectiveness, they have not achieved the level of effectiveness of the reactive CZTS alloy sorbents 351 disclosed herein.

Referring to fig. 29, a table 364 illustrates the ability of a prior art sorbent 365 to be post-treated after use in an emissions control system to capture and remove contaminants 367 including nitrogen species 368, phosphorous species 369, heavy metals 370, sulfur species 371, mercury 372, and selenate 373. The ability to separate these contaminants 367 from the prior art sorbent in the gaseous emission 374 and/or non-gaseous emission 375, except for the nitrogen species 368 in the gaseous emission 374, is very poor and nearly absent. Similarly, table 364 shows that little ability to reuse the prior art sorbent 366 after separation of contaminants 367 exists other than the gaseous effluent 376 containing nitrogen species 368.

Referring to fig. 30, table 378 illustrates the ability of the reactive CZTS alloy sorbent 339 disclosed herein to post-treat after use in an emissions control system to capture and remove contaminants 367 including nitrogen species 368, phosphorus species 369, heavy metals 370, sulfur species 371, mercury 372, and selenate 373. The ability to separate the contaminants 367 in the gaseous emissions 374 and/or non-gaseous emissions 375 from the disclosed reactive CZTS alloy adsorbent 339 is particularly advantageous because it means that the contaminants 367 can be more easily treated or recycled, and because the reactive CZTS alloy adsorbent 339 can be reused in the emissions control system (as shown in table 378). In particular, table 378 illustrates the ability to reuse the reactive CZTS alloy sorbents 340 disclosed herein after separating them from the contaminants 367 in the gaseous emissions 376 and the non-gaseous emissions 377.

Referring to FIG. 31, a block diagram illustrates a system and method for removing pollutants from gaseous emissions 250. The gaseous emissions 250 are monitored and analyzed in step 379 to determine the type and level of pollutants in the gaseous emissions 250. The monitoring may be intermittent spot checks of a periodic system or continuous on-line monitoring and analysis. Based on the type and/or level of pollutants remaining in the gaseous emissions 250 as determined by step 379, the flow of emissions is directed through a pre-filter inlet manifold 380 such that the gaseous emissions 250 are further directed through

suitable pre-filters

381, 382, 383, and/or 384. Selection of the

appropriate pre-filters

381, 382, 383, and/or 384 is accomplished by the selection method shown in FIG. 28.

The prefilter shown in fig. 31 is packed with a reactive CZTS alloy adsorbent 351 shown in fig. 28. For example, the prefilter 381 is filled with a CZTS alloy 352 of sulfur (S) as shown in fig. 28. Prefilter 382 is filled with a CZTS alloy 353 of selenate (S) shown in fig. 28. The pre-filter 383 is filled with a ferrous oxide CZTS alloy 354 as shown in fig. 28. The pre-filter 384 is filled with a combination of

CZTS alloy sorbents

352, 353 and/or 354. Additional pre-filters may be added to pre-filter inlet manifold 380, each filled with a different combination of

CZTS alloy sorbents

352, 353 and/or 354, to effectively treat a particular level and/or type of contaminants remaining in gaseous effluent 250.

After directing the contaminated gaseous effluent 250 through a suitable pre-filter, a pre-filter outlet manifold 385 directs the effluent into the fluidized bed 253. For the gaseous effluent 250, the housing of the fluidized bed 253 is disposed in a direction substantially parallel to the platform 271. The contaminants are separated from the sorbent in step 258 and returned to the fluidized bed 253 through the sorbent return 260.

After the gaseous effluent 250 exits the fluidized bed 253, a post-filter monitoring step 386 determines a new level and/or type of contaminants remaining in the gaseous effluent 250 and directs the gaseous effluent 250 through a post-filter inlet manifold 387. Selection of the appropriate post-filter 388, 389, 390 and/or 391 is accomplished by the selection method shown in fig. 28. The post-filter shown in fig. 31 is packed with the reactive CZTS alloy adsorbent 351 shown in fig. 28. For example, the post-filter 388 is filled with a CZTS alloy 352 of sulfur (S) as shown in fig. 28. The post-filter 389 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The post-filter 390 is filled with a ferrous oxide CZTS alloy 354 as shown in fig. 28. Post-filter 391 is filled with a combination of

CZTS alloy sorbents

352, 353 and/or 354. The post-filter outlet manifold 392 directs the gaseous emissions 250 to the gaseous system exhaust 256a, with some of the gaseous emissions 250 being exhausted through a controlled gaseous release stack 257 and some of the gaseous emissions 250 being exhausted through a suitable waste treatment step 262.

Additional post-filters may be added to post-filter inlet manifold 387, each post-filter filled with a different combination of

CZTS alloy sorbents

352, 353, and/or 354 to effectively treat a particular level and/or type of contaminants remaining in gaseous emission 250.

All

pre-filters

381, 382, 383, 384 and post-filters 388, 389, 390, 391 may be directed through the sorbent cleaning step 258 and the sorbent return port 260, respectively. Step 258 includes separating contaminants from the CZTS alloy adsorbent 351 so that the contaminants can be recycled and/or collected for disposal 261 as appropriate. Any depleted CZTS alloy sorbent 351 may be treated by treatment step 259. Replacement of the particular CZTS alloy adsorbent 351 for each

particular pre-filter

381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be performed after step 258. Not shown are specific schemes and/or schematics for directing sorbent from

pre-filters

381, 382, 383, 384 and/or post-filters 388, 389, 390, 391 to the sorbent cleaning step 258 and for directing sorbent from the sorbent cleaning step 258.

Referring to FIG. 32, a block diagram illustrates a system and method for removing pollutants from non-gaseous emissions 295. The non-gaseous emissions 295 are monitored and analyzed in step 379 to determine the type and level of pollutants in the non-gaseous emissions 295. The monitoring may be intermittent spot checks of a periodic system and/or continuous on-line monitoring and analysis. Based on the type and/or level of pollutants remaining in the non-gaseous emissions 295 determined by step 379, the flow of emissions is directed through a pre-filter inlet manifold 380 such that the gaseous emissions 295 are further directed through

suitable pre-filters

381, 382, 383, and/or 384. Selection of the

appropriate pre-filters

The prefilter shown in fig. 32 is filled with the reactive CZTS alloy adsorbent shown in fig. 28. For example, the prefilter 381 is filled with a CZTS alloy 352 of sulfur (S) as shown in fig. 28. Prefilter 382 is filled with a CZTS alloy 353 of selenate (S) shown in fig. 28. The pre-filter 383 is filled with a ferrous oxide CZTS alloy 354 as shown in fig. 28. The pre-filter 384 is filled with a combination of

CZTS alloy sorbents

352, 353 and/or 354. Additional pre-filters may be added to the pre-filter inlet manifold 380, each filled with a different combination of

CZTS alloy sorbents

352, 353 and/or 354 to effectively treat a particular level and/or type of contaminants remaining in the non-gaseous emissions 295.

After the contaminated non-gaseous emissions 295 are directed through a suitable pre-filter, the pre-filter outlet manifold 385 directs the emissions into the fluidized bed 253. For the non-gaseous emissions 295, the housing of the fluidized bed 253 is disposed in a substantially perpendicular orientation to the platform 271. The contaminants are separated from the sorbent in step 258 and returned to the fluidized bed 253 through the sorbent return 260.

After the non-gaseous emissions 295 leave the fluidized bed 253, a post-filter monitoring step 386 determines a new level and/or type of contaminants remaining in the non-gaseous emissions 295 and directs the non-gaseous emissions 295 through a post-filter inlet manifold 387. Selection of the appropriate post-filter 388, 389, 390 and/or 391 is accomplished by the selection method shown in fig. 28. The post-filter shown in fig. 32 is packed with the reactive CZTS alloy adsorbent 351 shown in fig. 28. For example, the post-filter 388 is filled with a CZTS alloy 352 of sulfur (S) as shown in fig. 28. The post-filter 389 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The post-filter 390 is filled with a ferrous oxide CZTS alloy 354 as shown in fig. 28. Post-filter 391 is filled with a combination of

CZTS alloy sorbents

352, 353 and/or 354. The post-filter outlet manifold 392 directs the non-gaseous emissions 295 to the non-gaseous system exhaust 256b, with some of the non-gaseous emissions 295 being discharged through the environmentally controlled non-gaseous release port 273 and some of the non-gaseous emissions 295 being discharged through the appropriate waste treatment step 262. Additional post-filters may be added to post-filter inlet manifold 387, each post-filter filled with a different combination of

CZTS alloy sorbents

352, 353, and/or 354 to effectively treat a particular level and/or type of contaminants remaining in non-gaseous emission 295.

All

pre-filters

particular pre-filter

381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be performed after step 258. Specific roadmaps and/or schematics for directing the sorbent from pre-filter 388, 389, 390, 391 and/or post-filter 388, 389, 390, 391 to sorbent cleaning step 258 and for directing the sorbent from sorbent cleaning step 258 are not shown.

Referring to FIG. 33, an exemplary emissions control system is shown. The contaminated effluent is introduced into the fluidized bed 152 via inlet 165. It should be understood that the effluent may first pass through one or more pre-fluidized bed filters 151 (fig. 22 and 23), depending on the specific requirements of the application.

The fluidized bed 152 has a shell 16 in the shape of a counter venturi tube with a specific size ratio of length L to diameter D, which is at a minimum of 2.9: 1 and maximum 9.8: 1. This ratio is optimized for extended residence flow time of the contaminated effluent in the fluidized bed 152, the fluidized bed 152 being filled with a specialized reactive material 164 comprising one or more adsorbents. A preferred exemplary length L to diameter D ratio of the fluidized bed 152 is 4.4: 1, which has been determined by trial and error testing. One or more exemplary fluidized beds 152 may be connected in series or in parallel depending on the particular requirements of the application.

Preferably, the fluidized bed 152 has a predominantly circular cross-section. Although not shown in fig. 33, one or more of the various baffles and/or other application-specific flow restricting barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 also has predominantly outwardly extending

convex ends

168, 169 to promote extended residence flow time while minimizing turbulent flow through the reactive material 164. When the contaminated effluent stream enters the fluidized bed 152 at inlet 165, intimate contact with the reactive material 164 is initiated, resulting in random non-turbulence 166. Due to the predominantly outwardly extending

convex ends

168, 169, the random non-turbulence 166 turns back on itself, resulting in an extended residence time in the fluidized bed 152 before the non-turbulence 166 exits from the fluidized bed 152 through the outlet 167. The reactive material 164 promotes random non-turbulence 166, which is a random, tortuous flow path for the contaminated emissions. It should be understood that the length L of the fluidized bed 152 does not include the convex ends 168, 169.

The fluidized bed 152 includes at least one monitoring sensor station 421 (i.e., a first monitoring sensor) that provides data, status, and feedback regarding the operating parameters. The monitoring sensor station 421 is equipped to monitor emissions flow levels, pressures, speeds, temperatures, and many other relevant parameters associated with the emissions control system. Based on the feedback information, the equipment may make some automatic adjustments, while other process and/or system parameters may need to be adjusted manually. The monitoring sensor station 421 provides information about the effectiveness of the sorbent inside the fluidized bed 152 and helps determine when to clean and/or regenerate the sorbent.

In an exemplary embodiment of the present disclosure, the fluidized bed 152 has at least one

side outlet

403, 409, 415 leading to the

sorbent processing subsystems

400, 401, 402, respectively. The

sorbent processing subsystems

400, 401, 402 shown in fig. 33 are located outside of the fluidized bed 152, but alternatively they may be installed inside of the fluidized bed 152.

The fluidized bed 152 includes at least one closed loop sorbent outlet monitoring sensor station 422 and at least one closed loop sorbent return monitoring sensor station 423 that provide data, status and feedback regarding operating parameters. The monitoring sensor station 422 is configured to monitor emissions flow levels, pressures, speeds, temperatures, and many other relevant parameters associated with the emissions control system. Based on the feedback information, some automatic adjustments may be made using programmable equipment, while other process and/or system parameters may require manual adjustments. The monitoring sensor 423 identifies the sorbent condition as the sorbent passes through one of the

outlets

403, 409, or 415 of the

subsystems

400, 401, or 402, respectively. The monitoring sensor station 423 is configured to monitor emissions flow levels, pressures, speeds, temperatures, and many other relevant parameters associated with the emissions control system.

Based on the feedback information, some automatic adjustments may be made using programmable equipment, while other process and/or system parameters may require manual adjustments. The monitoring sensor 423 identifies the sorbent condition as the sorbent passes through one of the

return ports

407, 414, or 420 of the

subsystems

400, 401, or 402, respectively, after cleaning and/or regeneration. The monitoring sensor station 424 (i.e., a second monitoring sensor) is configured to monitor emissions flow levels, pressures, speeds, temperatures, and many other relevant parameters associated with the emissions control system. Based on the feedback information, some automatic adjustments may be made using programmable equipment, while other process and/or system parameters may require manual adjustments. Monitoring sensor 424 monitors the condition and resulting volume of the adsorbent as it is processed in

stations

404, 410, or 416 within

subsystems

400, 401, or 402, respectively, as the cleaning and/or regeneration process occurs. The

monitoring sensors

421, 422, 423, 424 are configured to cooperate with each other and provide process condition and/or parameter adjustments to establish and maintain consistent and optimal sorbent efficiency at each station in the emissions control system. The sorbent within the

monitoring subsystems

400, 401, 402 will determine when and how much sorbent needs to be replenished from

stations

408, 413, and 419, respectively.

In another exemplary embodiment (not shown), the cleaning and/or regeneration subsystem is mounted and disposed within the interior of the fluidized bed 152. In this configuration, the functions of the

monitoring sensors

421, 422, 423, 424 and the

sorbent recirculation subsystems

400, 401, 402 occur inside the fluidized bed 152.

Still referring to fig. 33, when the fluidized bed 152 is filled with the reactive material 164 comprising CTZS adsorbent, the adsorbent treatment subsystem 400 is used to maintain optimal process conditions for the CZTS adsorbent. The sorbent discharge 403 allows for the transfer of sorbent into the sorbent processing station 404. The adsorbent treatment station 404 in subsystem 400 includes one or more chemical reagents that separate contaminants from the CZTS adsorbent as part of the cleaning and regeneration process. As a non-limiting example, the chemical reagents used in the sorbent processing station 404 may be selected from a group of fatty alcohols. Spent and/or depleted CZTS adsorbent may be processed through the adsorbent processing station 405. The exhaust pollutants removed from the exhaust may be recycled back to the various industries through the pollutant treating port 406. A batch refill station 408, such as a new/fresh sorbent vessel, provides a supplemental supply of CZTS sorbent to replace sorbent that has been removed and/or spent during the removal of contaminants from the effluent. The CZTS adsorbent return port 407 completes a closed loop back into the fluidized bed 152.

When the fluidized bed 152 is filled with the reactive material 164 comprising a CTZS alloy adsorbent, then the adsorbent treatment subsystem 401 is used to maintain the optimum process conditions for the CZTS alloy adsorbent. The sorbent discharge 409 allows for the transfer of sorbent into the sorbent processing station 410. The sorbent treatment station 410 in subsystem 401 includes one or more chemical reagents that separate contaminants from the CZTS alloy sorbent as part of the cleaning and regeneration process. As a non-limiting example, the chemical reagents used in the sorbent processing station 410 may be selected from a group of fatty alcohols. Spent and/or depleted CZTS alloy sorbent may be processed through a processing station 411. The exhaust pollutants removed from the exhaust may be recycled back to the various industries through the pollutant treating port 412. The batch refill station 413 provides a supplemental supply of CZTS alloy sorbent that replaces sorbent that has been removed and/or failed during the removal of contaminants from the effluent. The CZTS alloy sorbent return port 414 completes a closed loop back into the fluidized bed 152.

When the fluidized bed 152 is filled with the reactive material 164 comprising the carbon-based adsorbent, then the adsorbent handling subsystem 402 is used to maintain optimal process conditions for the carbon-based adsorbent. Sorbent discharge 415 allows for the transfer of sorbent into sorbent processing station 416. The adsorbent treatment station 416 in subsystem 402 includes one or more chemical reagents that separate contaminants from the carbon-based adsorbent as part of the cleaning and regeneration process. As non-limiting examples, the chemical agent used in the sorbent processing station 416 may be a solvent, such as methyl ethyl ketone, methylene chloride, and/or methanol. The spent and/or depleted carbon-based adsorbent may be treated by adsorbent treatment station 417. The exhaust pollutants removed from the exhaust may be recycled back into the various industries through the pollutant treating port 418. The batch refill station 419 provides a supplemental supply of carbon-based adsorbent that replaces adsorbent that has been removed and/or spent during the removal of contaminants from the effluent. The carbon-based adsorbent return port 420 completes a closed loop back into the fluidized bed 152.

According to an exemplary embodiment of the present disclosure, and as shown in fig. 33, the fluidized bed 152 may be a single unit having one or more

sorbent processing subsystems

400, 401, 402 configured for one or more sorbents. According to another exemplary embodiment (not shown), a plurality of fluidized beds 152 may be configured in series with one another, wherein each fluidized bed 152 is configured for one or more

sorbent processing subsystems

400, 401, 402. According to another exemplary embodiment (not shown), a plurality of fluidized beds 152 may be configured in parallel with one another, wherein each fluidized bed 152 is configured for one or more

sorbent processing subsystems

400, 401, 402.

Monitoring sensors

421, 422, 423, 424 are only some non-exhaustive examples of measurement devices that may be applied to an emissions control system. Those skilled in the art will appreciate that there may be many additional types of monitoring sensors located in many other stations of the emissions control system, which are not shown in the illustrated embodiment. The specific monitoring sensor for gaseous pollutant emissions may be different from the specific monitoring sensor for non-gaseous pollutant emissions. Similarly, the monitoring sensor required for one type of contaminant may be different from the monitoring sensor required for another contaminant.

In accordance with another aspect of the present disclosure, an emissions control method for removing pollutants from emissions is disclosed. The method as shown in fig. 33 comprises the steps of: directing the effluent into a processing system comprising a fluidized bed apparatus 152 in the shape of a reverse venturi, the fluidized bed apparatus containing one or more sorbents that chemically bond with the contaminants entrained in the effluent; and a fluidized bed apparatus 152 that directs the effluent away from the counter-venturi shape after the contaminants have bound to the sorbent. According to the method, the adsorbent is selected from the group comprising: copper Zinc Tin Sulfur (CZTS) adsorbents, Copper Zinc Tin Sulfur (CZTS) alloy adsorbents, and carbon-based adsorbents. The method further comprises the following steps: the sorbent is directed through one or more

sorbent processing subsystems

400, 401, 402 for cleaning and regeneration. The method comprises the following steps: separating spent and depleted sorbent from the sorbent directed through the

sorbent processing subsystem

400, 401, 402, treating the spent and depleted sorbent, separating contaminants from the sorbent directed through the

sorbent processing subsystem

400, 401, 402, treating or recycling the contaminants, and returning the recycled sorbent to the reverse venturi-shaped fluidized bed apparatus 152. Optionally, the method may comprise the steps of: fresh adsorbent is directed to a fluidized bed apparatus 152 in the shape of a reverse venturi to replace spent and depleted adsorbent.

In embodiments where the counter-venturi shaped fluidized bed apparatus 152 includes a plurality of

sorbent processing subsystems

400, 401, 402, the method may further comprise the steps of: the different sorbents in the fluidized bed apparatus 152 maintaining the inverse venturi shape are separated from each other, at least one process parameter of the fluidized bed apparatus maintaining the inverse venturi shape is detected with one or

more monitoring sensors

421, 422, 423, 424, the effluent is directed through one or more of the different sorbents based on the at least one process parameter detected by the

monitoring sensors

421, 422, 423, 424, and then the different sorbents are directed through different

sorbent processing subsystems

400, 401, 402 dedicated to processing the particular type of sorbent. For example, in the illustrated embodiment, a Copper Zinc Tin Sulfur (CZTS) adsorbent is directed through the first adsorbent treatment subsystem 400, a Copper Zinc Tin Sulfur (CZTS) alloy adsorbent is directed through the second adsorbent treatment subsystem 401, and a carbon-based adsorbent is directed through the third adsorbent treatment subsystem 402.

One type of carbon-based adsorbent, known as activated carbon, is typically made from a material such as coal or coke. Another type of carbon-based adsorbent, known as biochar, is typically made from one of many organic substances such as wood, sugar cane bagasse, coconut shells, and fruit shells. The manufacturing process for both activated carbon and biochar is a near complete combustion process, producing essentially pure elemental carbon. Biochar is more cost effective to manufacture than activated carbon because it can be produced in an oxygen deficient environment using any one or combination of a number of organic materials, a process known as pyrolysis. Pyrolysis is the process of thermal decomposition of materials at high temperatures in an inert and/or oxygen-deficient atmosphere. Activated carbon requires additional conversion energy beyond that required for biochar in order to convert coal and/or coke into a practical and usable form. The transformation of the chemical composition of the combustion mass is permanent and irreversible. The permanence and irreversibility resulting from the manufacturing combustion process of carbon-based sorbents is one of the primary reasons for the need for the cleaning, conditioning, and regeneration equipment and methods of use described herein.

One of the most desirable properties of a good adsorbent is surface area. The surface area in activated carbon and biochar is optimized by varying the combustion conditions to create pores at the carbon surface. The higher the percentage of pores in the carbon surface, the greater the surface area available for capturing contaminants. Typical activated carbon adsorbents typically have a surface area of 500 square meters per gram (m)²Per gram) to 1,500 square meters per gram (m)²Is/g). Typical biochar surface areas are typically 400 square meters per gram (m)²G) to 800 square meters per gram (m)²Is/g). However, there are very expensive, cost-prohibitive manufacturing processes that can produce up to 3,000 square meters per gram (m)²Per g) of activated carbon surface. Factors that affect the porosity of the carbon-based adsorbent are temperature, oxygen content in the combustion, degassing gases (such as steam), and the initial properties of the feedstock used in the combustion.

The treated carbon source also brings about other desirable effects, mainly an increase in adsorption of the target pollutants. Some of the more common surface treatments used to treat carbon surfaces are coating, impregnating and extruding activated carbon with metals. One metal commonly used is elemental ferrite (Fe). Additional process materials are chlorides or bromides of various metals, such as lead chloride (PdCl) and cuprous chloride (CuCl). These metals serve to increase the adsorption properties of most ionic contaminants. Ionic contaminants are often difficult to remove due to their oxidation states (such as Se being selenate, N being nitrate, Hg being oxide or chloride). Organic contaminants are easier to remove than inorganic contaminants, but industry is still seeking treatments to increase the absorption properties of adsorbents.

When a large portion of the surface area is exposed to contaminants, the carbon-based adsorbent becomes saturated. There is no known method of regenerating carbon-based sorbents such as activated carbon or biochar in the industry. There are industrial processes for partially cleaning or recovering activated carbon in a separate process, wherein contaminated activated carbon is placed in a furnace and some contaminants can be volatilized. Using this hearth combustion method can result in significant carbon losses between 10% and 20%. The carbon loss is due to the production of carbon dioxide (CO) during the volatile combustion of the furnace₂). The significant carbon loss during the furnace burnout must be replaced with a correspondingly large amount of replacement activated carbon.

The furnace combustion method for volatizing pollutants does not allow for the collection or capture of the volatized pollutants. In contrast, the present disclosure includes a sorbent processing subsystem 402 for cleaning, conditioning, and/or regenerating carbon-based sorbents. The cleaning and/or regeneration station 416 includes a treatment station 418, wherein contaminants that have been separated from the carbon-based adsorbent can be suitably treated and/or recycled back to a suitable industrial use.

Subsystem 402 may be configured to clean, condition, and/or regenerate the various carbon-based sorbents in station 416 because the process is effectively the same for most carbon-based sorbents. For example, the process for cleaning, conditioning and/or regenerating contaminated activated carbon is essentially the same as that required for biochar, except that the chemical reagents used to regenerate each product may be different because they absorb different contaminants.

The present disclosure for cleaning, conditioning, and/or regenerating activated carbon and/or biochar does not use the furnace burnout process as a function of subsystem 402 and station 416. Rather, the present disclosure includes cleaning, conditioning, and/or regeneration processes in which chemical agents remove contaminated semi-volatiles and contaminated volatiles. This is when no carbon dioxide (CO) is emitted₂) Is accomplished in a manner that is not possible with hearth combustion processes. Since the cleaning, conditioning, and/or regeneration process of the present disclosure does not emit carbon dioxide (CO)₂) What is, what isThe loss of carbon-based sorbents is less than 2%, which is well below the 10% to 20% carbon loss experienced using the furnace firing process.

Furthermore, known furnace combustion processes for cleaning carbon-based sorbents are primarily limited to activated carbon sorbents. There is no known process for cleaning the biochar adsorbent. The use of a furnace combustion process can also negatively impact the surface area of the carbon-based sorbent, especially without monitoring and accurately controlling furnace conditions. If the furnace combustion process is perfectly carried out, the resulting surface area of the contaminated carbon-based adsorbent will be improved compared to the remaining surface area in the contaminated state. However, the resulting surface area of the carbon-based sorbent after the furnace combustion process can be significantly reduced compared to the original surface area prior to first use.

The present disclosure utilizes the contact time created by the tortuous path of the fluidized bed apparatus 152 to collect the contaminants, and then utilizes the additional contact time created by the tortuous path in station 416 to clean, condition, and/or regenerate the adsorbent and separate the contaminants. The longer the contaminated sorbent remains in subsystem 402, the more contaminants are separated and the cleaner, better conditioned and/or more viable the sorbent becomes.

Referring to fig. 34, a block diagram depicting method steps for cleaning, conditioning, and/or regenerating a carbon-based adsorbent is shown. Such chemical cleaning, conditioning and regeneration processes do not involve a furnace combustion process for cleaning the carbon-based sorbent. Instead, one or more sorbent processing subsystems 402 containing one or more chemical reagents are used. Thus, the original surface area of the carbon-based adsorbent can be restored using the disclosed chemical cleaning process. Tests have shown that passing fresh, unused carbon-based adsorbent through subsystem 402 and method step 500 prior to initial exposure to contaminants can increase the surface area of the carbon-based adsorbent above that produced by the combustion process initially used to make the carbon-based adsorbent. This is especially true for biochar.

Referring to fig. 33 and 34, the contaminated carbon-based adsorbent enters the adsorbent treatment subsystem 402 and station 416 in method step 501, where it is chemically treated in method step 502Reagents such as heated solvent sprays. The heated solvent is recycled in method step 503 for at least 45 minutes. The heated solvent chemically removes the contaminants from the carbon-based adsorbent. Tests show that the optimum effective temperature range of the heated solvent is 125 degrees Celsius (C.) to 145 degrees Celsius (C.), the lower effective temperature limit is at least 5 degrees Celsius (C.) above ambient temperature, and the upper effective temperature limit is 210 degrees Celsius (C.). An effective lower temperature limit of approximately 5 degrees celsius (c) above ambient temperature requires an extended contact time for the solvent to separate the contaminants from the adsorbent. By passing through a nitrogen atmosphere (N)₂) And heating the solvent in vacuo under an argon (Ar) environment, an effective upper temperature limit of approximately 210 degrees celsius (° c) can be achieved. The solvent used in method step 502 may include, but is not limited to, methyl ethyl ketone, methylene chloride, or methanol.

After the heated solvent is recycled for a sufficient period of time in method step 503, the contaminants are removed from the carbon-based adsorbent in method step 504, which causes the carbon-based adsorbent to be separated from the solvent saturated with contaminants in method step 505. Next, the carbon-based adsorbent is rinsed with hot water in method step 506. Tests show that the optimal effective temperature range of the heated water is 63 degrees centigrade (DEG C) to 83 degrees centigrade (DEG C), the lower limit of the effective temperature is 5 degrees centigrade (DEG C) higher than the ambient temperature, and the upper limit of the effective temperature is 98 degrees centigrade (DEG C).

The cleaned, conditioned, and/or regenerated carbon-based adsorbent is separated from any spent carbon-based adsorbent in method step 507, wherein the cleaned, conditioned, and/or regenerated carbon-based adsorbent is recycled through station 420 in method step 508, and returned to fluidized bed apparatus 152 in method step 509. Spent carbon-based adsorbent is treated in method step 510 by station 417. Spent and/or spent carbon-based adsorbent is replaced with fresh carbon-based adsorbent in method step 511 by station 419.

As shown in method step 512, the solvent saturated with the contaminants chemically removed from the carbon-based adsorbent in method step 505 is recovered using a distillation process. The recovered solvent is recycled in process step 514. The spent solvent is treated in method step 513. The separated contaminants, along with the unusable contaminants treated in method step 516, and the usable contaminants recycled in method step 517, are passed through station 418 in method step 515.

It is to be understood that other adsorbents, such as CZTS, CZTS alloys, and/or other adsorbents such as particulate iron oxide zeolites, may be cleaned, conditioned, and/or regenerated by passing the contaminated adsorbent through a subsystem similar to 400 and/or 401. The process steps and basic processes for cleaning these other sorbents are similar to process step 500, but with some minor differences in the chemicals used. For example, some of the chemical differences in CZTS adsorbents and CZTS alloy adsorbents require the use of hot aliphatic alcohols as solvents/chemicals. In addition, different equipment may be used to allow the CZTS adsorbent and CZTS alloy adsorbent to be cleaned, conditioned and/or regenerated. For example, a rotary vacuum dryer can be used to volatilize contaminants and capture them in a scrubber system.

It should be understood that although the steps of the method are described and illustrated herein in a particular order, the steps may be performed in a different order without departing from the scope of the present disclosure unless the order of the steps is otherwise indicated. Likewise, it is understood that the methods described and illustrated herein may be performed without the inclusion of all of the steps described above or the addition of intervening steps not discussed, all without departing from the scope of the present disclosure.

Many modifications and variations of the present disclosure are possible in light of the above teachings and may be practiced otherwise than as specifically described within the scope of the appended claims. These should be construed to cover any combination of the novelty of the present invention which finds its utility. The use of the word "said" in the device claims refers to a precondition that it is a positive recitation intended to be included in the scope of the claims, whereas the word "the" preceding it is not intended to be included in the scope of the claims.

Claims

1. An emissions control system comprising a fluidized bed apparatus for removing contaminants from emissions, the fluidized bed apparatus comprising:

a housing in the shape of an inverted venturi, the housing including an inlet portion for receiving the emissions at a predetermined inlet flow rate, an outlet portion for discharging the emissions at a predetermined outlet flow rate, and an enlarged portion disposed between the inlet portion and the outlet portion of the housing for trapping the contaminants in the emissions;

the inlet portion, the outlet portion, and the enlarged portion of the housing are arranged in fluid communication with one another;

a mass of reactive material disposed within the enlarged portion of the housing;

the mass of reactive material having a reactive outer surface disposed in contact with the effluent, the mass of reactive material comprising a carbon-based sorbent; and

at least one sorbent treatment subsystem disposed in fluid communication with the housing of the fluidized bed apparatus, the at least one sorbent treatment subsystem comprising a solvent for separating the contaminants from the carbon-based adsorbent after exposure of the carbon-based adsorbent to the emissions.

2. The emissions control system of claim 1, wherein the at least one sorbent processing subsystem is internal to the housing of the fluidized bed apparatus.

3. The emissions control system of claim 1, wherein the at least one sorbent processing subsystem is external to the housing of the fluidized bed apparatus.

4. The emissions control system of claim 1, wherein the at least one sorbent processing subsystem comprises an inlet for receiving contaminated sorbent from the housing of the fluidized bed apparatus, a cleaning and regeneration station, a sorbent processing station, a contaminant processing station, a batch refill station, and a return port for returning cleaned sorbent to the housing of the fluidized bed apparatus.

5. The emissions control system of claim 1, wherein the solvent comprises at least one of methyl ethyl ketone, methylene chloride, and methanol.

6. The emissions control system of claim 1, wherein the at least one sorbent processing subsystem is configured to heat the solvent to a temperature within an optimal effective temperature range of 125 degrees celsius to 145 degrees celsius.

7. The emissions control system of claim 1, wherein the at least one sorbent processing subsystem is configured to heat the solvent to a temperature at least 5 degrees celsius and no greater than 210 degrees celsius above ambient temperature.

8. The emissions control system of claim 1, wherein the at least one sorbent treatment subsystem comprises water for rinsing the carbon-based sorbent to separate the carbon-based sorbent and the solvent containing contaminants.

9. The emissions control system of claim 8, wherein the at least one sorbent treatment subsystem is configured to heat the water to a temperature within an optimal effective temperature range of 63 degrees celsius to 83 degrees celsius.

10. The emissions control system of claim 8, wherein the at least one sorbent treatment subsystem is configured to heat the water to a temperature at least 5 degrees celsius and no greater than 98 degrees celsius above ambient temperature.

11. The emissions control system of claim 1, wherein the at least one sorbent treatment subsystem does not include a furnace firing station.

12. The emissions control system of claim 1, wherein the at least one sorbent treatment subsystem does not emit carbon dioxide during cleaning and regeneration of the carbon-based sorbent.

13. The emissions control system of claim 1, wherein the carbon-based adsorbent comprises at least one of activated carbon and biochar.

14. An emissions control system comprising a fluidized bed apparatus for removing contaminants from emissions, the fluidized bed apparatus comprising:

a quantity of reactive material disposed within the enlarged portion of the housing;

at least one adsorbent treatment subsystem comprising a solvent for treating the carbon-based adsorbent prior to exposure of the carbon-based adsorbent to the emissions.

15. The emissions control system of claim 14, wherein the solvent chemically interacts with the carbon-based adsorbent and increases the porosity of the reactive outer surface of the quantity of reactive material.

16. An emissions control method for removing pollutants from emissions, comprising the steps of:

directing the effluent through at least one prefilter containing a prefilter sorbent;

directing the effluent from the at least one pre-filter and into a processing system having a reverse venturi-shaped fluidized bed apparatus containing reactive material that chemically bonds with the contaminants entrained in the effluent;

selecting a carbon-based adsorbent as the reactive material in the reverse venturi-shaped fluidized bed apparatus;

trapping the contaminants in the reactive material contained in the reverse venturi-shaped fluidized bed apparatus; and

directing the carbon-based adsorbent through at least one adsorbent treatment subsystem containing a solvent that cleans and conditions the carbon-based adsorbent.

17. The method of claim 16, further comprising the steps of:

heating the solvent in the sorbent processing subsystem; and

spraying a heated solvent onto the carbon-based adsorbent to clean and condition the carbon-based adsorbent.

18. The method of claim 17, wherein the solvent is heated to a temperature within an optimal effective temperature range of 125 degrees celsius to 145 degrees celsius.

19. The method of claim 17, wherein the solvent is heated to a temperature at least 5 degrees celsius and no greater than 210 degrees celsius above ambient temperature.

20. The method of claim 17, further comprising the steps of:

recycling the heated solvent in the sorbent treatment subsystem for at least 45 minutes.

21. The method of claim 16, further comprising the steps of:

rinsing the carbon-based adsorbent in the adsorbent treatment subsystem with water to clean the carbon-based adsorbent.

22. The method of claim 21, further comprising the steps of:

heating the water in the sorbent processing subsystem to a temperature within an optimal effective temperature range of 63 degrees Celsius to 83 degrees Celsius.

23. The method of claim 21, further comprising the steps of:

heating the water in the sorbent processing subsystem to a temperature at least 5 degrees Celsius above ambient temperature and no greater than 98 degrees Celsius.

24. The subsystem of claim 16, further comprising the steps of:

separating the spent carbon-based adsorbent from the clean carbon-based adsorbent;

treating the spent carbon-based adsorbent; and

directing the cleaned sorbent back to the counter-venturi shaped fluidized bed apparatus.

25. The method of claim 24, further comprising the steps of:

replacing the spent carbon-based adsorbent with a new carbon-based adsorbent and directing the new carbon-based adsorbent to the reverse venturi-shaped fluidized bed apparatus.

26. The subsystem of claim 16, further comprising the steps of:

separating the contaminants from the solvent using a distillation process and recycling the solvent.