CN110755998B

CN110755998B - Emission control systems using CZTS, CZTS-based alloys, and/or carbon-based sorbents and methods of use

Info

Publication number: CN110755998B
Application number: CN201910668184.1A
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 Technologies LLC
Current assignee: Chemical And Metal Technologies LLC
Priority date: 2018-07-23
Filing date: 2019-07-23
Publication date: 2023-05-02
Anticipated expiration: 2039-07-23
Also published as: CN110755998A; JP7281354B2; JP2020037098A

Abstract

An emission control system for gaseous and non-gaseous pollutant emissions is disclosed that includes a fluidized bed apparatus containing a reactive sorbent material. The reactive sorbent material may be CZTS, CZTS alloy or carbon-based sorbent material. The fluidized bed apparatus is configured with one or more closed loop sorbent recirculation subsystems. The sorbent recirculation subsystem includes the following functions: the adsorbents are separated from each other, the adsorbents are separated from contaminants for treatment and/or recycling, the adsorbents are cleaned and/or regenerated for return to the fluidized bed apparatus, the spent and spent adsorbents are treated, and the spent and spent adsorbents are replaced with fresh adsorbents to maintain consistent adsorbent function of the fluidized bed apparatus. The monitoring sensor provides useful information in methods for establishing and maintaining consistent process parameter control.

Description

Emission control systems using CZTS, CZTS-based alloys, and/or carbon-based sorbents and methods of use

Cross Reference to Related Applications

This application is a partial continuation-in-process application of U.S. patent application Ser. No. 15/606,704, filed on 5, 26, 2017, which is a partial continuation-in-process application of U.S. patent application Ser. No. 14/808,563, filed on 24, 2015, 7, which claims the benefit of U.S. provisional application Ser. No. 62/029,044, filed on 25, 7, 2014, and U.S. provisional application Ser. 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, which is not necessarily prior art.

Many industries in many economic sectors have this or that emission. Such emissions can be divided into two basic groups, one being gaseous and the other being non-gaseous. Emissions in gaseous and non-gaseous species typically contain hazardous contaminants. Emissions in the gaseous train may be in the form of exhaust gases 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 slurry materials. If the level of harmful contaminants in the emissions reaches and/or exceeds the allowable limit, the contaminants must be neutralized, captured, collected, removed, disposed of, and/or properly sequestered by one or more of these methods.

Many industries rely on burning fuels as a method of accomplishing some aspects of their respective processes. For example, in a first example, a steelworks burns and/or smelts metal during the manufacture of metal shapes, extrudates and other metal castings. Processes used in the metal industry include operations in which particles are emitted as metal vapors and ionized metals. Contaminants harmful to the environment, plants, animals and/or humans are released into the air via the metal vapor. To some extent, the metal vapors and/or hazardous contaminants in the metal vapor compounds must be properly collected and disposed of. In a second example, industries that mine precious metals such as gold, silver, and platinum include metal and metal vapor emissions that contain heavy metal contaminants and particulates that are considered detrimental if not captured, collected, and properly disposed of. In a third example, the emissions of the natural gas burning industry typically contain relatively high levels of contaminants that are considered harmful if they are not captured, collected, and properly disposed of. In a fourth example, energy manufacturers using coal as a combustible consumable to produce steam in boilers for rotating electric generators have considerable emissions, which contain metal vapors and metal compounds that are considered harmful to the environment, plants, animals, and humans. Among other hazardous contaminants, metal vapor emissions typically contain mercury (Hg).

Due to the global jet pattern, 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 being deposited in the united states and/or the sea water therebetween. In a similar manner, many mercury-containing emissions produced in the united states may actually be deposited in europe and/or the sea water therebetween. To accomplish this, many mercury-containing emissions produced in europe may actually be deposited in china and/or india. Thus, the sequestration of mercury and other harmful pollutants in emissions from industrial processes is a global problem with global applications, which requires global effort to address.

National and international regulations, costs, monitoring and a series of ever-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 is as high as 1,960 metric tons per year worldwide. The number is calculated from the data analyzed in 2010. Worldwide, the largest contributors to this particular type of emissions are coal (24%) and gold mining (37%) activities. In the united states, the proportion of emissions from coal burning is higher than in gold mining activities.

The main problem of animal and human exposure to mercury is that it is a bioaccumulative substance. Thus, any amount of mercury ingested by a fish or other animal will remain in the animal (i.e., accumulate) and will be transferred to a human or other animal when the fish or other animal is ingested by the human or other animal. In addition, mercury is not expelled from the body of the ingestion subject. In the food chain, the longer-to-live and/or larger predators that eat large numbers of other animals have the greatest risk of accumulating excess mercury. Humans eating too much mercury-containing animals, particularly fish, experience a variety of well-known medical problems, including neurological diseases and/or reproductive problems.

There are three main types of mercury emissions: artificial emissions, re-emissions, and naturally occurring emissions. The artificial emissions are mainly the result of industrial activities. The artificial emission sources include industrial coal burning plants, natural gas burning facilities, cement manufacturing plants, oil refining facilities, chlor-alkali industry, vinyl chloride industry, mining operations and smelting operations. Re-emissions can occur when mercury deposited in the soil is re-dispersed via floods or forest fires. Mercury absorbed in the soil and/or deposited in the soil may be released into the water back via stormwater runoff and/or flooding. Thus, soil erosion contributes to this problem. Forest fires, whether natural disasters, fires or deliberate deforestation, can re-expel mercury back into the air and/or water source, and can only be redeposited 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 described above, coal-fired plants release large amounts 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 burning plants in the united states are equipped with emissions control systems that capture, sequester, and/or recover harmful elements, such as mercury. In coal-fired plants, coal is combusted to boil water, turning the water into steam for operating an electric generator. The flue gas emissions from the combustion of coal are typically conveyed through a conduit 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 gas ₂ ) And hydrogen chloride (HCl). A typical duct system then directs the flue gas stream to a wet or dry scrubber where more sulfur dioxide, hydrogen chloride, and fly ash are removed. The flue gas flow is directed through a baghouse where particles are separated from the flow of gas in the flue gas, similar to the way a household vacuum cleaner bag works. The flue gas passes through a filter-like bag having holes that allow the flow of gas but do not allow the passage of larger particles flowing in the flow. Shaking and/or cleaning filtration The surface of the bag is used to collect the captured particles so that they can be handled. Often, these deposits are themselves harmful emissions and must therefore be treated. The remaining flue gas passing through this type of emission control system is then allowed to escape through the high stack and be released into the atmosphere.

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

In order 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, which generally fall into one of three categories.

The first category is a set 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 noble metals, are activated carbon and/or biochar. Activated carbon is typically halogenated with bromine. Biochar is a form of charcoal rich in carbon. Injecting sorbent into the flue gas helps capture contaminants 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 injection of activated carbon at various points of the emissions control system after combustion of the coal. Some exemplary methods and/or systems of the first class 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 category is a set of methods and/or systems for pretreating the coal prior to combustion of the coal in an effort to reduce mercury levels in the coal. Some exemplary methods and/or systems of the second class 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 presented in these exemplary patents produce large amounts of unusable coal, which is also considered hazardous waste. Thus, the methods and/or systems of the second known type are inefficient and expensive to operate. In addition, pretreatment of coal typically requires a significant amount of capital and physical space, and thus it is impractical to retrofit many existing emission control systems with the necessary equipment.

The third category is a set of methods and/or systems for injecting catalyst into an emissions control device upstream of an activated carbon injection system. The catalyst in these methods and/or systems ionizes mercury, making it easier to collect and remove from flue gases. However, these methods and/or systems are inefficient and costly to operate, making the methods and/or systems of the third class of known schemes not cost-effective. Examples of the third class 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 adsorbent materials by using microwaves and fluidized bed reactors. The method selectively evaporates mercury from the sorbent, where it can be captured in a special filter or condensed and collected. The use of microwave generation makes the process impractical for large-scale commercial applications and therefore is only used for the regeneration of expensive adsorbents. Another example is found in U.S. patent application publication No. 2006/0120925, which discloses a method of: any of several matrix materials are used to create a chemical attraction to mercury as the flue gas passes through the emission control device, thereby removing mercury from the flue gas. This approach is also impractical for large-scale commercial use. Accordingly, current emission control systems and methods generally 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 are concerned with metal vapor emissions, other forms of emissions containing hazardous contaminants, such as mud and/or slurry-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 treatment, 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 process for removing hazardous contaminants utilized activated carbon (in one form or another) through which the emissions were passed. Thus, by 2017, the demand for activated carbon in the united states is expected to grow annually, requiring over 10 hundred million pounds per year, and industrial costs of over $1 to $1.50 per pound per year. This amounts to about $10 billion per year. The growing demand for activated carbon is expected to be due in large part to the enforcement of EPA-issued regulations that require utilities and industrial manufacturers to upgrade coal-fired power plants to meet increasingly stringent requirements.

In addition to more stringent gas emission regulations, the EPA has imposed more stringent regulations on non-gaseous emissions by the clean Water Act (The Clean Water Act), which must be fully adhered to by 2016 years ago. The combination of ever-increasing regulations for all types of emissions can affect the types of emissions produced by a variety of different industries. Some industries, such as power producers that burn fuel to generate electricity, produce primary gaseous emissions that contain harmful pollutants. According to industry standards, these gaseous emissions are exposed to activated carbon materials, which strive to capture sufficient amounts of harmful contaminants such that the gaseous emissions are at or below the allowable limits of the contaminants. The process of removing harmful contaminants from gaseous emissions resulting from the combustion of these fuels results in and/or produces secondary non-gaseous emissions in the form of liquid or slurry materials containing the harmful contaminants. Harmful contaminants in the secondary non-gaseous emissions must also be properly captured and/or sequestered to prevent the emission of harmful contaminants into the environment. Both primary gaseous emissions and secondary non-gaseous emissions require means to adequately capture and/or recover and/or limit enough harmful contaminants to comply with environmental regulations. The industrial costs associated with the known available methods of accomplishing the removal of harmful contaminants from secondary non-gaseous emissions are almost cost prohibitive, such that some industries are forced to shut down the facility if they cannot pass costs to the consumer.

According to some practices, non-gaseous emissions are considered detrimental because they contain higher levels of contaminants, which are discarded and sequestered for long term storage in a pool, stack, or dry bed. 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 contaminated area. One example of a non-gaseous emission is fly ash, which is a natural product from the combustion of coal. The composition of fly ash is essentially the same as pozzolan. 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 up to 10% of the coal burned in the united states is composed of non-combustible materials that become ash. As a result, the concentration of harmful trace elements in the coal ash is 10 times higher than those in the raw coal.

Fly ash is considered a pozzolanic material and has long been used 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 dust, which consists of very fine particles that rise with the flue gas. The ash that does not rise is commonly referred to as bottom ash. Early in the coal-fired plant, 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, an electrostatic precipitator is used to capture the fly ash before it can reach the stack and be discharged to the atmosphere. Typically, the bottom ash is mixed with the captured fly ash to form so-called fly ash. Typically, fly ash contains higher levels of hazardous contaminants than bottom ash, which is why bottom ash is mixed with fly ash such that the proportion level of hazardous contaminants meets most non-gaseous emission standards. However, future standards may reclassify fly ash as a hazardous material. Fly ash, if reclassified as a hazardous material, would 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 in the united states alone increases by over $50 billion per year due to the banning of fly ash in concrete production. The increase in cost is a direct result of using more expensive replacement materials instead of fly ash. Furthermore, due to their unique physical properties, no other known materials are suitable as a direct replacement for fly ash in cement.

Reports indicate that more than 1.3 billion tons of fly ash are produced annually in the united states by 450 coal-fired power plants. Some reports estimated that only 40% of this fly ash was reused, indicating that up to 5200 tens of thousands of tons of fly ash can be reused each year, leaving batches of up to 7800 tens of thousands of tons of fly ash per year stored in the slurry pond and pile. Fly ash is typically stored in wet slurry 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 to the surrounding environment. In addition to the airborne mass of stored fly ash, the long term storage systems required to store fly ash present a threat of damage and/or failure. In 2008, a well-known damage case occurs in tennessee, and a dam of a wet storage fly ash pond collapses, causing 540 ten thousand cubic yards of fly ash to leak. Leakage damages several houses and contaminates nearby rivers. At the time of this application, the cleaning costs are still on the order of dollars, perhaps over 12 hundred million.

In another example, the non-gaseous emissions may be as a byproduct in a typical wastewater production system of a coal burning facility. In a typical wastewater generation system, a large amount of water comes from the boiler discharge and cooling water process. These large amounts 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, which is typically discharged from the scrubber system, is diluted with a large amount of wastewater from the boiler discharge and/or cooling water process, and then treated in a large continuous mixing tank containing lime to form gypsum, which is then pumped into a settling tank. During this process, a certain amount of mercury and other heavy metals are entrained in the gypsum and stabilized for wallboard and cement. Such gypsum is generally considered non-leaching and is not considered a pollution hazard. However, water from the settling pond is typically discharged into the waterway. Current regulations allow for such sustained emissions, but the pressing regulations suggest that certain pollutants and/or the levels of these pollutants are forced to act as harmful pollutants.

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

Another source of contaminated non-gaseous emissions is marine vessel waste emissions and/or ballast emissions. Commercial vessels such as cargo ships and tankers have both waste and ballast emissions. Recreational mail wheels also have effluent at harbor sites to be treated. In addition, military and defense vessels have a large volume of discharged sewage.

Offshore drilling operations create another type of drainage that is notable. On-site sewage waste treatment on offshore rigs is much cheaper than transporting the waste to land for treatment. Therefore, it is necessary to effectively filter the offshore waste before it is discharged to the ocean to maintain proper and acceptable ecological requirements. Almost all contaminated emissions vary in the type of contaminant and/or the specific concentration of the contaminant in the emissions. Thus, a one-cut process for a suitable adsorbent optimized for all possible pollutant emissions applications is not possible. There is a need to provide an application specific sorbent solution for optimizing effective emission control based on specific pollutants in the emissions. There is also a need to be able to adjust the sorbent application during use to correspond to changes in the level and/or type of contaminants remaining in the emissions.

There are also various known commercial emission 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, commercially available under the trade name MERSORB-LW, uses a particulate coal-based absorbent to remove mercury from secondary non-gaseous emissions by co-precipitation and absorption. Another treatment method 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 a porous cellulose support modified with polyethylenimine 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, commercially available as 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 contaminant in the effluent exceeds the allowable level, instead of removing the contaminant to reduce the level, an additional uncontaminated volume is added to the effluent such that the resulting PPM level is reduced to the allowable level, although the allowable actual amount of contamination remains unchanged. There is an urgent need to overcome this dilution by providing an effective emission control method that not only reduces the PPM level of contaminants, but also removes contaminants from the emissions.

Disclosure of Invention

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

In accordance with one aspect of the present disclosure, an apparatus for removing contaminants from emissions is disclosed. The device comprises a housing shaped as a reverse venturi. 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. Depending on the reverse venturi shape of the housing, the enlarged portion cross-sectional area is greater than the inlet portion cross-sectional area and the outlet portion cross-sectional area. Due to this geometry of the housing, the emissions entering the enlarged portion of the housing slow down and pass through the enlarged portion of the housing at a lower velocity relative to the velocity of the 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 increases.

The device also includes a quantity of reactive material including one or more sorbents disposed within the enlarged portion of the housing. A number of reactive materials have reactive outer surfaces that are disposed in contact with the emissions. In addition, a significant amount of the reactive material contains an amalgam-forming metal at the reactive outer surface. The amalgam-forming metal in the volume of reactive material chemically bonds with at least some of the contaminants in the emissions that pass through the enlarged portion of the housing to the reactive outer surface of the volume of reactive material. One or more sorbent recirculation subsystems are disposed in fluid communication with the housing. Each sorbent recycling subsystem receives sorbent from the housing via a sorbent discharge port and returns cleaned sorbent to the housing via a sorbent return port. The sorbent recycling subsystem includes a chemical reagent for separating contaminants from the sorbent in a cleaning and regeneration process before the cleaned sorbent 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: directing the effluent into a treatment system comprising a reverse venturi-shaped fluidized bed apparatus comprising one or more adsorbents chemically bound to contaminants carried in the effluent; and directing the effluent away from the inverted venturi shaped fluidized bed apparatus. According to the method, the adsorbent is selected from the group comprising: copper Zinc Tin Sulfide (CZTS) adsorbents, copper Zinc Tin Sulfide (CZTS) alloy adsorbents, and carbon-based adsorbents. The method further includes the step of directing the sorbent through one or more sorbent recirculation subsystems for chemical cleaning and regeneration.

It is important to maintain optimal process conditions for the adsorbent used to remove the polluting emissions from the reverse venturi-shaped fluidized bed apparatus. Thus, the adsorbent is directed from the reverse venturi-shaped fluidized bed apparatus and into the adsorbent recirculation subsystem. The sorbent recirculation subsystem is designed to clean and/or regenerate the sorbent to optimal conditions prior to returning the sorbent to the reverse venturi-shaped fluidized bed apparatus. The sorbent recycling subsystem is also designed to separate and direct spent and depleted sorbent from the remainder of the sorbent that can be cleaned and/or regenerated, to treat the spent and depleted sorbent. The sorbent recycling subsystem is also designed to separate captured contaminants from the sorbent for recycling in various industries or for proper disposal if no recycling option is available. The sorbent recycling subsystem is further designed to replenish and/or replace the sorbent that has been separated for disposal and/or that has been consumed during normal operation for removing contaminants from contaminated emissions.

In accordance with another aspect of the present disclosure, the sorbent recirculation subsystem includes one or more monitoring sensors that provide continuous on-line testing and monitoring feedback to maintain constant and consistent optimal sorbent conditions. One exemplary embodiment of the present disclosure provides at least three separate locations in which three separate sorbent recirculation subsystems are installed and configured. The first sorbent recirculation subsystem location is provided to the CZTS sorbent. The second sorbent recirculation subsystem location is provided to the CZTS alloy sorbent. The third sorbent recycling subsystem location is provided to the carbon-based sorbent. Specific emissions requirements may dictate which adsorbent recovery subsystem is particularly desirable. Depending on the level of contaminants in the reverse venturi's fluidized bed apparatus, the reverse venturi's fluidized bed apparatus may be configured to use all three sorbent recirculation subsystems, not to use the sorbent recirculation subsystem, or multiple facilities of the same sorbent recirculation subsystem may be arranged at multiple locations along the reverse venturi's fluidized bed apparatus and used simultaneously.

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

The reverse venturi-shaped fluidized bed apparatus may be of a specific size with a length to diameter ratio to provide an optimal restrictive residence time for the effluent as it passes through the specific adsorbent contained in the apparatus. Through 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 preferred is 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 the predominantly circular outwardly projecting male ends 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 in contact with adsorbent) is maximized because the flow of effluent turns randomly on itself, minimizing cavitation turbulence, thereby increasing maximized intimate contact. The predominantly circular outwardly projecting male ends provide a relatively smooth return flow at both ends of the fluidized bed apparatus and the cavitation turbulence of the effluent is minimized. Cavitation turbulence through filters is known to impede and/or disrupt flow. There is a need to extend the residence time in and through the fluidized bed apparatus to optimize contaminant capture and removal from the effluent; however, if the flow is cavitation turbulence, the extended residence time is not optimized. A variety of baffles and/or other application specific flow restriction barriers may be incorporated into the housing of the fluidized bed apparatus.

In accordance with another aspect of the present disclosure, an exemplary contaminant removal system is provided with a reconfigurable segmented component. Each system component may be isolated, bypassed, combined, and/or reconfigured to meet the requirements of a particular application.

In accordance with another aspect of the present disclosure, an emissions control system includes a plurality of reactive sorbents in a fluidized bed apparatus, including Copper Zinc Tin Sulfide (CZTS) sorbents, CZTS alloy sorbents, and/or carbon-based sorbents. The fluidized bed apparatus also has additional ports to clean and/or replace the adsorbent material. The plurality of sorbent recirculation subsystems disclosed herein provide methods for CZTS sorbents, CZTS alloy sorbents, and/or carbon-based sorbents. The example emission control system may also include one or more pre-and/or post-filters that contain a quantity of reactive sorbent. The prefilter and postfilter may be connected in parallel or in series with the fluid bed apparatus, depending on the specific requirements of the application.

Emissions contaminants from industrial applications include: hg (mercury), as (arsenic), ba (barium), cd (cadmium), cr (chromium), cu (copper), pb (lead), sn (tin), P (phosphorus), NO ₂ (Nitrogen dioxide, NO) ₃ (nitrate salt), NH ₃ (ammonia). Long lists of contaminants eliminate the ability to have a one-shot emission control scheme. Furthermore, an emission control scheme that may be active on one contaminant in a gaseous emission may not be active on the same contaminant in a non-gaseous emission Effectively, and vice versa.

International standards and regulations, federal standards and regulations, state standards and regulations, and local standards and regulations set various levels of Parts Per Million (PPM) allowable for 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 gaseous emissions as compared to non-gaseous emissions.

Testing the contaminated emissions may be conducted spot checks and/or use continuous on-line monitoring equipment to determine the type and level of contaminants present in the emissions. Depending on the test results, specific pre-and/or post-filters may be selected to direct the polluting emissions. Each pre-filter and/or post-filter contains a specific mass of reactive adsorbent as a broad spectrum treatment option for specific contaminants 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 on-line monitoring provides the ability to adjust the selection of particular pre-and/or post-filters to optimally correspond to the particular pollutants present in the emissions at any given time during the flow of the emissions.

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

In addition to permanent installation 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 railcar systems. By providing temporary bypass for emissions, transportable system applications are useful to provide bypass for field construction systems so that permanent field construction systems can be serviced, inspected, and/or repaired. The transportable system can also be used to provide additional filtering capability for permanent field construction devices when the flow of 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. In general, the sorbents improve the capacity of the disclosed emission device to better capture, sequester, and/or recycle mercury and other hazardous materials with efficiencies not previously possible using known emission control systems and methods. Another significant benefit of the adsorbents disclosed herein is that the adsorbents can be used to treat both gaseous and non-gaseous emissions, thereby overcoming many of the drawbacks 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 adsorbents described herein provide improved capacity to treat gaseous emissions sufficiently effectively to prevent the need for secondary treatment of non-gaseous emissions produced as a by-product of the primary gaseous emissions treatment process. The adsorbent disclosed herein is also beneficial in that it is reusable. By the regeneration process, the detrimental contaminants that chemically bond with the amalgam-forming metal in the adsorbent can be collected (i.e., removed) from the adsorbent, thereby restoring the adsorbent's ability 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 illustrating 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 emission control system shown in FIG. 2, wherein the emission 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 the 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 the 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, wherein a series of staggered baffles are disposed in an enlarged portion of a housing creating a serpentine flow path for emissions;

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 a housing creating a helical flow path for emissions;

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 in accordance with the present disclosure with a plurality of spaced baffles disposed in an enlarged portion of a housing;

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

FIG. 8 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the present disclosure, wherein a plurality of segments are 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, wherein a plurality of intertwined lines are disposed in an enlarged portion of the housing, forming a fleece-like material therein;

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

FIG. 11 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with 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 to replace the segments shown in the exemplary reverse venturi device shown in FIGS. 8 and 11;

fig. 13B is a front view showing one exemplary crystal wafer that may be used in combination with other crystal wafers to replace the fragments shown in the exemplary reverse venturi apparatus shown in fig. 8 and 11.

FIG. 13C is a front view showing one exemplary coil that in combination with other coils may be used 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 in accordance with the present disclosure including two separate serially connected enlarged portions;

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

FIG. 16 is a side cross-sectional view illustrating another exemplary reverse venturi apparatus constructed in accordance with the present disclosure.

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

FIG. 18A is a block diagram illustrating a method for removing contaminants from the gaseous effluent shown in FIG. 17, wherein the method is modified by adding the step of injecting an adsorbent into the gaseous effluent at a first point of introduction and subsequently passing the gaseous effluent through a reverse venturi apparatus;

FIG. 18B is a block diagram illustrating a method for removing contaminants from the gaseous effluent shown in FIG. 17, wherein the method is modified by adding the step of injecting an adsorbent into the gaseous effluent at a second point of introduction and subsequently passing the gaseous effluent through a reverse venturi apparatus;

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

FIG. 20 is a block diagram illustrating a method for removing contaminants from the non-gaseous effluent shown in FIG. 19, wherein the method is modified by the addition of a step of treating a portion of the non-gaseous effluent extracted from the settling tank with an adsorbent;

FIG. 21 is a graph illustrating the percentage of contaminants removed from an emission by a known emission control system and the percentage of contaminants removed from an emission by the apparatus and methods disclosed herein;

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

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

FIG. 24 is a flow chart illustrating an extended non-turbulent effluent stream through an exemplary reverse venturi-shaped fluidized bed apparatus and exemplary method steps for cleaning and recirculating an adsorbent separating contaminants from the effluent;

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 a housing of the reverse venturi-shaped fluidized bed apparatus is oriented relatively parallel to the platform plate for removing contaminants from gaseous emissions;

FIG. 26 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 a housing of the reverse venturi-shaped fluidized bed apparatus is oriented laterally with respect to the platform plate to remove contaminants from non-gaseous emissions;

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

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

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

FIG. 30 is a table illustrating the disclosed broad spectrum CZTS alloy sorbent and its 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 different filters containing specific effective sorbents that match 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 a different filter containing a specific effective adsorbent that matches the type and/or level of contaminants in the non-gaseous emissions; and

FIG. 33 is a flow chart illustrating an extended non-turbulent effluent stream through an exemplary reverse venturi-shaped fluidized bed apparatus, and exemplary method steps for cleaning and recycling a sorbent that separates contaminants from the effluent through the use of a series of sorbent recycling subsystems for CZTS sorbents, CZTS alloy sorbents and/or carbon-based sorbents.

Detailed Description

Referring to the drawings, wherein like reference numerals designate corresponding parts throughout the several views, there are shown apparatus and methods 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 may 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, in order to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to one skilled in the art that the exemplary embodiments may be embodied in many different forms without the use of specific details and 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 techniques have not been 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," "includes," and "including" 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 should not be construed as necessarily requiring their implementation in the particular order discussed or illustrated, unless specifically identified as an implementation order. It should also be 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 can 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 fashion (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 the context clearly indicates otherwise. 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," "lower," "upper," and the like, may be used herein to facilitate a description to describe one element or feature's relationship to another element or feature as illustrated. 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 term "below" as illustrated may include both upward and downward directions. 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 to convey liquid and/or liquid-like emissions and gaseous and/or gaseous emissions. No preference is given or implied to the actual method of transportation of the emissions, regardless of the type of emissions. In addition, it should be understood that the terms "contaminant" and "contaminant" are used interchangeably throughout 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 the power line 8. The combustion 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, which generator 6 generates 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 systems (FIG. 1), the emissions 10 include a number of hazardous pollutants such as fly ash, mercury (Hg), metal vapor, sulfur dioxide (SO ₂ ) Hydrogen chloride (HCl)Other toxic fumes.

Referring to FIG. 2, a schematic diagram of a newer coal-fired power plant 200 is shown, including a typical emissions control system 202. The emission control system 202 facilitates capturing and collecting some of the harmful pollutants in the gaseous emissions 10. The emission control system 202 transfers the gaseous emission 10 from the fluidized bed reactor 1, where combustion occurs, to a wet or dry scrubber 11, where the wet or dry scrubber 11 removes some sulfur dioxide and fly ash contaminants from the gaseous emission 10. Instead of, or in addition to, delivering the gaseous effluent 10 to the wet or dry scrubber 11, the effluent control system 202 may deliver the gaseous effluent 10 to the spray dryer 12, where some sulfur dioxide, toxic fumes, and other contaminants 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 gaseous effluent 10. The system collects and removes many contaminants 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 emission control system 202 shown in fig. 2 is that nano-sized contaminants (such as mercury) contained in the metal vapor emissions readily pass through the wet or dry scrubber 11, spray dryer 12, and fabric filter unit 13 of the emission control system 202.

Referring to FIG. 3, a schematic diagram of a modified coal fired power plant 300 is shown that includes the sorbent injector 14 and the reverse venturi apparatus 15 in addition to the emissions control system 202 shown in FIG. 2. The sorbent injector 14 operates to add sorbent into the gaseous effluent 10 and may optionally be disposed upstream of the reverse venturi apparatus 15. More specifically, in the example shown in fig. 3, the sorbent injector is 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 of the reverse venturi device 15 are possible. One major advantage of this location is that the existing facility is able to install the reverse venturi apparatus 15 and simply apply for "modify existing license (Modification to Existing Permit)", saving time and money as compared to applying for new licenses for entirely new emissions control systems. In operation, gaseous emissions 10 are 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 amounts of mercury, heavy metals, nano-sized particles, and other contaminants. The resulting gaseous effluent 10 leaving the stack 9 is thus stripped of almost all harmful pollutants.

Referring to fig. 4A-D, the reverse venturi apparatus 15 includes a housing 16 shaped as a reverse venturi. It should be appreciated that a venturi may be generally described as a conduit that narrows from a larger cross-section down to a smaller cross-section first, and then expands from the smaller cross-section back to the larger cross-section. Thus, the term "reverse venturi" as used herein describes an opposing conduit that first expands from a smaller cross-section to a larger cross-section and then narrows down from the larger cross-section 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 gaseous emissions 10 at a predetermined inlet flow rate, characterized by an inlet velocity V ₁ And pressure P ₁ . The outlet portion 20 of the housing 16 is sized to discharge gaseous emissions 10 at a predetermined outlet flow rate, characterized by an outlet velocity V ₃ And pressure P ₃ . 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 contaminants in the gaseous emissions 10. The enlarged portion 19 of the housing 16 has an inner surface 68, the inner surface 68 generally facing 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.

Entry of the housing 16The mouth portion 18 has an inlet portion cross-sectional area a transverse to the central axis 17 ₁ And the outlet portion 20 of the housing 16 has an outlet portion cross-sectional area A transverse to the central axis 17 ₃ . Inlet section cross-sectional area A ₁ Can be equal to the outlet portion cross-sectional area A ₃ (i.e. can be in cross-section with the outlet portion A ₃ The same) such that the predetermined inlet flow rate is equal to (i.e., the same as) the predetermined outlet split. Alternatively, the inlet section cross-sectional area A ₁ Can be in cross-section area A with the outlet portion ₃ Different (i.e., greater or less) such that the predetermined inlet flow rate is different (i.e., less than or greater than) the predetermined outlet flow rate. It should be understood that the term "flow" as used herein refers to the volumetric flow of the effluent.

The enlarged portion 19 of the housing 16 has an enlarged portion cross-sectional area A ₂ Which cross-sectional area is transverse to the central axis 17 and is larger than the inlet portion cross-sectional area A ₁ And outlet portion cross-sectional area A ₃ . The enlarged portion 19 is thus dimensioned such that the flow velocity V of the gaseous effluent 10 within the enlarged portion 19 of the housing 16 ₂ Less than the flow velocity V of the gaseous effluent 10 in the inlet portion 18 of the housing 16 ₁ And is less than the flow velocity V of the gaseous effluent 10 in the outlet portion 20 of the housing 16 ₃ . This reduced flow rate in turn increases the residence time of gaseous effluent 10 within enlarged portion 19 of housing 16. It should be understood that the term "residence time" as used herein refers to the average amount of time required for molecules in the gaseous effluent 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 the amount of time it takes for all emissions in the enlarged chamber 21 to be refreshed. 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 unchanged regardless of the thickness variation of the housing 16. Thus, the cross-sectional area A of the enlarged portion ₂ Reflecting the size of the expansion chamber 21 and being delimited by the inner surface 68.

Due to the geometry of the housing 16, the internal pressure P of the gaseous effluent 10 through the inlet portion 18 of the housing 16 ₁ And the internal pressure P of the gaseous effluent 10 through the outlet portion 20 of the housing 16 ₃ Greater than the internal pressure P of the gaseous effluent 10 passing through the enlarged portion 19 of the housing 16 ₂ . The pressure difference is related to the flow velocity V of the gaseous effluent 10 in the enlarged portion 19 of the housing 16 ₂ Less than the flow velocity V of the gaseous effluent 10 in the inlet portion 18 of the housing 16 ₁ And is less than the flow velocity V of the gaseous effluent 10 in the outlet portion 20 of the housing 16 ₃ In combination with the fact that the gaseous effluent 10 is caused to stay in the enlarged portion 19 of the housing 16. Due to the pressure and velocity differences mentioned above and because the gaseous emission 10 will naturally expand to occupy the whole volume of the enlarged chamber 21, an expansion force is thus exerted on the gaseous emission 10 in the enlarged portion 19 of the housing 16. This, in combination with the effects of laminar flow, aerodynamic dynamics, and gas behavior physics, the resulting increase in residence time improves the ability of the reverse venturi apparatus 15 to effectively capture and thereby remove contaminants 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, the enlarged portion 19, and the outlet portion 20 of the housing 16 shown in FIGS. 4A-D all have a circular cross-sectional area A ₁ 、A ₂ 、A ₃ . 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 16 ₁ 、A ₂ 、A ₃ May have a non-circular shape, with various combinations of circular and non-circular cross-sectional areas being possible and considered to be within the scope of the present disclosure. In some constructions, the enlarged portion 19 of the housing 16 can have a diverging end 22 and a converging end 23. According to these configurations, the enlarged portion 19 of the housing 16 extends from the inlet portion cross-sectional area A at the diverging end 22 ₁ Tapering outwardly to an enlarged portion cross-sectional area A ₂ . In other words, the cross-section of the enlarged portion 19 of the housing 16 increases at the diverging end 22 in a direction away from the inlet portion 18 of the housing 16. Conversely, enlarged portion 19 of housing 16 extends from enlarged portion cross-sectional area A at converging end 23 ₂ Inwardly tapering to an outlet portion cross-sectional area A ₃ . In other words, the enlarged portion 19 of the housing 16The cross-section decreases at the converging end 23 in a direction moving towards the outlet portion 20 of the housing 16. Thus, it should be appreciated that gaseous emissions 10 in enlarged portion 19 of housing 16 generally flow from diverging end 22 to 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 A ₁ 、A ₂ 、A ₃ In embodiments of (2), the diverging end 22 and the converging end 23 of the housing 16 may have a generally conical shape. However, alternative shapes of the diverging end 22 and 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 converging end 23 may have polygonal shapes to improve ease of manufacture while avoiding any significant adverse effect on the flow of gaseous effluent 10 through the housing 16 of the reverse venturi apparatus 15. In another alternative configuration, the enlarged portion 19 of the housing 16 may have a sausage-like shape with a relatively abrupt transition 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 preferred over a sudden transition because laminar flow behavior of the gaseous effluent 10 may be preferred. However, a slight disturbance to the laminar flow of the gaseous effluent 10 at the abrupt transition is not considered an overwhelming loss, but may instead provide enhanced flow in areas where increased residence time is not required.

With continued reference to fig. 4A-D and with additional reference to fig. 5-11, a quantity of reactive material 24 is disposed within enlarged portion 19 of housing 16. The quantity of reactive material 24 has a reactive outer surface 25 that is disposed in contact with the gaseous emissions 10. In addition, 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 contaminants in the gaseous effluent 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 way, contaminants bound to the reactive outer surface 25 of the volume of reactive material 24 remain trapped in the enlarged portion 19 of the housing 16 and are thus removed from the flow of gaseous effluent 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 the group of metals that is capable of forming a compound with one or more contaminants in the gaseous effluent 10. As a 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 effluent 10 while providing a residence time long enough to enable the amalgam-forming metal in the bulk reactive material 24 to chemically bond with the contaminants in the gaseous effluent 10. Thus, to achieve this balance, the enlarged portion 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 enough time for the contaminants in the gaseous effluent 10 to chemically bond to the amalgam-forming metal in the bulk reactive material 24. Thus, the range of the expanded section cross-sectional area A2 is calculated to achieve a residence time of the coal-fired power plant 100 with an output ranging 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 arts. 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 appreciated 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.

A large 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 FIGS. 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 effluent 10 through the enlarged portion 19 of the housing 16. Thus, the blocking elements 26a-j increase the residence time of the gaseous effluent 10 through the enlarged portion 19 of the housing 16. Several embodiments discussed below completely disrupt the flow of gaseous emissions 10 through enlarged portion 19 of housing 16 such that the resulting tortuous flow path 27 is completely random, which greatly enhances the opportunity for chemical reactions between contaminants in gaseous emissions 10 and the bulk of the amalgam-forming metal in reactive material 24.

In each of the configurations shown in fig. 5-11, the blocking elements 26a-j present a large surface area such that the reactive outer surface 25 of the bulk of the 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 bulk reactive material 24 and the contaminants in the gaseous contaminant 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 emission 10. Thus, the amount of contaminants that the enlarged portion 19 of the housing 16 may remove from the gaseous effluent 10 passing through the enlarged chamber 21 is proportional to the size of the reactive outer surface 25 of the volume of reactive material 24 in the enlarged portion 19 of the housing 16. Furthermore, the complex surface shape and/or texture of the barriers 26a-j may provide additional surface area to facilitate physical capture of the contaminants, whether or not the 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 effluent by the sorbent injector 14 contains an amalgam-forming metal. In this way, the amalgam-forming metal in the adsorbent chemically bonds with at least some of the contaminants in the gaseous effluent 10 before the gaseous effluent 10 enters the enlarged portion 19 of the housing 16. While the sorbent may have many different compositions, the sorbent may be, for example, zinc (Zn) powder or a Copper Zinc Tin Sulfide (CZTS) compound. Because the adsorbent chemically bonds with at least some of the contaminants in the gaseous emissions 10 before the gaseous emissions 10 enter the enlarged portion 19 of the housing 16, the adsorbent assists in removing the large amount of reactive material 24 from the gaseous emissions 10.

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 staggered 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 contaminants in the gaseous emissions 10 by the large amount of reactive material 24 forming a series of staggered baffles 26a. In one variation, the series of staggered baffles 26a are made of zinc. In another variation, the series of staggered baffles 26a are made of a non-zinc material coated with zinc. It should be appreciated that the placement of the staggered 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 26a. It should also be appreciated that if the series of staggered baffles 26a become saturated during operation of the reverse venturi apparatus 15, the series of staggered baffles 26a may be replaced and/or cleaned as desired.

Referring to fig. 6A-B, alternatively, at least one blocking element 26A-j is in the form of a helical baffle 26B. The helical baffle 26b extends helically within the enlarged portion 19 of the housing 16 along the central axis 17 and about the central axis 17. Thus, the helical baffle 26b imparts a helical shape to the tortuous flow path 27. The spiral 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 contaminants in the gaseous emissions 10 by the large amount of reactive material 24 forming the spiral baffle 26b. In one variation, the helical baffle 26b is made of zinc. In another variation, the helical baffle 26b is 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 housing 16. The rotation of the helical baffle 26b may artificially accelerate or artificially slow the flow of gaseous emissions 10 through the enlarged portion 19 of the housing 16, depending on the direction of the helical baffle rotation. It should be appreciated that if the helical baffle 26b becomes saturated during operation of the reverse venturi apparatus 15, the helical baffle 26b may be replaced and/or cleaned as desired.

Referring to fig. 7A-B, at least one blocking element 26a-j is a plurality of baffles 26c. Each baffle 26c extends transversely from an inner surface 68 of enlarged portion 19 of housing 16 through enlarged portion 19 of housing 16. Baffles 26c are spaced apart from each other along central axis 17, and each baffle 26c includes an aperture 28 that allows gaseous emissions 10 to flow through baffle 26c. Of course, it should be understood that any number of baffles 26c are possible, including configurations that include only a single baffle 26c. It should also be appreciated that the size, shape, and number of apertures 28 in each baffle 26c may vary. For example, the baffles 26c may be provided in the form of a screen, with apertures 28 formed between intersecting lines of the screen. The apertures 28 in the baffles 26c limit the flow of the gaseous effluent 10 in the enlarged portion 19 of the housing 16, thus increasing the residence time of the gaseous effluent 10 in the enlarged portion 19 of the housing 16. This improves the capture and removal of contaminants in the gaseous emissions 10 by the large amount of reactive material 24 forming the baffles 26c. 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 should be appreciated that if the baffle 26c becomes saturated during operation of the reverse 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 26c. By using different sized apertures 28 in different baffles 26c, the flow of gaseous emissions 10 may be accelerated and/or restricted to enhance the capture and removal of contaminants in gaseous emissions 10 by the large amount of reactive material in baffles 26c. In a similar manner, baffles 26c need not be equally spaced in enlarged chamber 21 nor need apertures 28 in one of baffles 26c be the same size, shape, or the same location as apertures 28 in an adjacent baffle 26c. 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 effluent 10 in the enlarged portion 19 of the housing 16 may be increased so as to promote increased contact along the physical and chemical capture and collection locations of the bulk of the reactive material 24.

In other alternative configurations shown in fig. 8-11, 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 blocking element 26a-j may include various forms of blocking media 26d-j. Similar to barrier elements 26a-c, barrier medium 26d-j can be made of zinc or a non-zinc material coated with zinc. Zinc is readily melted, allowing complex shapes to be cast using conventional molding methods, dewaxing processes, centrifugation processes, and the like. Other construction methods 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 with zinc or galvanized as a surface covering. The blocking medium 26d-j may be used to completely fill the entire expansion chamber 21, partially fill the expansion chamber 21, or fill between baffles 26c previously described in connection with fig. 7A-B.

Fig. 8 shows a configuration in which at least one blocking element 26a-j is a plurality of fragments 26d contained in enlarged portion 19 of 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 26d. For this purpose, the plurality of fragments 26d may be provided with an irregular shape, such that the fragments 26d loosely fill 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. Spongy zinc is a popcorn-shaped zinc structure that is made by immersing molten zinc in a cooling liquid such as water. The molten zinc droplets thus produced solidify into a relatively small spherical structure with a very high surface area to volume ratio. In addition, the surface area of the resulting structure has a sponge-like surface texture. These structures may be produced in a range of sizes for a particular application. Some steel processes can produce steel plates of complex spherical structure like sponge zinc, which can be coated with zinc.

The loosely packed nature of the plurality of fragments 26d in fig. 8 gives a random shape to the tortuous flow path 27, which increases the residence time of the gaseous effluent 10 in the enlarged portion 19 of the housing 16. This in turn enhances the capture and removal of contaminants in the gaseous emissions 10 by the large amount of reactive material 24 forming the plurality of fragments 26 d. If multiple fragments 26d in fig. 8 become saturated during operation of reverse venturi apparatus 15, they may be replaced and/or cleaned as desired.

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

Referring to fig. 10, another alternative configuration is shown in which at least one of the blocking elements 26a-j is a filter element 26f. 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 as the gaseous emissions 10 flow from the inlet portion 18 through the enlarged portion 19 of the housing 16 to the outlet portion 20 of the housing 16, the pores in the filter element 26f allow the gaseous emissions 10 to pass through the filter element 26f. The arrangement of the filter element 26f, which may be made of sintered metal, gives the tortuous flow path 27 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 contaminants in the gaseous emissions 10 by the large amount of reactive material 24 forming the filter element 26f. The sintered metal of the filter element 26f is preferably made of zinc or a non-zinc material coated with zinc. It should 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 desired.

Referring to FIG. 11, at least one blocking element 26a-j is shown as a combination of a plurality of baffles 26c shown in FIGS. 7A-B with 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 fragments 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 transversely from an inner surface 68 of the enlarged portion 19 of the housing 16 through the enlarged portion 19 of the housing 16. In addition, a plurality of baffles 26c are spaced relative to one another along the central axis 17 such that the baffles 26c divide the expansion chamber 21 into a plurality of portions. Apertures 28 in each baffle 26c allow gaseous emissions 10 to flow through baffle 26c. A plurality of fragments 26g-j are disposed between adjacent baffles 26c (i.e., in portions of the expansion chamber 21).

As shown in fig. 11 and 12A-D, a plurality of fragments 26g-j form a quantity of reactive material 24. The plurality of fragments 26g-j may be provided in different sizes, wherein the plurality of fragments 26g-j are grouped in similar sizes (i.e., fragments 26g, 26h, 26i, and 26j are in different groups) and separated from fragments of another size by baffles 26 c. For example, the set of fragments 26g-j may be arranged such that the fragments 26g-j decrease in size as they move 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 one moves in the general flow direction of the gaseous effluent 10 in the enlarged portion 19 of the housing 16. In one variation, the fragments 26g-j are made of zinc. For example, the fragments 26g-j may be formed into a popcorn-like structure by dropping molten zinc into a cooling liquid, having a particularly large surface area and a random sponge-like surface texture. It will be appreciated 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 the form of loose material, 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 barrier 26k forms a large quantity of reactive material 24 and has an asterisk-like shape, which is similar to the shape of a children's toy known as "Jacks". Fig. 13B shows another example in which the alternatively shaped blocking elements 26k-m are a plurality of crystal flakes 26l (one shown) that form a large quantity 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. The crystal flakes 26l have a snowflake-like shape. Fig. 13C shows another example in which an 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 appreciated that the barrier 26k and the plurality of crystal flakes 26l may 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 may be manufactured, for example, by entangling zinc wire on a mandrel shaft similar to a spring shape, except that after entangling around the mandrel shaft, the entire entangled coil is cut along the length of the mandrel shaft so that a single coil is produced. It should also be appreciated that the alternatively shaped blocking elements 26k-m may or may not completely fill the expansion chamber 21.

It should be appreciated that the various types of blocking elements 26a-k described above may be mixed and matched to create various combinations. Examples of mixing and matching include combining one or more baffles 26A-c shown in FIGS. 5, 6A-B and 7A-B with a plurality of

fragments

26d and 26g-j shown in FIGS. 8 and 11. Other examples of blending and matching include combining a plurality of intertwined lines 26e shown in fig. 9 with a plurality of

fragments

26d and 26g-j shown in fig. 8 and 11. Other alternative constructions are possible that combine the various types of blocking elements 26a-k described above with other filter materials such as activated carbon. Activated carbon may resemble a sponge and collect contaminants by surface contact. Thus, a limited amount of activated carbon may be introduced into enlarged portion 19 of 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 disposed relatively stationary throughout the enlarged chamber 21. This is in contrast to typical emissions control systems that release activated carbon into a stream 10 of gaseous emissions. Activated carbon may be used more efficiently because it is not free-flowing with gaseous emissions. Those skilled in the art will readily appreciate that the disclosed variations of reverse venturi apparatus 15 are merely exemplary, and that many combinations well beyond the several examples disclosed herein are possible and desirable for addressing a particular application.

Referring to fig. 14, another exemplary reverse venturi apparatus 15 'is shown that 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 the other 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 effluent 10 is elongated. According to this configuration, gaseous emissions 10 are directed from enlarged portion 19 through conduit 38 and to enlarged portion 19' where additional contaminants are collected and/or captured. It should also be appreciated that the present disclosure is not limited to the use of only one or two expansion sections 19, 19' in series, as some applications with large emissions and/or heavy pollution levels may require multiple expansion sections connected together in series.

Referring to FIG. 15, another exemplary reverse venturi apparatus 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 conduit 41 or conduit 42. The three-way outlet valve 40 directs the gaseous effluent 10 to exit from either conduit 41 or conduit 42 without flowing back directly from conduit 41 into conduit 42 and vice versa. As gaseous emissions 10 are directed through conduit 41, gaseous emissions 10 enter enlarged portion 19 through inlet portion 18 and exit through outlet portion 20. As gaseous emissions 10 are channeled through conduit 42, gaseous emissions 10 enter enlarged portion 19 "through inlet portion 18" and exit through outlet portion 20 ". One advantage of the reverse venturi apparatus 15 "shown in fig. 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 service.

Over time, chemical reactions and/or physical capture of contaminants occurring on the reactive outer surface 25 of the quantity of reactive material 24 may result in a saturation point of the quantity 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 a large amount of the reactive material 24 in the

enlarged portions

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

The process of removing contaminants from the saturated bulk of the reactive material will depend inter alia on the type of contaminant and the type of amalgam forming metal used. The passage 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 stops, a pouring and/or draining channel is 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 nozzle 81 is positioned to spray the deoxyacid onto the quantity of reactive material 24 in the

enlarged portions

19, 19 "of the housing 16. In operation, the deoxygenated acid washes the contaminant volume of reactive material 24 to regenerate the volume of reactive material 24. Alternatively, a drain 82 may be provided in fluid communication with the

enlarged portions

19, 19 "of the housing 16 to convey the used deoxidized acid and contaminant solution away from the

enlarged portions

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

Referring to fig. 16, another exemplary reverse venturi apparatus 15 is shown in which the enlarged chamber 45 has a significantly larger volume compared to the volumes of the inlet conduit 43 and the outlet conduit 44. The enlarged portion 46 may be circular, square, triangular, oval, or any of a number of shapes (where rectangular shapes are shown) as may be desired to achieve an enlarged tortuous flow path 77 for the gaseous effluent to flow through the enlarged portion 46.

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

18A-B, the block diagram of FIG. 17 has been modified with the introduction point option of sorbent injection and additional steps have been added wherein the gaseous effluent passes through the reverse venturi apparatus 15 described above. In fig. 18A, a first sorbent introduction point 55 is shown located between furnace 47 and ESP 48. Alternatively, in FIG. 18B, the second sorbent introduction point 56 is shown positioned between the FGD unit 49 and the FF unit 50. Which option is considered to be the most suitable adsorbent will depend on the existing configuration and conditions of the plant. There are many other points of introduction and/or combinations of points of introduction where the adsorbent may be introduced instead of the two options depicted in fig. 18A-B, so these two options are shown for illustration purposes. The reverse 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 constructed according to any of the foregoing examples described above, as may be suitable for various applications. Finally, the final 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: the fuel is combusted in furnace 47 to produce gaseous emissions containing pollutants, the gaseous emissions from furnace 47 are directed to ESP 48, and a first portion of the particulate pollutants in the gaseous emissions are removed using ESP 48. In accordance with the step of using ESP 48 to remove a first portion of the particulate contaminants in the gaseous effluent, a first concentrate 52 is formed that contains the first portion of the particulate contaminants that have been removed from the gaseous effluent by ESP 48. It should be appreciated that, in operation, ESP 48 utilizes an induced electrostatic charge to remove fine contaminant particles from gaseous emissions. The method further comprises the steps of: the gaseous effluent from ESP 48 is directed to FGD unit 49 and sulfur dioxide contaminants in the gaseous effluent are removed using FGD unit 49. According to the step of removing sulfur dioxide contaminants in the gaseous effluent using the FGD unit 49, a second concentrate 53 is formed comprising sulfur dioxide contaminants that have been removed from the gaseous effluent by the FGD unit 49. The method further comprises the steps of: the gaseous effluent from FGD unit 49 is directed to FF unit 50 (i.e., a baghouse) and a second portion of the particulate contaminants in the gaseous effluent are removed using FF unit 50. According to the step of removing a second portion of the particulate contaminants in the gaseous effluent using FF unit 50, a third concentrate 54 is formed that contains the second portion of the particulate contaminants that have been removed from the gaseous effluent by FF unit 50. It should be appreciated that in operation, contaminant particles are removed from the gaseous emissions as they pass through one or more fabric filters (not shown) of FF unit 50.

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

emissions control devices

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

Alternatively, the method may comprise the step of injecting the adsorbent into the gaseous effluent. In accordance with this step and as shown in fig. 18A, the sorbent may be injected into the gaseous effluent at a first sorbent introduction point 55 disposed between furnace 47 and 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 adsorbent contains an amalgam forming metal such that the adsorbent combines with at least some of the heavy metal contaminants in the gaseous effluent before the gaseous effluent enters the reverse venturi apparatus 15. By injecting sorbent into the gaseous effluent 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 that were 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 is capable of regeneration and rejuvenation so that the harmful 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 a Fluidization Gas Desulfurization (FGD) unit 59 and/or from the wet scrubber unit 58 into a lime treatment unit 60 and then to a settling tank 61. After a suitable period of time, the non-gaseous effluent will be led from the settling tank 61 to a process system 64 for preparation of the drying process or to a dewatering system 62. The non-gaseous emissions directed through the process 64 for drying treatment are ready for treatment in the landfill 65. The non-gaseous effluent directed through the dewatering system 62 (which may sometimes include a recirculation system) is ready for a second industrial process 63, which may involve, for example, the manufacture of gypsum and/or cement. Non-gaseous effluent not directed from the settling tank 61 into the dewatering system 62 or to the process 64 for drying treatment is directed to discharge into a flume 66. The final non-gaseous emissions released into waterway 66 are not regulated as in the next few years. The proposed EPA water emission regulations and requirements will have extremely stringent restrictions compared to current emissions that are allowed into waterways. Industries that require contaminated liquid emissions to be discharged into waterways have current emissions control technology that is 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 adsorbents described above. The treatment tank 67 is located after the non-gaseous emissions are directed from the settling tank 61 and before they are discharged to the waterway 66. The method shown in fig. 20 includes the steps of: the non-gaseous emissions containing contaminants are collected, passed through the FGD unit 59 and/or the wet scrubber 58 to remove some of the contaminants in the non-gaseous emissions, the non-gaseous emissions are directed from the FGD unit 59 and/or the wet scrubber 58 to the discharge of the lime treatment unit 60, and passed 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 steps of: directing the non-gaseous emissions from the lime treatment unit 60 to a settling tank 61, wherein some of the contaminants in the non-gaseous emissions are removed by settling; dewatering a first portion of the non-gaseous effluent in a settling tank 61 and using the dewatered byproduct in a secondary industrial process 63; and removing a second portion of the non-gaseous effluent from the settling tank 61 and subjecting the second portion of the non-gaseous effluent to a drying treatment process 64. Depending on the step of dewatering the first portion of the non-gaseous effluent in the settling tank 61 and using the dewatered byproducts in the secondary industrial process 63, the dewatering process may comprise recycling the first portion of the non-gaseous effluent, and the secondary industrial process 63 may involve, for example, the manufacture of gypsum or the manufacture of cement. Depending on the step of removing the second portion of the non-gaseous effluent from the settling tank 61 and subjecting the second portion of the non-gaseous effluent to the drying treatment process 64, the drying treatment process 64 may include depositing the second portion of the non-gaseous effluent in a landfill 65.

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 adsorbent contains an amalgam-forming metal that binds with a heavy metal contaminant in a third portion of the non-gaseous effluent. Thus, when the heavy metal contaminants combine with the adsorbent and settle/precipitate out of the non-gaseous effluent, the adsorbent traps the heavy metal contaminants in the treatment tank 67. The method may then continue with directing non-gaseous emissions from treatment tank 67 to waterway 66 for discharge. It should be appreciated that the design of the treatment tank 67 may allow non-gaseous emissions (i.e., wastewater streams) to continuously pass 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 described above, one exemplary sorbent is elemental zinc powder. Zinc powder is made of elemental zinc. The zinc may be present in powder form or in particulate form. One method that may be used to extend the useful life of zinc dust and/or particles at high temperatures for certain gas emission applications and to reduce and/or prevent premature oxidation is to mix the particles and/or powder with or coat 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 optimal particle size range for zinc powder is 0.5 nm to 7,500 microns. Furthermore, powder mixtures having a range of different sized particles have been found to be beneficial, particularly if the particle size ranges from 0.5 nm to 7,500 microns. Similarly, the optimal particle size range for zinc particles is 7,500 microns to 3.0 inches. Furthermore, it has been found that particle mixtures having a range of different sized particles are beneficial, particularly if the particle size ranges from 7,500 microns to 7,500 inches.

In another exemplary embodiment, the sorbent is CZTS, which has elemental Cu ₂ ZnSnS ₄ . CZTS may also include other phases of copper, zinc, tin and sulfur, which are also beneficial. The CZTS and/or related phases of copper, zinc, tin and sulfur may be blended in stoichiometric proportions and then mechanochemical compounding may be performed in a mill. In addition, CZTS may be mixed with any of several clay such as bentonite or zeolite and calcium hydroxide (CaOH) in equal proportions. The optimal particle size range for CZTS powder is 0.5 nm to 7,500 microns. It has been found in testing and development that CZTS powder mixtures with a range of different sized particles are beneficial, particularly if the particle size ranges from 0.5 nm to 7,500 microns. In applications where specialized CZTS particles are preferred, it has been found that the optimum particle size is 7,500 microns to 3.0 inches. Furthermore, it has been found that a CZTS particle mixture having a range of particles of different sizes is beneficial, particularly if the particle size ranges from 7,500 microns to 3.0 inches.

For most contaminants, CZTS is the smallest particle size within the above range and most effective when the highest amount of CZTS in the metal phase is present. It should be appreciated 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., danshin (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 combination of milling equipment that achieves the desired particle size in sequential combinations. An exemplary starting particle size range is 325 mesh screen to 100 mesh screen, with 1 mesh screen being equal to 7,500 microns. The received particles are treated with predetermined copper: zinc: tin: sulfur=1.7: 1.2:1.0: the molar ratio of 4.0 was further weighed. After confirmation of mesh size and molar ratio, the particles were mechanochemically compounded into CZTS and its other phases by milling. The milling time is controlled to achieve optimal performance for a particular application. It should also be appreciated that grinding may be accomplished using a wet grinding process by adding a suitable solvent such as glycol ether, glycol, ammonia, or other alcohols, or by dry grinding in an inert gas atmosphere.

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

According to the above method, the adsorbent may be introduced into the gaseous effluent, wherein the gaseous effluent has a temperature of about 750 degrees Fahrenheit or less. The adsorbent 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 method of introduction may be selected based on the emissions control system existing in the plant to facilitate retrofitting. One convenient method may be to inject CZTS into the gaseous effluent instead of activated carbon, wherein the same injection apparatus 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 contaminants. Alternatively, when CZTS is blended with zeolite, the treatment of non-gaseous emissions applications may be optimized. In addition to the particular materials blended with CZTS, the proportions of the blend may be application specific to provide optimized contaminant removal capability.

18A-B, where CZTS is used to treat gaseous emissions, a fabric filter unit 50 should be placed downstream of the CZTS introduction points 55,56 so that the fabric filter unit 50 captures sorbent particles and increases the contact time of the gaseous emissions with the sorbent. The deposition of the adsorbent on the fabric filters (i.e., bags) of the fabric filter unit 50 allows for additional contact time between the gaseous emissions and the adsorbent and allows for the adsorbent to be collected for subsequent recovery. The small particle size of the adsorbent allows carrying the adsorbent in the flow of the stream of gaseous emissions, such as dust carried by wind. During the period of time that the adsorbent is entrained in the flow of gaseous emissions, the adsorbent is in contact with contaminants that also travel in the flow of gaseous emissions, and thus may chemically react with and bind with the adsorbent. Upon reaching the fabric filter unit 50, the gaseous emissions continue through the filters in the fabric filter unit 50 while the combined adsorbent and contaminant particle size 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 size 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 rated filter may be used in the fabric filter unit 50.

In other applications of non-gaseous emissions, CZTS may be introduced into the treatment tank 67 shown in FIG. 20. In this configuration, CZTS is optimally introduced into the treatment tank 67 and properly agitated over a period of time, and then the non-gaseous effluent (e.g., wastewater) is subjected to pH adjustment, flocculation, and filtration prior to discharge. Thereafter, the CZTS in the treatment tank 67 may undergo a recovery process wherein contaminants are collected from the CZTS. The used CZTS may be recovered by leaching mercury from 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 water discharge regulations set by the EPA that were in effect in 2016 are much more stringent than air regulations. The current EPA water law levels listed in nanograms per liter (ng/L), micrograms per liter (μg/L) and/or g/L are: mercury @119ng/L; arsenic (As) @8 μg/L; selenium (Se) @10 μg/L; nitrogen dioxide (NO) ₂ ) And Nitrate (NO) ₃ ) @0.13g/L. Other heavy metals such as lead (Pb) and cadmium (Cd) also present EPA limitation levels. In many existing plants, water having a pollution level above the allowable emission regulations is directed to one or the other of a holding tank and/or other type of sludge holding storage tank. CZTS may treat solids in the holding tank by the same methods disclosed herein for treating non-gaseous emissions. The contact time of CZTS in the holding tank may be appropriately adjusted depending on the ionic form of heavy metals, sludge composition and/or pH. Proper pH adjustment, flocculation and subsequent filtration would allow for normal discharge, handling and/or use in other industries, 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 by-products of the disclosed process are non-leachable. These byproducts are therefore of valuable industrial use in gypsum wallboard and cement applications. The leaching test of metal sulfides by EPA is well known and the use in these products is well documented.

While activated carbon may be used in some alternative configurations, the limited use of activated carbon in these variations does not allow the activated carbon to escape into the effluent. For example, in one configuration, activated carbon may be embedded in the filter of fabric filter unit 50. The activated carbon cannot freely escape into the stream of gaseous emissions. Another limited use of activated carbon is possible, wherein the activated carbon coats CZTS in its crystalline form, producing CZTS with a thin layer of carbon having a thickness of about 1.0 nm or less. This helps encourage the entrapment of very small metallic vapor mercury particles. In a similar manner, the CZTS crystalline form may be coated with a thin nano-like layer of zeolite or other coating to specifically target specific detrimental contaminants for a particular application. Also, the activated carbon in this example cannot freely escape into the stream of gaseous emissions. In another configuration shown in fig. 33, the reverse venturi fluid bed apparatus includes an arrangement for cleaning and recirculating sorbent in the form of a series of sorbent recirculation subsystems for CZTS sorbent, CZTS alloy sorbent, and/or carbon-based sorbent.

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

Still referring to FIG. 21, the exemplary emission control system 80 may be a new emission control system based on the reverse venturi apparatus, sorbents, and/or methods disclosed herein, or it may be an existing emission control system that has been modified and expanded to include the reverse venturi apparatus, sorbents, and methods disclosed herein. Testing has demonstrated that the exemplary emission control system 80 is effective and capable of removing at least 98% of harmful contaminants, 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 through a system exhaust that releases gaseous emissions with environmental control 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, the application specific requirements may require one or more pre-fluidized bed filters 151.

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

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 restriction barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 also has dominant outwardly extending male ends 168 and 169 to promote extended residence flow time while minimizing turbulence through the reactive material 164. When the contaminated gaseous source 150 stream enters the fluidized bed 152 at inlet 165, intimate contact with the reactive material 164 is initiated, creating random non-turbulent flow 166. Due to the predominantly outwardly extending male ends 168 and 169, the random non-turbulent flow 166 turns itself, resulting in an increased residence time in the fluidized bed 152 before the non-turbulent flow 166 exits from the fluidized bed 152 through the outlet 167. The reactive material 164 promotes random non-turbulent flow 166, which is a random tortuous flow path for the contaminated gaseous source 150. It should be appreciated that the length L of the fluidized bed 152 does not include the male ends 168 and 169.

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

Referring to fig. 23 and 24, an exemplary method of emissions control is shown in which a contaminated non-gaseous source 161 is introduced into the system through one or more pre-fluidized bed filters 151, through a fluidized bed 152, through one or more post-fluidized bed filters 153, and through a system exhaust 154, which releases gaseous emissions with an environmental control release 162. It should be appreciated 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 the need for one or more pre-fluidized bed filters 151.

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

Preferably, the fluidized bed 152 also has dominant outwardly extending male ends 168 and 169 to promote extended residence flow time while minimizing turbulence through the reactive material 164. When a contaminated non-gaseous source 161 stream enters the fluidized bed 152 at inlet 165, intimate contact with the reactive material 164 is initiated, creating random non-turbulent flow 166. Due to the predominantly outwardly extending male ends 168 and 169, the random non-turbulent flow 166 turns around itself, resulting in an increased residence time in the fluidized bed 152 before exiting from the fluidized bed 152 through the outlet 167. The reactive material 164 promotes random non-turbulent flow 166, which is a random tortuous flow path for the contaminated non-gaseous source 161. It should be appreciated that the length L of the fluidized bed 152 does not include the male 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 restriction barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 has a side outlet 170 to the adsorbent cleaning station 156. The sorbent cleaning station 156 has the option of removing spent sorbent 157 from the system for disposal. In addition, the captured contaminant elements 158 captured from the contaminated non-gaseous source 161 through the reactive material 164 and separated from the reactive material 164 in the sorbent cleaning station 156 may be treated 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. Batch refill sorbent containers 168 provide a supplemental volume of reactive material 164 as needed to replace the removed spent sorbent 157. The system emissions 154 provide non-gaseous emissions through an environmental controlled release 162. Additional discharge of captured waste 163 is also provided.

Referring to fig. 25, an exemplary method is shown: the contaminated gaseous effluent 250 is passed through one or more pre-filters 251, through a fluidized bed 253, through one or more post-filters 255, through a system discharge 256, and finally released as a controlled release gaseous effluent 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. A barrier (not shown) inside the fluidized bed 253 provides a preferably tortuous flow path that is particularly suitable 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 fluidized bed 253 can be mounted on a truck 254 and configured to tilt the fluidized bed 253 about the pivot point 252. When gaseous emissions are 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 adsorbent is treated by station 259 and cleaned adsorbent is recycled back to the fluidized bed 253 from the adsorbent return port 260 through return port 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 a fluidized bed 253, through one or more post-filters 255, through a system discharge 256, and finally released as a controlled ambient non-gaseous effluent 273 and/or through a waste treatment process 274. The inlet P2 and the outlet P1 are configured to receive and discharge non-gaseous emissions. A barrier (not shown) inside the fluidized bed 253 provides a preferably 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 adsorbent is treated by station 259 and cleaned adsorbent is recycled back to the fluidized bed 253 from the adsorbent return port 260 through return port P6.

Referring to fig. 27, a table is shown in which the disclosed preferred reactive CZTS alloy sorbent 341 is compared to other sorbents, including activated carbon 342 and zeolite 343. The main types of contaminants 367 are listed as including nitrogen 368, phosphate 369, heavy metals 370, sulfur 371, mercury 372 and selenate 373. The contaminants 367 further list each of the listed adsorbents 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 contaminants 367 in the gaseous emissions 344 and/or the non-gaseous emissions 345. In contrast, activated carbon 342 is ineffective at capturing or removing contaminants 367 from gaseous emissions 346 and/or 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 list of sorbents is shown including the reactive CZTS alloy sorbents 351 and other sorbents of the present disclosure including corrosives 350, iron oxides 355, and zeolites 356. The reactive CZTS alloy sorbent 351 includes a CZTS alloy 352 of sulfur (S), a CZTS alloy 353 of selenate (S), and a CZTS alloy 354 of ferrous oxide. The CZTS alloy sorbent 351 is effectively co-reactive with the group of contaminants: selenate 357, total ionized sulfur (Total Ionized Sulfurs) 358, total ionized nitrogen 359 (Total Ionized Nitrogens), and total ionized phosphate (Total Ionized Phosphates) 360. The reactive CZTS alloy sorbent 351 is capable of capturing and removing these contaminants from gaseous and non-gaseous emissions.

In contrast, the etchant 350 is effective only on the total ionized sulfur 358. Iron oxide 355 is effective only for selenate 357 and has very slow reaction characteristics (effective only for non-gaseous emissions) with Total nitrogen (Total nitrogenis) 359 and Total ionized phosphate (Total Ionized Phosphates) 360. Zeolite 356 is effective only for total ionized nitrogen 359 and total ionized phosphate 360. As a result, known sorbents such as the corrosive 350, iron oxide 355, and zeolite 356 have limited effective properties compared to the broad spectrum characteristics of the reactive CZTS alloy sorbent 351 disclosed herein. Even though known sorbents have some degree of effectiveness, none of them reach the level of effectiveness of the reactive CZTS alloy sorbent 351 disclosed herein.

Referring to fig. 29, table 364 illustrates the capacity of a prior art sorbent 365 for post-treatment after use in an emission control system to capture and remove contaminants 367 including nitrogen 368, phosphorus 369, heavy metals 370, sulfur 371, mercury 372, and selenate 373. In addition to the nitrogen 368 in the gaseous emissions 374, the ability to separate these contaminants 367 from prior art adsorbents in the gaseous emissions 374 and/or the non-gaseous emissions 375 is very poor and virtually non-existent. Similarly, table 364 shows that the ability to reuse prior art adsorbent 366 after separation of contaminants 367 is virtually absent in addition to 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 be post-treated after being used in an emissions control system to capture and remove contaminants 367 including nitrogen 368, phosphorous 369, heavy metals 370, sulfur 371, mercury 372, and selenate 373. The ability to separate contaminants 367 in gaseous emissions 374 and/or non-gaseous emissions 375 from the disclosed reactive CZTS alloy sorbent 339 is particularly advantageous because it means that the contaminants 367 can be more easily handled or recycled, and because the reactive CZTS alloy sorbent 339 can be reused in an 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 contaminants 367 in gaseous emissions 376 and non-gaseous emissions 377.

Referring to fig. 31, a block diagram illustrates a system and method for removing contaminants from gaseous emissions 250. The gaseous emissions 250 are monitored and analyzed in step 379 to determine the type and level of contaminants 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 contaminants remaining in gaseous emissions 250 as determined by step 379, the flow of emissions is directed through prefilter inlet manifold 380 such that gaseous emissions 250 are further directed through appropriate prefilters 381, 382, 383, and/or 384. The 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 filled with the reactive CZTS alloy sorbent 351 shown in fig. 28. For example, the prefilter 381 is filled with the CZTS alloy 352 of sulfur (S) as shown in fig. 28. The prefilter 382 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The prefilter 383 is filled with the ferrous oxide CZTS alloy 354 shown in fig. 28. The prefilter 384 is filled with a combination of CZTS alloy sorbents 352, 353 and/or 354. Additional prefilters may be added to prefilter inlet manifold 380, each prefilter being filled with a different combination of CZTS alloy adsorbents 352, 353, and/or 354, to effectively treat specific levels and/or types of contaminants remaining in gaseous emissions 250.

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

After gaseous effluent 250 exits fluidized bed 253, post-filter monitoring step 386 determines new levels and/or types of contaminants remaining in gaseous effluent 250 and directs gaseous effluent 250 through post-filter inlet manifold 387. The selection of the appropriate post-filters 388, 389, 390 and/or 391 is accomplished by the selection method shown in fig. 28. The post-filter shown in fig. 31 is filled with the reactive CZTS alloy sorbent 351 shown in fig. 28. For example, the post-filter 388 is filled with the CZTS alloy 352 of sulfur (S) shown in fig. 28. Post-filter 389 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The post-filter 390 is filled with the ferrous oxide CZTS alloy 354 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 exiting through the controlled gaseous release stack 257 and some of the gaseous emissions 250 exiting through the appropriate waste treatment step 262.

Additional post-filters may be added to the post-filter inlet manifold 387, each of which is filled with a different combination of CZTS alloy sorbents 352, 353 and/or 354 to effectively treat specific levels and/or types of contaminants remaining in the gaseous effluent 250.

All of the 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 260, respectively. Step 258 includes separating contaminants from the CZTS alloy sorbent 351 so that the contaminants may be recycled and/or properly collected for treatment 261. Any depleted CZTS alloy sorbent 351 may be processed by a processing step 259. Replacement of a particular CZTS alloy sorbent 351 for each particular pre-filter 381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be performed after step 258. Specific routing and/or schematic diagrams for directing the sorbent from the pre-filters 381, 382, 383, 384 and/or post-filters 388, 389, 390, 391 to the sorbent cleaning step 258 and for directing the sorbent from the sorbent cleaning step 258 are not shown.

Referring to fig. 32, a block diagram illustrates a system and method for removing contaminants from non-gaseous emissions 295. The non-gaseous emissions 295 are monitored and analyzed in step 379 to determine the type and level of contaminants in the non-gaseous emissions 295. The monitoring may be intermittent spot check and/or continuous on-line monitoring and analysis of the periodic system. Based on the type and/or level of contaminants remaining in the non-gaseous emissions 295 as determined by step 379, the flow of the 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. The 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. 32 is filled with the reactive CZTS alloy sorbent shown in fig. 28. For example, the prefilter 381 is filled with the CZTS alloy 352 of sulfur (S) as shown in fig. 28. The prefilter 382 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The prefilter 383 is filled with the ferrous oxide CZTS alloy 354 shown in fig. 28. The prefilter 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 pre-filter being filled with a different combination of CZTS alloy sorbents 352, 353 and/or 354 to effectively treat specific levels and/or types of contaminants remaining in the non-gaseous emissions 295.

After the contaminated non-gaseous effluent 295 is directed through a suitable prefilter, a prefilter outlet manifold 385 directs the effluent into the fluidized bed 253. For non-gaseous emissions 295, the shell of the fluidized bed 253 is disposed in a direction substantially perpendicular to the platform 271. The contaminants are separated from the adsorbent in step 258 and returned to the fluidized bed 253 through the adsorbent return port 260.

After the non-gaseous effluent 295 exits the fluidized bed 253, a post-filter monitoring step 386 determines a new level and/or type of contaminants remaining in the non-gaseous effluent 295 and directs the non-gaseous effluent 295 through a post-filter inlet manifold 387. The selection of the appropriate post-filters 388, 389, 390 and/or 391 is accomplished by the selection method shown in fig. 28. The post-filter shown in fig. 32 is filled with the reactive CZTS alloy sorbent 351 shown in fig. 28. For example, the post-filter 388 is filled with the CZTS alloy 352 of sulfur (S) shown in fig. 28. Post-filter 389 is filled with CZTS alloy 353 of selenate (S) shown in fig. 28. The post-filter 390 is filled with the ferrous oxide CZTS alloy 354 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 discharge 256b, with some of the non-gaseous emissions 295 being discharged through an environmentally controlled non-gaseous discharge 273 and some of the non-gaseous emissions 295 being discharged through an appropriate waste treatment step 262. Additional post-filters may be added to the post-filter inlet manifold 387, each of which is filled with a different combination of CZTS alloy sorbents 352, 353 and/or 354 to effectively treat specific levels and/or types of contaminants remaining in the non-gaseous emissions 295.

All of the 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 260, respectively. Step 258 includes separating contaminants from the CZTS alloy sorbent 351 so that the contaminants may be recycled and/or properly collected for treatment 261. Any depleted CZTS alloy sorbent 351 may be processed by a processing step 259. Replacement of a particular CZTS alloy sorbent 351 for each particular pre-filter 381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be performed after step 258. Specific routing and/or schematic diagrams for directing the sorbent from the pre-filters 388, 389, 390, 391 and/or post-filters 388, 389, 390, 391 to the sorbent cleaning step 258 and for directing the sorbent from the sorbent cleaning step 258 are not shown.

Referring to FIG. 33, an exemplary emissions control system is shown. Contaminated effluent is introduced into the fluidized bed 152 via inlet 165. It should be appreciated 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 reverse venturi shaped housing 16 having a specific length L to diameter D dimension ratio at a minimum of 2.9:1 and maximum 9.8: 1. This ratio is optimized for the extended residence flow time of the contaminated effluent in the fluidized bed 152, with the fluidized bed 152 being filled with a specialized reactive material 164 comprising one or more adsorbents. The preferred exemplary length L to diameter D ratio of the fluidized bed 152 is 4.4:1, which has been determined by a trial and error test. 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 restriction barriers disclosed herein may be incorporated into the fluidized bed 152. The fluidized bed 152 also has dominant outwardly extending male ends 168, 169 to promote extended residence flow time while minimizing turbulence through the reactive material 164. As 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-turbulent flow 166. Due to the predominantly outwardly extending

convex ends

168, 169, the random non-turbulent flow 166 turns around itself, resulting in an increased residence time in the fluidized bed 152 before the non-turbulent flow 166 exits from the fluidized bed 152 through the outlet 167. The reactive material 164 promotes random non-turbulent flow 166, which is a random tortuous flow path for the contaminated emissions. It should be appreciated that the length L of the fluidized bed 152 does not include the male 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 apparatus may make some automatic adjustments, while other process and/or system parameters may require manual adjustments. The monitoring sensor station 421 provides information regarding the efficiency of the adsorbent inside the fluidized bed 152 and helps determine when to clean and/or regenerate the adsorbent.

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

side outlet

403, 409, 415 leading to the

sorbent recycling subsystem

400, 401, 402, respectively. The

sorbent recycling subsystem

400, 401, 402 shown in fig. 33 is located outside of the fluidized bed 152, but alternatively they may be mounted 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 conditions 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 related 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 a sorbent condition when 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., the second monitoring sensor) is configured to monitor emissions flow level, pressure, speed, temperature, and many other related 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. As the cleaning and/or regeneration process occurs, the monitoring sensor 424 monitors the conditions and resulting volume of the adsorbent as the adsorbent is processed in

stations

404, 410, or 416 within

subsystems

400, 401, or 402, respectively. The

monitoring sensors

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

monitoring subsystems

400, 401, 402 will determine when and how much, respectively, the

secondary stations

408, 413, and 419 need to replenish the adsorbents.

In another exemplary embodiment (not shown), the cleaning and/or regeneration subsystem is installed and configured inside the fluidized bed 152. In this configuration, the functions of the

monitoring sensors

421, 422, 423, 424 and the

sorbent recirculation subsystem

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, then the adsorbent recirculation subsystem 400 is used to maintain optimal process conditions for the CZTS adsorbent. The sorbent discharge 403 allows for transfer of the sorbent into the sorbent recycling station 404. The sorbent recycling station 404 in subsystem 400 includes one or more chemicals that separate contaminants from the CZTS sorbent as part of the cleaning and regeneration process. As a non-limiting example, the chemical agent used in the sorbent recycling station 404 may be selected from a group of fatty alcohols. Spent and/or depleted CZTS sorbent may be processed by the sorbent processing station 405. Emissions contaminants removed from the emissions may be recycled back into the various industries through the contaminant treatment port 406. A batch refill station 408, such as a new/fresh sorbent vessel, provides a supplemental supply of CZTS sorbent that replaces the sorbent that has been removed and/or spent during the removal of contaminants from the effluent. The CZTS sorbent return port 407 completes the closed loop back into the fluidized bed 152.

When the fluidized bed 152 is filled with the reactive material 164 comprising CTZS alloy sorbent, then the sorbent recirculation subsystem 401 is used to maintain optimal process conditions for the CZTS alloy sorbent. The sorbent discharge 409 allows for transfer of the sorbent into the sorbent recycling station 410. The sorbent recycling station 410 in subsystem 401 includes one or more chemicals that separate contaminants from the CZTS alloy sorbent as part of the cleaning and regeneration process. As a non-limiting example, the chemical agent used in the sorbent recycling station 410 may be selected from a group of fatty alcohols. The spent and/or depleted CZTS alloy sorbent may be processed by the processing station 411. Emissions contaminants removed from the emissions may be recycled back into the various industries through the contaminant treatment port 412. Batch refill station 413 provides a supplemental supply of CZTS alloy sorbent that replaces the sorbent that has been removed and/or failed during the removal of contaminants from the emissions. 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 that includes a carbon-based adsorbent, then the adsorbent recirculation subsystem 402 is used to maintain optimal process conditions for the carbon-based adsorbent. The sorbent discharge 415 allows for transfer of the sorbent into the sorbent recycling station 416. The sorbent recycling station 416 in subsystem 402 includes one or more chemicals that separate contaminants from the carbon-based sorbent as part of the cleaning and regeneration process. As a non-limiting example, the chemical reagent used in the sorbent recycling 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 processed by an adsorbent processing station 417. Emissions contaminants removed from the emissions may be recycled back into the various industries through the contaminant treatment port 418. The batch refill station 419 provides a supplemental supply of carbon-based sorbent that replaces the sorbent that has been removed and/or failed during the removal of contaminants from the emissions. The carbon-based adsorbent return port 420 completes the closed loop back into the fluidized bed 152.

According to one 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 recycling subsystems

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

sorbent recycling subsystems

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

sorbent recycling subsystems

400, 401, 402.

Monitoring sensors

421, 422, 423, 424 are just a few 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 emission control system, which stations 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 type of 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 includes the steps of: directing the effluent into a treatment system comprising a reverse venturi-shaped fluidized bed apparatus 152 comprising one or more adsorbents chemically bound to contaminants carried in the effluent; and a fluidized bed apparatus 152 that directs the effluent away from the reverse venturi shape after the contaminants bind to the adsorbent. According to the method, the adsorbent is selected from the group comprising: copper Zinc Tin Sulfide (CZTS) adsorbents, copper Zinc Tin Sulfide (CZTS) alloy adsorbents, and carbon-based adsorbents. The method further comprises the steps of: the sorbent is directed through one or more

sorbent recirculation subsystems

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

adsorbent recirculation subsystem

400, 401, 402, disposing of the spent and exhausted adsorbent, separating contaminants from the adsorbent directed through the

adsorbent recirculation subsystem

400, 401, 402, disposing of or recirculating the contaminants, and returning the recirculated adsorbent to the reverse venturi-shaped fluidized bed apparatus 152. Optionally, the method may comprise the steps of: the new adsorbent is directed to a reverse venturi shaped fluidized bed apparatus 152 to replace the spent and depleted adsorbent.

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

sorbent recirculation subsystems

400, 401, 402, the method may further include the steps of: the different adsorbents in the reverse venturi-shaped fluidized bed apparatus 152 are separated from one another, at least one process parameter of the reverse venturi-shaped fluidized bed apparatus is detected by one or

more monitoring sensors

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

monitoring sensors

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

adsorbent recirculation subsystems

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

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 unless otherwise indicated without departing from the scope of the disclosure. Likewise, it is to be understood that the methods described and illustrated herein may be performed without including all of the steps described above or with the addition of intermediate 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 novel features of the invention which are useful in their intended applications. The use of the word "the" in the apparatus claims refers to a precondition that is an active statement that is intended to be included in the scope of the claims, and that the word "the" is not intended to be included in the scope of the claims before the word.

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 a reverse venturi, the housing including an inlet portion for receiving the effluent at a predetermined inlet flow rate, an outlet portion for discharging the effluent at a predetermined outlet flow rate, and an enlarged portion disposed between the inlet portion and the outlet portion of the housing for capturing the contaminants in the effluent;

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

A quantity of reactive material disposed within the enlarged portion of the housing, the quantity of reactive material including a sorbent comprising a carbon-based sorbent having elemental Cu ₂ ZnSnS ₄ CZTS, CZTS alloys, or combinations thereof;

the quantity of reactive material having a reactive outer surface disposed in contact with the emissions; and

at least one sorbent recycling subsystem disposed in fluid communication with the housing, the sorbent recycling subsystem receiving sorbent from the housing via a sorbent discharge and returning cleaned sorbent to the housing via a sorbent return, the at least one sorbent recycling subsystem comprising a chemical reagent for separating contaminants from the at least one sorbent, the chemical reagent comprising a fatty alcohol,

wherein the at least one sorbent recycling subsystem comprises a first sorbent recycling subsystem, a second sorbent recycling subsystem, and a third sorbent recycling subsystem; or includes a first sorbent recirculation subsystem and a third sorbent recirculation subsystem; or a second sorbent recycling subsystem and a third sorbent recycling subsystem,

Wherein the first sorbent recirculation subsystem is connected in fluid communication with the housing of the fluidized bed device at a first sorbent recirculation subsystem location, the first sorbent recirculation subsystem dedicated to treating CZTS;

the second sorbent recirculation subsystem is connected in fluid communication with the housing of the fluidized bed apparatus at a second sorbent recirculation subsystem location, the second sorbent recirculation subsystem being dedicated to treating CZTS alloy;

the third sorbent recirculation subsystem is coupled in fluid communication with the housing of the fluidized bed device at a third sorbent recirculation subsystem location, the third sorbent recirculation subsystem being dedicated to treating carbon-based sorbents.

2. The emissions control system of claim 1, wherein the housing of the fluidized bed apparatus is permanently installed in the field.

3. The emissions control system of claim 1, wherein the housing of the fluidized bed apparatus is transportable.

4. The emissions control system of claim 1, wherein the housing of the fluidized bed device comprises a longitudinal plane that is horizontally oriented when the fluidized bed device is configured for gaseous emissions.

5. The emissions control system of claim 1, wherein the housing of the fluidized bed device comprises a longitudinal plane that is vertically oriented when the fluidized bed device is configured for non-gaseous emissions.

6. The emissions control system of claim 1, wherein the at least one sorbent recirculation subsystem is located outside of the housing of the fluidized bed apparatus.

7. The emissions control system of claim 1, wherein the at least one sorbent recirculation subsystem is located inside the housing of the fluidized bed apparatus.

8. The emission control system of claim 1, wherein the at least one sorbent recirculation subsystem has a closed loop configuration.

9. The emission control system of claim 1, wherein the at least one sorbent recycling subsystem includes a sorbent treatment station that separates spent and exhausted sorbent for treatment.

10. The emission control system of claim 1, wherein the at least one sorbent recirculation subsystem includes a pollutant treatment port that discharges pollutants separated from the emissions for recirculation or treatment.

11. The emission control system of claim 1, wherein the at least one sorbent recycling subsystem includes a batch refill station that supplies new sorbent to the sorbent return port to replace spent and exhausted sorbent.

12. The emission control system of claim 1, further comprising:

a first monitoring sensor located within the housing of the fluidized bed apparatus configured to monitor at least one process parameter of the fluidized bed apparatus; and

a second monitoring sensor included in the at least one sorbent recirculation subsystem, the second monitoring sensor configured to monitor at least one parameter of the sorbent in the sorbent recirculation subsystem.

13. The emission control system of claim 1, wherein the at least one sorbent recycling subsystem is configured to treat carbon-based sorbents including methyl ethyl ketone, methylene chloride, methanol, or a combination thereof for separating contaminants from at least one of the carbon-based sorbents.

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

Directing the effluent into a treatment system comprising a reverse venturi-shaped fluidized bed apparatus comprising at least one adsorbent that is chemically bound to contaminants entrained in the effluent;

directing the effluent away from the reverse venturi-shaped fluidized bed apparatus;

at least one adsorbent is selected from a group of materials comprising carbon-based adsorbents and further comprising a material having elemental Cu ₂ ZnSnS ₄ CZTS, CZTS alloys, or combinations thereof; and

directing the at least one adsorbent through at least one adsorbent recirculation subsystem for chemical cleaning and regeneration, the at least one adsorbent recirculation subsystem comprising a chemical agent for separating contaminants from the at least one adsorbent, the chemical agent comprising a fatty alcohol,

Wherein the first sorbent recirculation subsystem is connected in fluid communication with the housing of the fluidized bed device at a first sorbent recirculation subsystem location, the first sorbent recirculation subsystem being dedicated to treating CZTS;

15. The emission control method according to claim 14, further comprising the step of:

separating spent and depleted adsorbent from adsorbent directed through the adsorbent recirculation subsystem and disposing of the spent and depleted adsorbent;

separating contaminants from the adsorbent directed through the adsorbent recycling subsystem and treating or recycling the contaminants;

returning the recycled adsorbent to the reverse venturi-shaped fluidized bed apparatus; and

Directing new adsorbent to the reverse venturi-shaped fluidized bed apparatus to replace the spent and depleted adsorbent.

16. The emission control method of claim 14, further comprising:

the different adsorbents in the fluidized bed apparatus maintaining the reverse venturi shape are separated from each other;

detecting at least one process parameter of the inverted venturi-shaped fluidized bed apparatus with at least one monitoring sensor;

directing the effluent through one or more different sorbents based on the at least one process parameter detected by the at least one monitoring sensor;

directing CZTS through the first sorbent recirculation subsystem;

directing CZTS alloy through the second sorbent recirculation subsystem; and

the carbon-based adsorbent is directed through the third adsorbent recirculation subsystem.