TWI629093B - System and method for increasing the service life and/or catalytic activity of an scr catalyst and control of multiple emissions - Google Patents

Abstract

The present invention relates generally to the field of emissions control equipment for boilers, heaters, kiln or other flue gas or combustion gas generating devices (e.g., in power plants, processing plants, etc.), and more particularly to reducing or preventing SCR catalysts. Novel and useful methods and equipment for poisoning and/or pollution. In another embodiment, the present invention is directed to methods and apparatus for increasing the useful life and/or catalytic activity of an SCR catalyst while controlling various emissions. In yet another embodiment, the present invention relates to controlling, mitigating, and/or reducing a boiler, heater, kiln or other flue gas or combustion gas generating device (eg, located in a power plant, a processing plant, etc.) A method and apparatus for the amount of selenium contained in and/or discharged from one or more components of an emission control device.

Description

System and method for increasing the service life and/or catalytic activity of SCR catalysts and controlling multiple emissions Related application materials

U.S. Patent Application Serial No. 13/117,332, entitled "System and Method for Increasing the Service Life and/or Catalytic Activity of an SCR Catalyst and Control of Multiple Emissions", is hereby incorporated by reference. U.S. Patent Application Serial No. 13/117,332, filed on Jan. 21, 2010, entitled,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Priority 12/691, 527 and its continuation of its application, U.S. Patent Application Serial No. 12/691,527, which is filed on April 22, 2009, entitled "System and Method for Protection of SCR Catalyst" Priority of Patent Application No. 61/171,619 is a non-provisional case. The entire contents of these patent applications are hereby incorporated by reference in their entirety.

The present invention relates generally to the field of emissions control equipment for boilers, heaters, kiln or other flue gas or combustion gas generating devices (e.g., in power plants, processing plants, etc.), and more particularly to reducing or preventing SCR catalysts. Novel and useful methods and equipment for poisoning and/or pollution. In other embodiments, the method and apparatus of the present invention are designed to protect the SCR catalyst. In another embodiment, the present invention is directed to methods and apparatus for increasing the useful life and/or catalytic activity of an SCR catalyst while controlling various emissions. In yet another embodiment, the present invention relates to controlling, mitigating, and/or reducing a boiler, heater, kiln or other flue gas or combustion gas generating device (eg, located in a power plant, a processing plant, etc.) A method and apparatus for the amount of selenium contained in and/or discharged from one or more components of an emission control device. In still another embodiment, the invention relates to a method for adding at least one upstream of one of a wet flue gas desulfurization (WFGD) unit and/or a dry flue gas desulfurization (DFGD) unit by addition. A method and apparatus for controlling the formation of selenium species in one or both of a gas phase or an aqueous phase with a metal additive.

Nitric oxide (NO) NO _x refers arising during combustion, the cumulative emissions of nitrogen dioxide (NO ₂₎ and trace amounts of other nitrogen oxide species. It can be obtained due to high temperature and oxygen and nitrogen from both the air and the fuel, so the combustion of any fossil fuel will produce some degree of NO _x. After the NO _x emissions using low NO _x combustion technology and combustion technology be controlled. One technique involves combustion selective catalytic reduction (SCR) system after this, these catalyst systems facilitate NO _x with a reagent (usually ammonia) to produce the chemical reaction between water vapor and molecular nitrogen.

SCR technology are used worldwide to control NO _x emissions from a source of combustion. The technology from the late 1970s in Japan, from the late 1980s in Germany and _x control has been widely used in the United States from the 1990s for NO from the utility boiler. Industrial scale SCRs have been designed to operate primarily in the temperature range of 500 °F to 900 °F, but often operate in the range of 550 °F to 750 °F. SCR is typically designed to conform to the maximum allowable under the specified NO _x reduction efficiency of the dissipation of ammonia. Ammonia dissipation is the unreacted ammonia concentration (expressed in parts per million by volume) from which the SCR is discharged.

Relating to industrial and power generation use of NO _x removal additional technical details, the reader is referred to "Steam / its generation and use" ( first edition 41, Kitto and Stultz edited, copyright in 2005, The Babcock & Wilcox Company, Barberton, Ohio, USA), in particular Chapter 34, "Nitrogen Oxides Control", the contents of which are incorporated herein by reference in its entirety.

Regulatory regulations issued by the EPA are expected to increase the proportion of utility boilers equipped with SCR. SCRs are typically designed to provide a maximum efficiency of about 90%. This restriction is not eligible for SCR NO _x destruction induced a higher level of capability provided any theory. It is a practical limit setting that prevents excessive ammonia slip. The problem is explained below.

In an SCR, ammonia and NO _x according to one of the stoichiometry of the following reaction (a) to (d) or by the reaction:

4NO+4NH ₃ +O ₂ → 4N ₂ +6H ₂ O (a)

12NO ₂ +12NH ₃ → 12N ₂ +18H ₂ O+3O ₂ (b)

2NO ₂ +4NH ₃ +O ₂ → 3N ₂ +6H ₂ O (c)

NO+NO ₂ +2NH ₃ → 2N ₂ +3H ₂ O (d).

The above catalytic reaction takes place using a suitable catalyst. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Catalyst blends are generally divided into three categories: base metals, zeolites, and precious metals.

The base metal catalyst uses titanium oxide having a small amount of vanadium, molybdenum, tungsten or a combination of several other active chemicals. The base metal catalyst is selective and operates in a specified temperature range. The main disadvantage of the base metal catalyst is that it may oxidize SO ₂ to SO ₃ ; the degree of oxidation varies depending on the catalyst chemical composition. The amount of SO ₃ formed can be reacted with the ammonia residue to form various ammonium sulfate salts.

The zeolite catalyst is an aluminosilicate material, which acts similarly to the base metal catalyst. One of the possible advantages of zeolite catalysts is its higher operating temperature of about 970 °F (521 °C). Such catalyst can oxidize SO ₂ to SO ₃ and must be carefully matched to the flue gas conditions.

Precious metal catalysts are usually manufactured from platinum and rhodium. Precious metal catalysts also require careful consideration of flue gas composition and operating temperatures. Although such catalyst to effectively reduce NO _x, but also may be used as their oxidation catalyst under appropriate temperature conditions of CO into CO _2. However, the oxidation of SO ₂ to SO ₃ and high material costs often make precious metal catalysts less attractive.

As is known to those skilled in the art, various SCR catalysts are poisoned when contaminated with various compounds including, but not limited to, specific phosphorus compounds such as phosphorus oxide (PO) or phosphorus pentoxide (P ₂ O ₅ ). . In addition, it is well known that SCR catalysts deteriorate over time and must be periodically replaced at significant cost and lost capacity. In a typical 100 MWe coal-fired power plant, the downtime and cost associated with a catalyst with poor replacement performance would be around $1 million or more.

More specifically, when the SCR catalyst is exposed to dust-laden flue gas, there are numerous mechanisms including clogging, masking, and deactivation of the catalyst and degradation of catalyst performance over time. The most common toxic element of the catalyst, the arsenic, is burned when burning domestic eastern coal (ie coal mined in the eastern United States). The most common sensoric toxicant, phosphorus, and calcium sulphate are the most common shielding mechanisms when burning western coal (ie coal mined in the western United States). The method of recovering the used catalyst is called a regeneration washing or a rejuvenation method. The initial step of the regeneration process involves removing the toxic chemicals by treating the catalyst with various different chemical baths that dissolve the poison. Although this treatment is excellent in removing the desired poison, it produces wastewater having a very high arsenic concentration.

In other states, the Powder River Basin/Lignite coal-fired power plant, any coal/biomass co-combustion, or any coal/bone meal co-combustion or even pure-mass burning power plants suffer from phosphorus contamination of the SCR catalyst.

Further, in addition to control NO _x emissions must be considered and / or to comply with emission control amenable to various other state, the EPA and / or air purification Specification (Clean Air Act regulation). A boiler, heater, kiln, or other means to generate a combustion gas or flue gas emission control of a number of other (e.g. means located at power plants, processing plants, etc.) must be considered in terms include, but are not limited to, mercury, SO _x and specific particle.

In addition, in most cases, if not all, it is desirable to remove various gases from the flue gas by one or more wet flue gas desulfurization (WFGD) units or one or more dry flue gas desulfurization (DFGD) units. SO _x compound. As known in the art are familiar with those of the present, it is common (and in most cases is now needed) also removed together with the removal of SO _x and / or reduce the amount of mercury in the flue gas. One suitable mercury control method is mercury oxidation and capture by the use of one or more halogen compounds to achieve the above mercury oxidation and subsequent capture of the oxidized mercury compound (eg, in the form of a halohalide). It has been found that when the mercury control system is completely or partially via the use of one or more halogen compounds (eg, halogenated salts such as calcium bromide, etc.), such compounds have a negative impact on the formation of selenium species in the flue gas, which in turn is selenium discharged liquid effluent from one or more units or out of WFGD and / or by one or more negative effects to control the amount of particulate matter generated DFGD unit of the same flue gas stream of SO _x in. However, it should be noted that the present invention is not limited to the above. In fact, in one embodiment, the invention relates to controlling, mitigating and/or reducing a boiler, heater, kiln or other flue gas or combustion gas generating device (eg, located in a power plant, a processing plant, etc.) A method and apparatus for the amount of selenium contained in and/or discharged from one or more components of an emission control device. In another embodiment, the invention relates to a point for use upstream of one of a wet flue gas desulfurization (WFGD) unit and/or a dry flue gas desulfurization (DFGD) unit (hereinafter A method and apparatus for controlling the formation of selenium species in one or both of a gas phase or an aqueous phase by adding at least one metal additive will be described in detail. In another embodiment, the present invention provides a method for simultaneously controlling the formation of selenium species in at least one of the gas phase or the aqueous phase while further controlling the gas phase phosphorus and gas in at least one of the emissions from the combustion process. A method and apparatus for at least one of phase sodium, vapor phase potassium, and/or mercury.

Under the circumstances described above, there is a need for a method of providing any economical and environmentally suitable method and/or system for controlling selenium emissions from one or more components of an emission control device for use with a combustion process. Additionally or alternatively, there is a need to control selenium emissions while controlling one or more gas phase compounds (such as phosphorus, sodium, and/or potassium) while increasing the catalyst lifetime and/or catalyst activity of the SCR catalyst, and even in some instances. A method used to control other capabilities of mercury emissions.

The present invention relates generally to the field of emissions control equipment for boilers, heaters, kiln or other flue gas or combustion gas generating devices (e.g., in power plants, processing plants, etc.), and more particularly to reducing or preventing SCR catalysts. Novel and useful methods and equipment for poisoning and/or pollution. In another embodiment, the method and apparatus of the present invention are designed to protect the SCR catalyst. In yet another embodiment, the present invention is directed to methods and apparatus for increasing the useful life and/or catalytic activity of an SCR catalyst while controlling various emissions. In yet another embodiment, the invention relates to controlling, mitigating and/or reducing emissions from boilers, heaters, kilns or other flue gases or combustion gases A method and apparatus for the amount of selenium contained in and/or discharged from one or more components of a body control device (e.g., at a power plant, a processing plant, etc.). In yet another embodiment, the invention relates to a method for adding at least upstream of one of a wet flue gas desulfurization (WFGD) unit and/or a dry flue gas desulfurization (DFGD) unit by addition. A method and apparatus for controlling the formation of selenium species in one or both of a gas phase or an aqueous phase with a metal additive.

Accordingly, one aspect of the present invention is directed to a method of increasing the active life of an SCR catalyst, the method comprising the steps of: (a) providing at least one compound carrying iron to the furnace or before the flue gas enters the SCR a combustion zone or a flue gas stream of the boiler; and (b) allowing at least one iron-carrying compound and any gaseous phosphorus compound present in the combustion zone or flue gas or before the flue gas enters the SCR Phosphorus compound reaction; (c) providing at least one halide-carrying compound to the combustion zone or flue gas stream of the furnace or boiler prior to the flue gas entering the SCR, provided that the halide-carrying compound is not Iron halide; and (d) allowing the at least one halide-carrying compound to react with and/or oxidize any mercury present in the combustion zone or flue gas, wherein the process is achieved at an operating time of at least about 2,000 hours Either or both of the catalytic activity and/or catalytic lifetime are increased by at least about 10%.

In another aspect of the invention, a method of increasing the active life of an SCR catalyst is provided, the method comprising the steps of: (i) providing at least one compound carrying iron to the furnace before the flue gas enters the SCR Or the combustion zone of the boiler or the flue gas stream; and (ii) the flue gas enters the Prior to SCR, at least one iron-carrying compound is allowed to react with any gaseous phosphorus compound or phosphorus-containing compound present in the combustion zone or flue gas; (iii) at least one of the flue gases is carried before the SCR enters the SCR The halide compound is provided to the combustion zone or flue gas stream of the furnace or boiler, provided that the halide-carrying compound is not an iron halide; and (iv) allows the at least one halide-carrying compound to be present in the Any mercury in the combustion zone or flue gas reacts and/or oxidizes any mercury, wherein the process achieves at least about 10% increase in catalytic activity and/or catalytic lifetime over a period of at least about 3,000 hours of operation.

In another aspect of the invention, there is provided a method of simultaneously chelating one or more phosphorus compounds or phosphorus-containing compounds (in the form of one or more less reactive iron-phosphorus containing compounds) and oxidized mercury, the method comprising The steps of: (A) providing at least one iron-carrying compound to the combustion zone or flue gas stream of the furnace or boiler; (B) allowing at least one iron-carrying compound to be present in the combustion zone or flue gas Any of the gaseous phosphorus compounds or phosphorus-containing compounds are reacted to form one or more less reactive iron-phosphorus containing compounds; (C) providing at least one halide-carrying compound to the flue gas prior to entering the SCR a combustion zone or a flue gas stream of the furnace or boiler, wherein the halide-carrying compound is not an iron halide; and (D) allowing the at least one halide-carrying compound to be present in the combustion zone or flue gas Any mercury reacts and/or oxidizes any mercury, wherein the process results in at least about 10% increase in catalytic activity and/or catalytic lifetime over a period of at least about 4,000 hours of operation.

In another aspect of the invention, a simultaneous chelation is provided Or a plurality of phosphorus compounds or phosphorus-containing compounds (in the form of one or more less reactive iron-phosphorus containing compounds) and oxidized mercury, the method comprising the steps of: (I) providing at least one compound carrying iron To the combustion zone or flue gas stream of the furnace or boiler; (II) allowing at least one iron-carrying compound to react with any of the gaseous phosphorus compounds or phosphorus-containing compounds present in the combustion zone or flue gas to form one or a plurality of lower reactivity iron-phosphorus compounds; (III) providing at least one halide-carrying compound to the combustion zone or flue gas stream of the furnace or boiler prior to the flue gas entering the SCR, the condition being The halide-carrying compound is not an iron halide; and (IV) allows the at least one halide-carrying compound to react with any mercury present in the combustion zone or flue gas and/or oxidize any mercury, wherein the method is obtained Either or both of the catalytic activity and/or the catalytic lifetime increase by at least about 15% at an operating time of at least about 3,000 hours.

In another aspect of the invention, there is provided a method of chelation of one or more phosphorus compounds or phosphorus-containing compounds (in the form of one or more less reactive iron-phosphorus containing compounds) while simultaneously chelation of mercury, the method comprising The method of providing at least one iron-carrying compound to a combustion zone or a flue gas stream of a furnace or a boiler; allowing at least one iron-carrying compound and any gaseous phosphorus compound present in the combustion zone or flue gas Or reacting the phosphorus-containing compound to form one or more less reactive iron-phosphorus containing compounds; providing at least one halide-carrying compound to the combustion zone or smoke of the furnace or boiler prior to the flue gas entering the SCR a gas stream, the condition being such that the halide-carrying compound is not an iron halide; and allowing the at least one halide-carrying compound to react and/or oxidize with any mercury present in the combustion zone or flue gas Any mercury wherein the process is such that at least about 15% of the catalytic activity and/or catalytic lifetime is increased by at least about 4,000 hours of operation time.

In another aspect of the invention, a method for controlling selenium species formation in at least one component of a flue gas and/or emission control device is provided, the method comprising the steps of: before the flue gas enters the SCR Providing at least one metal-carrying compound to a combustion zone or flue gas stream of a furnace or boiler; and allowing the at least one metal-carrying compound to be present in the combustion zone, flue gas, gas phase, and/or emission control Reaction of any selenium and/or selenium compound in at least one component of the apparatus, wherein the method permits control of selenium species formation in one or more gas phases and/or in the at least one component of the emission control device, thereby The amount of selenium emitted in the flue gas and/or from one or more components of the emission control device is reduced.

In another aspect of the invention, a method of simultaneously increasing the active life of an SCR catalyst and controlling selenium species formation in at least one component of a selenium species formation and/or emission control device in a flue gas is provided, the method comprising Steps of providing at least one iron-carrying compound to the combustion zone or flue gas stream of the furnace or boiler before the flue gas enters the SCR; and allowing at least one to carry while the flue gas enters the SCR Any of the gaseous compounds and any of the gaseous phosphorus compounds or phosphorus-containing compounds present in the combustion zone or flue gas and any of the components present in the combustion zone, the flue gas, the gas phase and/or the emission control device Selenium and/or selenium compound reaction wherein the process achieves at least about 10% increase in catalytic activity and/or catalytic lifetime at an operating time of at least about 2,000 hours while allowing control of one or more gas phases Medium and / or emission control The selenium species in the at least one component is formed to cause a reduction in selenium emissions in the flue gas and/or from one or more components of the emission control device.

In another aspect of the invention, a method for controlling at least one component of the selenium species in the flue gas and / or emission control device together with the forming method of the post-combustion CO ₂ capture process, the method comprising the step shown below : providing at least one metal-carrying compound to a combustion zone or flue gas stream of the furnace or boiler before the flue gas enters the SCR; and allowing the at least one metal-carrying compound to be present in the combustion zone, the flue gas Reacting any of the selenium and/or selenium compounds in at least one component of the gas phase and/or emission control device, wherein the method permits control of one or more gas phases and/or at least one component of the emission control device the speciation of selenium, resulting in the flue gas emission control device from the one or more components and / or at least reduced with the selenium compound in an amine emissions in the post combustion CO ₂ capture program and.

The various features of the novel features which are characteristic of the invention are particularly pointed out in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS For a fuller understanding of the present invention, the advantages of the invention,

12‧‧‧Boiler

14‧‧‧ Raw coal

16‧‧‧ coal silo

18‧‧‧ feeder

20‧‧‧ Coal Crusher

22‧‧‧ Burner

24‧‧‧burner area

26‧‧‧ furnace

28‧‧‧flue gas

30‧‧‧The upper part of the boiler

32‧‧‧Rectangle

34‧‧‧Vertical convection channel

36‧‧‧The upper part of the horizontal convection channel

38‧‧‧Horizontal convection channel

40‧‧‧Selective Catalytic Reduction (SCR) Equipment

42‧‧‧Air heater

44‧‧‧Particle collection device

47‧‧‧ESP (electrostatic dust collector)

48‧‧‧Stacking

49‧‧‧Circulating dry scrubber

50‧‧‧ spray dryer equipment

52‧‧‧ Burnout Air (OFA)

54‧‧‧Addition funnel area

100‧‧‧ system

110‧‧‧Iron as a substrate for phosphorus-reducing compounds

120‧‧‧Storage tools

130/135‧‧‧Delivery tools

150‧‧‧Control tools

140‧‧‧ Raw coal with iron-based phosphorus-reducing compounds added

160‧‧‧Operator interface

170/180/190/195‧‧‧Control or signal line

200‧‧‧Sensor/Location

1 is a schematic diagram of a petrochemical fuel combustion facility typically using an SCR system, and including a system for practicing the method of the present invention; and FIG. 2 is a diagram illustrating a A diagram of an example of improved catalytic activity and/or catalytic lifetime achieved by a system and method of an embodiment.

Detailed description of the invention

Although the ammonia often preferred in terms of economic factors, and therefore be described using ammonia as the NO _x reductant SCR system, but the present invention is not limited to ammonia based on the system. The concept of the invention can be used in any system that uses ammonia compounds. As used in the present invention, urea, compound terms such as ammonium sulfate, and ammonium cyanate and an organic amine (NH ₃₎ the amino compound is meant to include. These compounds are useful as reducing agents other than ammonia, but as mentioned above, ammonia is often preferred in terms of economic factors. Certain non-ammonia compounds (such as carbon monoxide or methane) may also be used, but there are losses in their effective aspects.

Furthermore, although the present invention describes mercury oxidation and the use of a halogen compound in the form of a halide salt (e.g., calcium bromide), the invention is not limited to this type of mercury oxidation and capture. Rather, any type of mercury control process can be used with the present invention and as the present invention, and in various embodiments, the ability to simultaneously control the amount of gas phase phosphorus and the formation of selenium species is sought. In other embodiments, the present invention seeks to simultaneously control the amount of gas phase phosphorus, the amount of mercury, and the selenium species formation properties in the flue gas.

Although the invention has been described as being associated with a boiler or fossil fuel boiler, it is not limited thereto. In contrast, the present invention is applicable to any combustion source that generates NO _x (whether such a combustion source is a boiler and used) or the steam generator. For example, the present invention should produce combustion flue gas containing NO _x or the kiln with combustion gas, or any other type of heater whole or in part and dried. Therefore, the following series should be considered as an example only.

As shown in Figure 1, the present invention is applicable to a boiler arrangement that uses wet flue gas desulfurization (WFGD or wet scrubber) to remove sulfur oxides from flue gas, as shown in the upper right side of Figure 1. In this configuration, the wet scrubber (in the direction of the flue gas flow through the system) is typically a particulate collection device (PCD), advantageously a fabric filter (FF) bag filter, or an electrostatic precipitator (ESP). . If desired, also be provided a wet electrostatic precipitator (wet ESP or the WESP), which may be provided as microparticles or SO ₃ ultimate "purification (Polishing)" stage. Alternatively, the present invention is applicable to a system that uses a spray dryer apparatus (SDA) or a dry scrubber to remove sulfur oxides from the flue gas, as shown in the lower right side of FIG. In this configuration, the SDA or dry scrubber (in the direction of the flue gas flow through the system) is typically a particulate collection device (PCD), advantageously a fabric filter (FF) or bag filter, or an electrostatic precipitator ( ESP) or even a wet electrostatic precipitator (wet ESP).

Further, the present invention can be applied to any SCR catalyst because of the seeding compound (such as but not limited to, H ₃ PO _4, PO or P ₂ O ₅₎ and phosphorus poisoning adversely affected. Therefore, the present invention is not limited to any type of SCR catalyst, but can be widely applied to a wide range of SCR catalyst systems. Suitable catalyst systems to which the present invention may be applied include, but are not limited to, honeycomb, plate or wave type configurations.

In one embodiment, the invention relates to reducing the rate of deactivation of an SCR catalyst on a Powder River Basin (PRB) coal fired unit. It should be noted that although the invention is described in relation to PRB coal, the present invention Ming is not limited to this. Rather, the invention is broadly applicable to any state in which the SCR catalyst is poisoned by one or more gaseous phosphorus compounds.

In one embodiment, it is suspected that phosphorus in the PRB coal causes staged combustion and rapid deactivation in other units. It is suspected that the deactivation system is caused by the gas phase phosphorus released by the carbothermal reduction reaction. In the reaction under the anoxic condition, the phosphorus-bearing compound releases the gas phase phosphorus by the following reaction: P ₂ O ₅ (solid phase compound) + 3C (s) → 2PO (g) + 3 CO (g).

The phosphorus vapor adhering to the active sites within a catalyst, to cause such portion for reducing the NO _x deactivated. The SCR catalyst deactivation results of the NO _x reduction system to the process can not be used without a catalyst of the same performance level.

In one embodiment, the present invention is directed to a system and method for preventing formation of a gas phase phosphorus species in a combustion environment, thereby reducing, mitigating, and/or eliminating SCR deactivation rates. In one embodiment, the present invention achieves the above objectives by adding at least one iron-carrying compound to the PRB coal prior to combustion.

In other embodiments, the present invention is directed to a system and method designed to increase catalytic activity and/or catalytic lifetime. In this case, the increase in catalytic activity and / or increased catalyst life of the system for a given standard boilers, fossil fuel boilers, kilns, or to produce flue gas heater or any other type of device containing the combustion gases of NO _x in Or known catalytic activity and/or lifetime decay rate to measure.

In one embodiment, the iron-bearing compound of the present invention is any iron compound (e.g., an iron oxide compound) that can undergo reduction in a common combustion environment such as a boiler, furnace, power plant, or the like. In other embodiments, the iron-bearing compound of the present invention may be a water-soluble, or water-insoluble, iron-bearing compound. Suitable water-soluble inorganic compounds with iron include, but are not limited to, iron (II) acetate (for example, Fe(C ₂ H ₃ O ₂ ) ₂ .4H ₂ O), iron (II) nitrate (for example, Fe (NO) ₃ ) ₂ .6H ₂ O), iron (III) nitrate (for example, Fe(NO ₃ ) ₃ .6H ₂ O or Fe(NO ₃ ) ₃ .9H ₂ O), iron (II) sulfate (for example, FeSO _{4 )} .H ₂ O, FeSO ₄ .4H ₂ O, FeSO ₄ .5H ₂ O or FeSO ₄ .7H ₂ O), iron (III) sulfate (for example, Fe ₂ (SO ₄ ) ₃ .9H ₂ O) or Or a mixture of many. Although various hydrated forms of iron-bearing compounds are listed herein, the invention is not limited to the above listed hydrated forms. Rather, any corresponding anhydrous form of the compound bearing iron listed above may also be used in conjunction with the present invention, if possible. In this case, when reference is made herein to a compound carrying iron, whether or not the chemical formula is given "bound water", it should be construed as including a hydrated form or an anhydrous form. Suitable water-insoluble compounds with iron include, but are not limited to, metallic iron, one or more iron oxides, iron carbonate or a mixture of two or more thereof. In addition, a wide range of water-soluble or water-insoluble organic compounds carrying iron can be used in combination with the present invention. As discussed below, the iron-bearing compound of the present invention may be supplied in any desired form including, but not limited to, in powder form, in solid form, as an aqueous solution, as an aqueous suspension or emulsion, or as a compound carrying iron. Or any combination of many different forms. In another embodiment, when two different forms of iron-carrying compounds are supplied in conjunction with the present invention, the iron-laden compounds supplied via the various forms may be the same or different. In a particular embodiment, the iron-carrying compound is iron (III) oxide (Fe ₂ O ₃ ), also known as hematite or hematite. In the embodiment using iron oxide (III), the important reaction occurring in the combustion part of the boiler or furnace is as follows: 3Fe ₂ O ₃ (s) + CO (g) → 2Fe ₃ O ₄ (s) + CO ₂ (g) (1)

Fe ₃ O ₄ (s) + CO (g) → 3 FeO (s) + CO ₂ (g) (2).

It should be noted that the above-mentioned first reaction of Fe ₃ O ₄ (also known as black iron oxide or magnetite) can also be more accurately written as FeO. Fe ₂ O ₃ . FeO or iron oxide (II) (also known as ferrous oxide, which is produced by the reduction of Fe ₂ O ₃ ) can be combined, combined and/or chelated in the combustion zone or boiler or furnace before reaching the SCR Any PO gas in the flue gas. This PO gas then forms an Fe-P compound in the form of a particulate phase before reaching the SCR. The particles will pass through the catalyst and prevent catalyst degradation.

In other embodiments, the present invention may use iron (II) carbonate, which is converted into the desired iron (II) oxide in the combustion zone by the reaction shown below: FeCO ₃ (s) → FeO (s) ) +CO ₂ (g) (3).

In another embodiment, the invention may employ a combination of one or more iron-containing compounds and one or more halide compounds, provided that the halide-containing compound is not an iron halide. Therefore, in this embodiment, at least one iron-containing compound is used in combination with at least one non-halogen-containing compound. In another embodiment, the at least one iron compound has the general formula AX, wherein A is equal to iron and X is an oxide or carbonate ion, an anion and/or a moiety, and the at least one halide compound has the formula BY, Wherein B is any atom, element or cation other than iron, and Y is a halide selected from chlorine, bromine, fluorine or iodine.

In one embodiment, halides suitable for use in conjunction with the present invention include, but are not limited to, potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide. , calcium bromide, calcium chloride, calcium fluoride, calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, other metal halides (eg, bromide, chloride, fluoride, and / Or iodide, the condition is that the metal is not iron), or any mixture of two or more thereof. In another embodiment, any one or more of the halide compounds according to the conditions defined above may be used in combination with one or more non-halide-containing iron compounds such as iron (II) carbonate. In another embodiment, the invention uses a combination of iron (II) carbonate and calcium bromide to control the amount of phosphorus in the flue gas or combustion gases while allowing control of mercury compounds in the flue gas or combustion gases or Contains mercury compounds and increases catalytic activity and/or service life. In yet another embodiment, the invention uses a combination of iron (II) carbonate and calcium chloride to control the amount of phosphorus in the flue gas or combustion gases while permitting control of mercury compounds in the flue gas or combustion gases Or containing mercury compounds and increasing catalytic activity and/or service life. In yet another embodiment, the present invention uses either or both of iron (II) carbonate and aluminum bromide and/or aluminum chloride to control the amount of phosphorus in the flue gas or combustion gas while allowing Controls mercury compounds or mercury-containing compounds in flue gases or combustion gases and increases catalytic activity and/or service life. As used herein, a mercury compound or a mercury-containing compound includes, but is not limited to, any compound containing mercury oxide or a combination elemental mercury. In another embodiment, the invention relates to the simultaneous permitting control of mercury compounds or mercury containing compounds that are predominantly or exclusively containing oxidized mercury.

Any iron suitable for use in conjunction with the present invention, as used herein The compounds can be used in hydrated or non-hydrated form. Thus, reference to any iron compound as defined herein includes any hydrated form, whether or not specifically recited in the chemical formula.

As is known in the art, (for example, see, for example, U.S. Patent Application Publication No. 2008/0107579, the disclosure of which is incorporated herein in its entirety by reference in its entirety herein in its entirety in Elemental mercury in combustion gases. Thus, the oxidation reaction, the halide portion of the applicable halide-containing compound allows the conversion of elemental mercury to one or more suitable environmental control techniques (eg, a wet scrubber or a spray-dry scrubber (SDA), smoke). a more advantageous form of subsequent capture or sequestration of a gas desulfurization system (FGD), a powdered activated carbon system (PAC) or a particulate collection system, such as a fabric filter (FF) or an electrostatic precipitator (ESP) . In one example, the addition of one or more halide-containing compounds also increases the amount of particulate bound mercury as is known in the art. In the context of numerous patents and published applications detailing the application of a halide-containing compound to allow for the recovery of mercury from flue gases or combustion gases, detailed discussion is omitted for the sake of brevity.

In any of the above embodiments, the one or more compounds carrying iron (and one or more halide compounds if desired) may be added to the coal via one or more pulverizers. In another embodiment, one or more of the iron-bearing compounds of the present invention (and one or more halide compounds if desired) may be designed to transport the one or more iron-carrying compounds via one or more / or a powdered, solid, aqueous suspension, suspension or aqueous solution of the one or more halide compounds is delivered to the furnace and / or boiler A supply line to the combustion zone is added to the boiler and/or furnace. To this end, Figure 1 illustrates an embodiment of several suitable designs for achieving this result.

Referring to Figure 1, there is illustrated a schematic of a typical petrochemical fuel combustion facility (commonly referred to as 10) having an SCR system, and which includes a system for carrying out the method of the present invention. As shown, a boiler 12 is provided for extracting heat from combustion of a fossil fuel, such as coal, via combustion with an oxidant, typically air. The heat is transferred to a working fluid, such as water, to generate steam for power generation or for industrial processes and/or heating via expansion through a turbine generator (not shown).

The raw coal 14 must be crushed to the desired fineness and dried to promote combustion. The raw coal 14 is temporarily stored in the coal silo 16 and then transferred to one or more coal shredders 20 using a gravity or volumetric feeder 18. In the embodiment shown in Figure 1, there are six (6) coal pulverizers, designated as coal pulverizers A through F. As is known to those skilled in the art, each coal pulverizer 20 grinds the coal to the desired fineness (e.g., 70% through a 200 mesh screen) and, when the coal is ground, will be from primary air. The heat of the fan is mainly sent to each coal pulverizer 20 to preheat and remove the moisture of the coal to the desired level at the time of the coal grinding. The primary air is also used to transport the pulverized coal (PC) out of each coal pulverizer 20 and along a plurality of pulverized coal supply lines (one such burner line is labeled as A in Figure 1; The single coal pulverizer 20 can be supplied to the burners 22 on the front and rear walls of the boiler 12 via 4 to 8 pulverized coal supply lines. The burners 22 are typically located at spaced apart heights on the opposite front and rear walls of the boiler 12, or in angular combustion or tangential firing units (not shown). The corner of the boiler in the setting. The invention may be used with, but not limited to, single wall combustion, opposed wall combustion, and angular or tangential combustion units. Typically, a single coal pulverizer 20 provides only coal to a burner 22 of a single height on the wall. Therefore, in the embodiment shown in Fig. 1, six coal pulverizers A to F are supplied corresponding burner heights A to F. However, as is known to those skilled in the art, other pulverizer and burner configurations are known (e.g., a single pulverizer is supplied to a plurality of walls and/or heights of burners, or a plurality of pulverizers are supplied at a single height). Burner), and the invention applies to any such configuration.

The combustion process begins in the combustor zone 24 of the furnace 26 of the boiler 12, releasing heat and producing a hot flue gas 28 that is transported upwardly above the boiler 12 over a heated surface, generally indicated as a rectangle 32. Part 30. The flue gas 28 is then conveyed across the heated surface in the vertical convection passage 34 into the upper portion 36 of the horizontal convection passage 38. The flue gas 28 is then conveyed through a selective catalytic reduction system (SCR) equipment 40, the flue gas in which the NO _x is reduced, then schematically indicated in the main and auxiliary air heater device 42. The air heater 42 extracts additional heat from the flue gas 28, lowers the temperature of the flue gas, and preheats the incoming air for combustion.

As shown in Figure 1, downstream of air heater 42, the flue gas 28 undergoes further processing to remove particulates and sulfur oxides. Two typical configurations of downstream equipment for accomplishing such tasks are shown on the right side of Figure 1. The first apparatus configuration of Figure 1 includes a particulate collection device (PCD), shown schematically at 44, for removing particulates from the flue gas 28, and which may actually comprise a fabric filter or an electrostatic precipitator. A wet flue gas desulfurization (WFGD) unit (also known as a wet scrubber) is provided downstream of the PCD 44 for removal of sulfur oxides from the flue gas 28. May (optionally) the cleaned flue gas scrubbing conveyed through a wet ESP 47 for removing fine particles or SO _3, and then conveyed into the stacker 48 to be discharged to the atmosphere.

The second apparatus configuration of FIG. 1 includes a spray dryer apparatus (SDA) (also known as a dry scrubber), schematically shown at 50, for removing sulfur oxides from the flue gas 28. A particulate collection device (PCD) 44 is provided downstream of the SDA 50 for removing particulates from the flue gas 28, as previously described. The cleaned, scrubbed flue gas is then sent to stack 48 for discharge to the atmosphere.

The third apparatus configuration of FIG. 1 includes a circulating dry scrubber (CDS), schematically indicated at 49, for the removal of sulfur oxides from the flue gas 28. A particulate collection device (PCD) 44 is provided downstream of the CDS 49 for removal of particulates from the flue gas 28. As in the above-described embodiments, PCD 44 may comprise any suitable particulate collection device including, but not limited to, fabric filters or electrostatic precipitators as described above. The cleaned, scrubbed flue gas is then sent to stack 48 for discharge to the atmosphere.

The fourth apparatus configuration shown in Figure 1 includes a first particulate removal device in the form of an electrostatic precipitator (ESP), schematically indicated at 44. ESP 44 is constructed to remove fine particles from the flue gas 28. A circulating dry scrubber (CDS), shown schematically at 49, is provided downstream of the ESP 44 for removal of sulfur oxides from the flue gas 28. A second particulate collection device (PCD) 44 is provided downstream of the CDS 49 for removal of any residual particulates from the flue gas 28. As in the above embodiments, the PCD 44 may comprise any suitable particulate collection device, It includes, but is not limited to, fabric filters or electrostatic precipitators as described above. The cleaned, scrubbed flue gas is then sent to stack 48 for discharge to the atmosphere. In other embodiments, the ESP 44 is interchangeably interchangeable with the fabric filter unit.

The fifth apparatus configuration shown in Fig. 1 includes a first particulate removal device schematically shown in one of the fabric filters or electrostatic precipitator (ESP) forms of 44. FF/ESP 44 is constructed to remove fine particles from the flue gas 28. A spray dryer unit (SDA) (shown schematically at 50) (also known as a dry scrubber) is provided downstream of the FF/ESP 44 for removal of sulfur oxides from the flue gas 28. A second particulate collection device (PCD) 44 is provided downstream of the SDA 50 for removal of any residual particulates from the flue gas 28. As in the above-described embodiments, PCD 44 may comprise any suitable particulate collection device including, but not limited to, fabric filters or electrostatic precipitators as described above. The cleaned, scrubbed flue gas is then sent to stack 48 for discharge to the atmosphere.

In order to further reduce NO _x emissions, the use of some of the 12 stage combustion boiler, in which only part of the stoichiometric amount of air supplied to the primary combustion zone 24, the remainder of the air for combustion, together with the absence of any combustion process efficiency is 100% required Any excess air is provided above the burner zone 24 via an exhaust air (OFA) port 52. If staged combustion is used in the boiler 12, a reducing atmosphere is created in the lower portion of the furnace 26 (including the addition funnel zone 54) due to the reduced air supplied to the burner zone 24.

According to a first embodiment of the invention, one or more suitable carriers are carried before the pulverized coal is supplied to the one or more burners 22 The iron compound (and one or more suitable halide compounds if desired) is added to one or more coal pulverizers 20. The system and equipment used to achieve this desired result is also shown in Figure 1, generally referred to as 100. System 100 includes a storage tool 120 for temporarily storing an iron-based phosphorus-reducing compound (and, if desired, a mercury-reducing compound), generally referred to as 110; as needed to deliver the compound 110 to a desired location (including valves) The delivery means 130, 135 of the seals, etc.; and the control tool 150, which is advantageously a microprocessor-based control tool, is accessed by an operator via an operator interface (I/O) station 160. The Human Interface (I/O) station includes display and data collection and storage tools as needed. Although not illustrated individually, in one embodiment, the system of the present invention can utilize separate storage, delivery, and control tools (as described above) for various individual iron and/or halide compounds. In another embodiment, the system of the present invention may comprise a set of storage, delivery and control tools for the iron compound or a compound used herein and a set of storage, delivery for a halide compound or a compound used herein. And control tools (according to the above).

In Fig. 1, the raw coal 14 to which the iron-based phosphorus-reducing compound 110 has been added is referred to as 140. Advantageously, the iron-based phosphorus-reducing compound 110 can be provided along with the raw coal 14 via a feeder 18, which allows for the close control and measurement of both the raw coal 14 and the iron-based phosphorus-reducing compound 110 in the coal pulverizer. 20 delivery. Alternatively, the iron-based phosphorus reduction compound 110 can be provided directly to the coal pulverizer 20 and/or to one or more individual burner lines A through F, and the pulverized coal can be supplied to the individual burners 22, The coal pulverizer 20 or the burner lines A to F Applicable sealing device for anti-positive pressure. The delivery means may be slurry based or pneumatic as desired by the iron as the substrate phosphorus reducing compound 110 and the details of the amount and location of the flue gas 28 introduced. The interconnect configuration of control or signal lines 170, 180, 190, and 195 interconnects the different devices to provide control signals, iron-based phosphorous reduction compound 110 content signals, and phosphorus content signals in the flue gas 28 ( The introduction of the phosphorus-reducing compound 110 from the sensor 200) to allow the iron-based phosphorus-reducing compound 110 to enter the flue gas 28 is controlled by an operator or automatically controlled. However, if there is no suitable instant sensor 200 suitable for measuring the gaseous phosphorus content of the flue gas 28, a flue gas sample may be taken at location 200 for later laboratory analysis via applicable test methods. It can be an inductively coupled plasma-measurement (ICP-MS). Based on laboratory results, the operator can use the operator interface 160 to manually enter the desired set point of the amount of iron introduced into the flue gas 28 as the amount of the substrate-reducing phosphorus-reducing compound 110 into the control tool 150. The conditions are not subsequently shown by the laboratory analysis to show any significant change in the gas phase phosphorus content of the flue gas 28, and may not require the introduction of a phosphorus-reducing compound 110 that controls the iron as a substrate. Conversely, the amount of iron-inducing compound 110 that introduces the flue gas 28 to the substrate may be simply related to the boiler load or coal feed rate value.

In yet another embodiment, the invention uses iron (II) oxide. In the present embodiment, the need for a reduction reaction is eliminated, so that the addition point of the iron oxide (II) of the present embodiment is wider than that of the previous embodiment. In this example, iron (II) oxide may be added after combustion and at any suitable point prior to SCR to combine, bind and/or sequester before reaching the SCR. Any PO gas in the flue gas of a boiler or furnace. In particular, the iron-based phosphorus-reducing compound may be supplied in one or more of the positions G to Q shown in FIG. More particularly, the iron-based phosphorus-reducing compound may also be supplied to the flue gas 28 at one or more of the following locations: G: into the burner zone 24 or below, at the front wall, rear One or more of the walls or side walls are separated from the combustor 22 via a tool; H: enters the furnace 26 at a location above the combustor zone 24, in one or more of the front, rear or side walls; , J: entering the furnace 26 near the OFA port 52 or via the OFA port 52 on one or both of the front or rear wall; K: entering the boiler 12 in the vertical convection passage 34; L: in the horizontal convection passage 38 The upper portion 36 enters the boiler 12; M, N, O, P: enters the boiler 12 in the horizontal convection passage 38; and/or Q: enters the boiler 12 in the addition funnel region below the horizontal convection passage 38.

In the above case, it should be noted that in addition to the introduction of one or more iron-based phosphorus-reducing compounds, the systems, methods and/or control equipment and/or techniques mentioned above may be used as described in detail above. One or more halide compounds according to the invention. Accordingly, in one embodiment, the present invention is directed to a method of supplying one or more iron-based compounds and/or one or more halide compounds in any manner according to various methods and/or systems described herein. System. In other implementations Among them, various types of compounds, even individual compounds of any type, can be supplied individually. In another embodiment, any combination of two or more compounds of any type (ie, whether the iron is a substrate or a halide compound) may be supplied together as long as one compound does not adversely react with the other compound. .

Further, in the above case, the reduced iron (or iron oxide (II)) of the present invention can remove the vapor phase phosphorus in the form of an iron-phosphorus alloy from the iron-phosphorus oxide compound upon contact with the burnt air. This significantly reduces the amount of gas phase phosphorus accumulation in the SCR catalyst. A further advantage of the present invention is that any phosphorus present in the significant portion will be iron-bonded via the addition of iron. The iron-bound phosphorus compound is less susceptible to leaching, thereby minimizing the transfer of phosphorus to the SCR catalyst. Further, the phosphorus ratio associated with the iron compound (e.g., iron oxide) and/or bound to the iron compound is more stable than the calcium compound (e.g., calcium oxide) and/or the phosphorus bound to the calcium oxide. In this case, in one embodiment, the present invention relates to an iron-phosphorus-oxygen compound suitable for most of the phosphorus-based chelate present in the combustion and/or flue stream, thereby substantially reducing energy and The case of calcium/phosphorus/oxygen compounds in the SO _x reaction. This in turn, due to the limitations present in the combustion and / or flue gas stream of calcium / phosphorus / oxygen compounds (which react with various SO _x compounds resulting from improper SCR catalyst poison will cause failure of the gaseous phosphorus compounds, or phosphorus The amount of /oxygen compound is substantially reduced by the amount of gaseous phosphorus produced in the combustion and/or flue gas stream.

In another embodiment, the iron-carrying compound and the halide compound of the present invention may be added via separate compounds or may be added via the same compound, and may be supplied in any suitable manner, including in the manner detailed in FIG. Suitable iron-bearing compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water-soluble or water-insoluble forms of the compound carrying iron, which Iron compounds include, but are not limited to, metallic iron, one or more iron oxides, iron carbonate, iron (II) acetate (eg, Fe(C ₂ H ₃ O ₂ ) ₂ .4H ₂ O), iron nitrate (II) (for example, Fe(NO ₃ ) ₂ .6H ₂ O), iron (III) nitrate (for example, Fe(NO ₃ ) ₃ .6H ₂ O or Fe(NO ₃ ) ₃ .9H ₂ O), iron sulfate ( II) (for example, FeSO ₄ .H ₂ O, FeSO ₄ .4H ₂ O, FeSO ₄ .5H ₂ O or FeSO ₄ .7H ₂ O), iron (III) sulfate (for example, Fe ₂ (SO ₄ ) ₃ . 9H ₂ O), iron (II) bromide (for example, FeBr ₂ ), iron (III) bromide (for example, FeBr ₃ , Fe ₂ Br ₆ or FeBr ₃ .6H ₂ O), iron (II) chloride ( For example, FeCl ₂ , FeCl ₂ .2H ₂ O or FeCl ₂ .4H ₂ O FeBr ₂ ), iron (III) chloride (for example, FeCl ₃ , Fe ₂ Cl ₆ , FeCl ₃ .21⁄2H ₂ O or FeCl ₃ .6H ₂ O), iron (II) iodide (for example, FeI ₂ or FeI ₂ .4H ₂ O), iron (III) iodate (for example, Fe(IO ₃ ) ₃ ) or a mixture of two or more thereof. Although various hydrated forms of iron-bearing compounds are listed herein, the invention is not limited to the above listed hydrated forms. Rather, any corresponding anhydrous form of the compound bearing iron listed above may also be used in conjunction with the present invention, if possible. In this case, when reference is made herein to a compound carrying iron, whether or not the chemical formula is given "bound water", it should be construed as including a hydrated form or an anhydrous form. Suitable halides include, but are not limited to, potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, calcium fluoride. Calcium iodide, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum iodide, other metal halides (eg, bromide, chloride, fluoride, and/or iodide, provided that the metal is not iron) , or any mixture of two or more thereof. If an existing skid is used, one or more aqueous reagents can be pumped from the storage tank to one or more coal feeders via a positive displacement pump where the coal is upstream of the pulverizer in the feed zone Upon passing, the reagent was sprayed onto the coal. In this example, if so used, one or more halide compounds that are soluble in water or an aqueous solvent are selected. Suitable soluble halides include, but are not limited to, potassium bromide, potassium chloride, potassium fluoride, potassium iodide, sodium bromide, sodium chloride, sodium fluoride, sodium iodide, calcium bromide, calcium chloride, iodide Calcium, aluminum bromide, aluminum chloride, aluminum iodide or any mixture of two or more thereof. In another embodiment, other transition metal halides (eg, bromides, chlorides, fluorides, and/or iodides) that are not iron halides may be used, as long as such compounds are present in this embodiment. Soluble in water or aqueous solvent.

In one embodiment, the present invention is advantageous in that it is applicable to both existing SCR (refurbishment) and new SCR. In addition, the present invention is applicable to a power plant using biomass as a fuel source. In one embodiment, the practice of the present invention can be achieved in a cost effective manner using low cost hardware designed to supply the necessary iron compounds to the combustion process. The present invention also does not affect the current design of the boiler and SCR.

In one embodiment, the amount of one or more iron compounds used in conjunction with the present invention varies depending on the amount of phosphorus in the coal to be combusted. In one embodiment, the invention is directed to a method and system for supplying a stoichiometric excess of one or more iron compounds at any point prior to the SCR. While not wishing to be bound by any theory, it has been found that the catalytic activity of SCR catalysts can be unexpectedly increased by supplying a stoichiometric excess of iron upstream of the SCR. And / or catalytic life. As can be seen in the graph of Figure 2, the addition of a stoichiometric excess of one or more of the iron-based compounds not only protects the SCR catalyst from poisoning via various phosphorus compounds, but also increases the catalysis during at least about 2,000 hours of operation. Both activity and catalytic lifetime.

Referring to FIG. 2, FIG. 2 is a diagram showing the actual deactivation of a catalyst which does not add the catalyst of the iron-bearing compound of the present invention and the actual deactivation of the catalyst to which the iron-bearing compound of the present invention is added and the iron without the addition of the present invention. The deactivation map observed for the compound. The y-axis of Figure 2 is the catalytic activity of the decimal, where 0.9 is equivalent to measuring 90% of the activity measured without the use of a new catalyst using any method known to those skilled in the art for determining catalytic activity. The x-axis of Figure 2 is the operating hours of the catalyst under discussion exposed to the average operating conditions of a 100 MWe coal-fired power plant.

In the above case, in one embodiment, the present invention achieves an increase in catalytic activity and/or an increase in catalytic lifetime by either, using, introducing and/or delivering one or more iron-based compounds. In one embodiment, the catalytic activity and/or catalytic lifetime of a given catalyst is at least about 2,000 compared to performing similar operating conditions without performing a one or more iron-based compounds as disclosed herein. An hour of operation time results in at least about 10% increase in either or both of the catalytic activity and/or the catalytic lifetime. Those skilled in the art will appreciate that various known methods can be used to measure baseline catalytic activity and catalytic activity of various catalysts, including SCR catalysts. Therefore, for the sake of brevity, the detailed discussion of this article is omitted.

In other embodiments, one or more iron-based compounds are supplied as disclosed herein, but are not subjected to similar operating conditions. The catalytic activity and/or catalytic lifetime of a given catalyst, the catalytic activity and/or catalytic lifetime of the present invention is increased by at least about 10% at about 2,000 hours of operation time, at about 2,000 hours of operation time. An increase of at least about 12.5%, an increase of at least about 15% over an operation time of about 2,000 hours, an increase of at least about 17.5% at an operation time of about 2,000 hours, and an increase of at least about 20% at an operation time of about 2,000 hours, at about 2,000 hours. The increase in operating time is at least about 22.5%, an increase of at least about 25% over an operation time of about 2,000 hours, an increase of at least about 27.5% at an operation time of about 2,000 hours, or an increase of at least about 30% at an operation time of about 2,000 hours. Here, as well as elsewhere in the specification and claims, individual values may be combined to form additional ranges and/or non-disclosed ranges.

In another embodiment, the present invention is achieved by performing catalytic activity and/or catalytic lifetime of a given catalyst when similar operating conditions are performed but without the supply of one or more iron-based compounds as disclosed herein. Either or both of the catalytic activity and/or catalytic lifetime increase by at least about 10% over an operating time of about 2,500 hours, at least about 12.5% at an operating time of about 2,500 hours, and at least about 15% at an operating time of about 2,500 hours. Increasing at least about 17.5% at about 2,500 hours of operation time, at least about 20% at about 2,500 hours of operation time, at least about 22.5% at about 2,500 hours of operation time, and increasing at least about 2,500 hours of operation time. 25%, increased by at least about 27.5% at an operating time of about 2,500 hours, or even increased by at least about 30% at an operating time of about 2,500 hours. Others here and in this specification and the scope of the patent application Individual values may be combined to form additional ranges and/or non-disclosed ranges.

In yet another embodiment, the present invention is based on catalytic activity and/or catalytic lifetime of a given catalyst when similar operating conditions are performed but no one or more iron-based compounds are disclosed as disclosed herein. Either or both of the catalytic activity and/or catalytic lifetime are increased by at least about 10%, at least about 12.5%, at least about 15%, at least about 17.5%, at least about 20%, at least about 22.5% at about 3,000 hours of operation time. At least about 25%, at least about 27.5%, or even at least about 30%. In yet another embodiment, the present invention is based on catalytic activity and/or catalytic lifetime of a given catalyst when similar operating conditions are performed but no one or more iron-based compounds are disclosed as disclosed herein. About 3,500 hours, about 4,000 hours, about 4,500 hours, about 5,000 hours, about 6,000 hours, about 7,000 hours, about 7,500 hours, about 8,000 hours, about 9,000 hours, about 10,000 hours, about 11,000 hours, about 12,000 hours, about 13,000 hours, about 14,000 hours, about 15,000 hours, or even about 16,000 hours of operation time results in at least about 10%, at least about 12.5%, at least about 15%, at least about at least about 10% of the catalytic activity and/or catalytic lifetime. 17.5%, at least about 20%, at least about 22.5%, at least about 25%, at least about 27.5%, or even at least about 30%. Here, as well as elsewhere in the specification and claims, individual values may be combined to form additional ranges and/or non-disclosed ranges.

As is known to those skilled in the art, the phosphorus content of coal is determined by a variety of known methods. So, in this example, the invention does not It is limited to any range of iron compounds used. Instead, use an excessive stoichiometric ratio. In one embodiment, the excess stoichiometric ratio of iron to phosphorus is from about 2.5:1 to about 10:1, or from about 3:1 to about 9:1, or from about 3.5:1 to about 8:1. Or, from about 4:1 to about 7.5:1, or from about 5:1 to about 7:1, or from about 5.5:1 to about 6.5:1, or even about 6:1. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims.

In other embodiments, when the coal used is Powder River Basin/Lignite coal, the amount of the iron compound used in combination with the present invention is within a given range. In the present embodiment, the amount of the iron compound is expressed as the amount of pounds per 1,000 pounds of coal in the Powder River Basin/Lignite coal system as an iron compound (hereinafter only referred to as "iron" in this case). In one embodiment, the amount of iron compound used ranges from about 5 pounds of "iron" / 1,000 pounds of coal to about 20 pounds of "iron" / 1,000 pounds of coal. In other embodiments, the amount of iron compound used is between about 5.5 pounds of "iron" / 1,000 pounds of coal to about 17.5 pounds of "iron" / 1,000 pounds of coal, or about 6 pounds of "iron" / 1,000. Pound coal to approximately 15 pounds of "iron" / 1,000 pounds of coal, or approximately 7 pounds of "iron" / 1,000 pounds of coal to approximately 12.5 pounds of "iron" / 1,000 pounds of coal, or approximately 7.5 pounds of "iron" /1,000 pounds of coal to about 10 pounds of "iron" / 1,000 pounds of coal, or even about 8 pounds of "iron" / 1,000 pounds of coal to about 9 pounds of "iron" / 1,000 pounds of coal. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims.

In other implementations, when using iron as defined above When both the substrate compound and the halide compound are compared, the amount of the iron-based compound to the one or more halide compounds is 95 parts by weight of the iron-based compound to about 5 by weight. Parts by weight of halide compounds. In other embodiments, the weight ratio of the iron-based compound to the halide compound is from about 95:5 to about 75:25, or from about 93.5:6.5 to about 80:20, or about 92:8. To about 82.5:17.5, or from about 91:9 to about 85:15, or even from about 90:10 to about 87.5:12.5. Thus, in one embodiment, the amount of the one or more halide compounds, if so used, can be calculated from the ratio of any of the above-described iron-based compounds via the ratios disclosed in this paragraph. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims.

In other embodiments, if so used in conjunction with the present invention to control mercury in a flue gas or combustion gas, the rate of injection of one or more halide compounds is based on a non-limiting example of a 100 MWe coal-fired power plant. In this case, the one or more halide compounds (if in solution) are injected at a rate of from about 0.25 gallons per hour to about 10 gallons per hour, or from about 0.5 gallons per hour to about 5 gallons per hour, or even It is in the range of from about 1 gallon per hour to about 4 gallons per hour. In other embodiments, the one or more halide compounds are any sufficient to produce between about 10 ppm to about 200 ppm, or between about 25 ppm to about 175 ppm, or about 50 ppm, regardless of the size of the power plant burning thermal power plant. A rate of halide (e.g., bromide, chloride or iodide) concentration between about 150 ppm is supplied to the flue gas or combustion gases. It should be noted that the application is applied to generate the smoke. Depending on the emission control technology of the gas or combustion gas plant, it may be desirable to use a lower halide concentration to prevent any type of beneficial effects of such downstream emissions technologies. In one embodiment of this example, the halide concentration is from about 10 ppm to about 125 ppm, or from about 25 ppm to about 100 ppm, or from about 50 ppm to about 75 ppm. Here, as well as elsewhere in the specification and claims, individual range values, even from different embodiments, may be combined to form additional ranges and/or non-disclosed ranges.

In view of the above, those skilled in the art will recognize that the amount of one or more iron or iron-based compounds necessary to supply a desired amount of iron to a flue gas or combustion gas in accordance with the present invention will result in such a smoke. The size of the device for the gas or combustion gas depends on the size of the device. The same is true for one or more halide compounds. That is, those skilled in the art will recognize that the amount of one or more halide compounds necessary to supply the desired amount of halide to the flue gas or combustion gas in accordance with the present invention will result in the production of such flue gas or combustion gases. The size of the device depends. Accordingly, the invention is not limited to any particular rate or range of supply.

In other embodiments, the amount of halide solution (25% by weight solution) supplied to the flue gas or combustion gas is from about 0.25 gallons per hour to about 6 gallons per hour for a 100 MWe coal-fired power plant, or From 0.5 gallons per hour to about 5 gallons per hour, or even from 1 gallon per hour to about 4 gallons per hour. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims. However, as mentioned above, the invention is not limited to only such supply rates. Instead, any supply rate can be used to achieve the desired halide concentration. degree.

It will be apparent to those skilled in the art that other additional factors may affect the amount of iron supported, iron and/or iron compounds supplied to various embodiments of the present invention. Such additional factors include, but are not limited to, the amount and/or type of phosphorus present in the coal or other combustible fuel; the size and/or output of the boiler, heater, kiln or other flue gas or combustion gas generating device; And the stoichiometric ratio desired to be obtained; the type and/or manner of combustion, the type and/or configuration of any applicable equipment or structure.

In other embodiments, one or more of the iron compounds and/or one or more halide compounds in combination with the present invention can be of any particle size and/or particle geometry. Suitable particle geometries include, but are not limited to, spheres, platelets, irregulars, ellipses, oblongs, or combinations of two or more different particle geometries. It will be apparent to those skilled in the art that various compounds or even the same compounds may be supplied in the form of one or more particle geometries. In one embodiment, one or more of the iron compounds and/or one or more halide compounds of the present invention, if water soluble, may be supplied separately or together in solution as long as they are to be delivered to the flue gas or combustion gases The active component does not react negatively. In this case, a solution concentration of at least about 15% by weight of one or more water-soluble iron compounds and/or one or more water-soluble halide compounds is used. In other embodiments, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or even at least about 50% by weight The solution concentration of one or more water-soluble iron compounds and/or one or more water-soluble halide compounds is used in combination with the present invention. Here And in the specification and elsewhere in the claims, individual range values may be combined to form additional ranges and/or non-disclosed ranges. Those skilled in the art will appreciate that in one embodiment, the solution concentration of any one or more water soluble iron compounds and/or one or more water soluble halide compounds should not individually exceed the one or more iron compounds and/or The amount of solubility of the one or more halide compounds.

In another embodiment, one or more of the iron compounds and/or one or more halide compounds of the invention may be supplied in powder form, in solution form, in aqueous suspension form, or a combination of two or more thereof. In the case of aqueous suspensions, the one or more iron compounds and/or the one or more halide compounds used in conjunction with the present invention should have a suitable particle size. In addition, the one or more iron compounds and/or the one or more halide compounds should be in contact with the flue gas, even if there is no need to incorporate one or more iron compounds and/or one or more halide compounds of the present invention into an aqueous solution. Or a suitable particle size that promotes a higher degree of reactivity when contacted by a combustion gas. In one embodiment, at least about 95% of the particles have a particle size of less than about 350 [mu]m (micrometers), at least about 95% of the particles have a particle size of less than about 350 [mu]m (micrometers), and at least about 95% of the particles have less than about At a particle size of 300 μm (micrometers), at least about 95% of the particles have a particle size of less than about 250 μm (micrometers), at least about 95% of the particles have a particle size of less than about 200 μm (micrometers), or even at least about 95% of the particles have less than about One or more of the iron compounds and/or one or more halide compounds having a particle size of 175 μm (micrometers) may be independently or in combination. Here and in the remainder of the specification and claims, individual range values may be combined to form additional ranges and/or non-disclosed The scope of the display.

Although not limited thereto, the iron compound suitable for use in conjunction with the present invention is iron (II) carbonate available from Prince Agri Products (a subsidiary of Phibro Animal Health Corporation, Ridgefield Park, New Jersey). The iron (II) carbonate is a powdered compound having a particle size of at least about 95% of particles having a particle size of less than 200 μm (micrometers). Additionally, the iron (II) carbonate concentration in this product is about 80% by weight, and in view of the use herein, the remaining 20% by weight is substantially completely non-reactive. If desired, the applicable halide compound for use in conjunction with the present invention is calcium bromide available from Tetra Chemical (The Woodlands, Texas).

Where one or more aqueous suspensions are used in combination with the present invention, such aqueous suspensions may additionally comprise one or more suitable anti-settling, suspending, thickening or emulsifying agents. Suitable anti-settling, suspending, thickening or emulsifying agents include, but are not limited to, sodium polyacrylate, carbomer, acrylates, and inorganic thickeners. Other suitable anti-settling, suspending, thickening or emulsifying agents are known to those skilled in the art, and therefore, for the sake of simplicity, this discussion is omitted herein. In other embodiments, suitable suspension or emulsification can be achieved via agitation and does not necessarily require the use of one or more anti-settling, suspending, thickening or emulsifying agents. In other embodiments, one or more combinations of anti-settling, suspending, thickening or emulsifying agents can be used in combination with agitation.

In another embodiment, one or more of the iron compounds and/or one or more halide compounds of the present invention should independently have at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65. % by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% % by weight, at least about 85% by weight, at least about 90% by weight, at least about 95% by weight, or even at least about 99% by weight or greater. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims.

As for one or more iron compound moieties which are not "iron compounds", such impurities should be non-reactive in the environment in which they are present. Alternatively, if reactive, such impurities should be readily captured, removed, and/or sequestered, or should not be added in large amounts to any further contamination of any downstream catalyst. In another embodiment, the amount of phosphorus-containing compound impurities in any one or more of the iron compounds and/or one or more halide compounds used in conjunction with the present invention should be independently less than about 5% by weight, less About 2.5% by weight, less than about 1% by weight, less than about 0.5% by weight, less than about 0.25% by weight, less than about 0.1% by weight, or even at least about 0.01% by weight. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims. In still another embodiment, the amount of phosphorus-containing compound impurities in any one or more of the iron compounds and/or one or more halide compounds used in conjunction with the present invention should be zero. That is, in this embodiment, the one or more iron compounds and/or the one or more halide compounds used in combination with the present invention should be independently free of any phosphorus-containing compound.

While not wishing to be bound by any theory, it is believed that the present invention utilizes various preferential reactions between phosphorus compounds or phosphorus-containing compounds to sequester various phosphorus or phosphorus-containing compounds that are detrimental to increasing SCR activity or useful life. Therefore, the reactions discussed in this paper should be interpreted as unrestricted Other additional reactions may occur in the combustion and/or flue gas stream.

In other embodiments, the present invention relates to injecting a blend of iron carbonate, other suitable iron compounds or one or more iron compounds and one or more non-ferrous halide compounds and coal into a furnace to use Fe active sites. A system and method for simultaneously activating mercury oxidation by supplementing an active catalytic site on the surface of an SCR catalyst. In one example, the implant material is a blend of iron carbonate (about 90% by weight) and a non-ferrous halide compound (eg, calcium bromide, 10% by weight). As is known to those skilled in the art, any iron present in coal ash (including but not limited to PRB coal ash) is not catalyzed when combined or combined with various citrates and/or aluminates in a coal combustion process. active. In PRB coal, more than 90% of the total iron is produced as a combined mineral, meaning that most of it is trapped in the vitreous cerium oxide and/or alumina compound during the combustion process, making it impossible for any other chemical reaction. use. Accordingly, the present invention provides "free" iron by separately injecting iron. Although not wishing to be bound by any theory, it is generally believed that the "free" iron settles on and/or deposits on the fly ash surface, which makes it available for other chemistry. The reaction is used.

The blended material containing "free" iron as defined above may then provide iron to increase the catalytic activity and/or catalytic lifetime of the DeNO _x catalyst, while providing one or more halide compounds of the invention. The halogen portion is used to assist or obtain oxidation of mercury. While not wishing to be bound by any theory, it is thought that when the fly ash is deposited on the surface of the SCR catalyst, the iron in the fly ash surface or by injection procedure is deposited on the catalyst surface of the iron can provide ammonia reacts with NO _x The part forms N ₂ and water. When the iron is continuously injected at a low injection rate, any depleted active iron sites are replaced at a reasonable rate by the new iron sites, thereby extending the length of the untreated catalyst similar to that explained in detail above. / or increase catalytic life and / or catalytic activity. The halogen portion of the halide compound oxidizes the elemental mercury to an oxidized form and makes it more easily removed by a wet or dry scrubber or by PAC injection.

While not wishing to be bound by any of the examples, the long-term iron carbonate injection test from a 100 MWe coal-fired power plant is supplied to support the information of the present invention. Before the catalyst is exposed to the combustion flue gas, the catalyst analysis by XRF technology shows negligible iron on the surface and in the whole catalyst. After about 2,000 hours of operation of the injection FeCO _3, and a catalyst obtained by XRF analysis sample. This sample shows 0.35% iron on the surface and 0.13% Fe in the whole. The previously used catalyst (not injected with FeCO ₃ from the same site) had 0.26% Fe on the surface and 0.06% Fe in the whole after 11,000 hours of operation. Baseline testing before injection display iron carbonate SO ₃ concentration in the flue gas outlet of the air heater is less than 1ppm. 8,000 hours after the multi-operation, the measured concentration of SO ₃ in air heater outlet, and it is about 2.6ppm. This confirms that the iron injection furnace does reach the SCR. The increase in SO ₃ concentration is related to the presence of iron on the surface of the catalyst, since Fe is also a good catalyst for converting SO ₂ to SO ₃ .

As mentioned above, Figure 2 illustrates the catalytic properties of injected or not. The upper line graph (with the lower font "X") is the original expected catalyst deactivation curve. This catalyst is expected to continue to operate for approximately 16,000 hours. The lower line diagram (diamond) shows the actual performance of this catalyst. Deactivated by phosphorus Therefore, the catalyst actually lasted only 6,800 hours. The middle line (triangle) illustrates the performance of at least the catalyst injected into the iron compound of the present invention. In this example, the catalyst is not installed as a new catalyst, but a regenerated catalyst, and its initial activity is 15% lower than that of the new catalyst.

Thus, in one aspect of the embodiment, the present invention is injected by one or more compounds carrying iron to provide additional sites for reaction with the DeNO _x, which can significantly improve the life of an SCR catalyst and / or catalytic activity than currently The period of time accepted or recognized. When used, one or more of the halide compounds of the present invention provides a halogen component that allows for increased mercury oxidation and enables downstream removal of mercury by any suitable technique (e.g., AQCS equipment).

In other embodiments, the present invention seeks to minimally control the smoke found in one or more emission control devices (eg, WFGD) by adding at least one metal compound to the above-described iron-bearing compound at any point described herein. The gas phase selenium and/or selenium species forming properties in at least one of the gas or aqueous environment. In yet another embodiment, the invention relates to the addition, at any point, to at least one metal compound described above with respect to the iron-bearing compound described herein to control, mitigate and/or reduce by boiler, heater, kiln or other flue. A method and apparatus for the amount of selenium contained in and/or discharged from one or more components of a gas or combustion gas generating device (e.g., at a power plant, a processing plant, etc.). In yet another embodiment, the invention is directed to use in a wet flue gas desulfurization (WFGD) unit and/or a dry flue gas desulfurization (DFGD) unit (also known as a semi-dry flue) a gas desulfurization unit including, but not limited to, a spray drying scrubber (SDA), a circulating dry scrubber (CDS), etc. Method and apparatus for controlling the formation of selenium species in one or both of the gas phase or the aqueous phase with less of a metal additive (eg, an aluminum metal additive or a transition metal additive such as iron, nickel, zinc, copper or other transition metal) . In this case, in Figure 1, when the term "SDA" is used, it shall be considered to include all types of DFGD units.

In other embodiments aspects, the present invention seeks to control at least one of the lowest in the amine-based post-combustion CO ₂ capture amount of selenium vapor in the program and / or properties of the selenium species are formed. In various amine-based post-combustion CO ₂ capture procedures, the amines used therein begin to degrade due to the effects of SO ₂ , CO ₂ , heat, O _{2 ,} and other degradation products. Amine or a large volume of inventory required of it by the post-combustion CO.'S ₂ capture process, the amine is deteriorated very bulky, and the regenerated amine need to make the operation more economical. This is typically accomplished via a heat recovery unit that produces a large amount of hot sludge and/or waste products. It has been observed that due to the recycling procedure, the selenium present in the inlet gas is removed by the procedure in the hot sludge of the heat recovery unit (this will occur in all amines that use heat recovery). Due to the nature of the heat recovery procedure, it concentrates the removed product (such as selenium) from the circulating solution. This makes the hot sludge a hazardous waste and becomes a problem to be solved when these programs are commercialized. When selenium is found in the waste stream, the post-combustion CO ₂ capture program will need to be shut down until the selenium problem is resolved. By binding additive by the addition of one or more metals of the present invention after the combustion of the CO ₂ upstream of the capture program selenium, this allows the CO ₂ capture process can operate continuously without concern concentrated selenium-containing waste.

Suitable metal compounds include water-soluble or water-insoluble compounds of iron, aluminum, nickel, zinc, copper, inorganic or organic compounds thereof, or a mixture of two or more thereof. Suitable iron-bearing compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water soluble forms of iron-bearing compounds, including iron-containing compounds including However, it is not limited to metal iron, one or more iron oxides, iron carbonate, iron (II) acetate (for example, Fe(C ₂ H ₃ O ₂ ) ₂ .4H ₂ O), iron (II) nitrate (for example, Fe(NO ₃ ) ₂ .6H ₂ O), iron (III) nitrate (for example, Fe(NO ₃ ) ₃ .6H ₂ O or Fe(NO ₃ ) ₃ .9H ₂ O), iron (II) sulfate (for example) , FeSO ₄ .H ₂ O, FeSO ₄ .4H ₂ O, FeSO ₄ .5H ₂ O or FeSO ₄ .7H ₂ O), iron (III) sulfate (for example, Fe ₂ (SO ₄ ) ₃ .9H ₂ O) , iron (II) bromide (for example, FeBr ₂ ), iron (III) bromide (for example, FeBr ₃ , Fe ₂ Br ₆ or FeBr ₃ .6H ₂ O), iron (II) chloride (for example, FeCl _{2 )} , FeCl ₂ .2H ₂ O or FeCl ₂ .4H ₂ O.FeBr ₂ ), iron (III) chloride (for example, FeCl ₃ , Fe ₂ Cl ₆ , FeCl ₃ .21⁄2H ₂ O or FeCl ₃ .6H ₂ O) Iron(II) iodide (for example, FeI ₂ or FeI ₂ .4H ₂ O), iron (III) iodate (for example, Fe(IO ₃ ) ₃ ) or a mixture of two or more thereof. Suitable aluminum-bearing compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water-soluble or water-insoluble forms of the compound bearing aluminum, which Compounds of aluminum include, but are not limited to, aluminum metal, aluminum acetate (eg, Al(C ₂ H ₃ O ₂ ) ₃ ), aluminum bromate (eg, Al(BrO ₃ ) ₃ .9H ₂ O), aluminum bromide ( For _{example, AlBr 3, Al 2 Br 6} , AlBr 3 .6H 2 O or AlBr ₃ .15H ₂ O), aluminum chloride (e.g., AlCl _3, Al ₂ Cl ₆ or AlCl ₃ .6H ₂ O), aluminum fluoride (for example, AlF ₃ , AlF ₃ .31⁄2H ₂ O or AlF ₃ .H ₂ O), aluminum hydroxide (for example, Al(OH) ₂ ), aluminum iodide (for example, AlI ₃ , Al ₂ I ₆ or AlI _{3 )} .6H ₂ O), aluminum nitrate (for example, Al(NO ₃ ) ₃ .9H ₂ O), alumina (for example, Al ₂ O ₃ , Al ₂ O ₃ .H ₂ O or Al ₂ O ₃ .3H ₂ O And aluminum sulfate (for example, Al ₂ (SO ₄ ) ₃ or Al ₂ (SO ₄ ) ₃ .18H ₂ O) or a mixture of two or more thereof. Suitable nickel-carrying compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water-soluble or water-insoluble forms of the compound carrying nickel, which Nickel compounds include, but are not limited to, metallic nickel, nickel acetate (eg, Ni(C ₂ H ₃ O ₂ ) ₂ or Ni(C ₂ H ₃ O ₂ ) ₂ .4H ₂ O), nickel bromate (eg, Ni) (BrO ₃ ) ₂ .6H ₂ O), nickel bromide (for example, NiBr ₂ or NiBr ₂ .3H ₂ O), nickel carbonate or basic nickel carbonate (for example, NiCO ₃ , 2NiCO ₃ .3Ni(OH) ₂ . 4H ₂ O or iridium ore), nickel chloride (for example, NiCl ₂ or NiCl ₂ .6H ₂ O), nickel fluoride (for example, NiF ₂ ), nickel hydroxide (for example, Ni(OH) ₂ or Ni (for example) OH) ₂ .XH ₂ O), nickel iodate (for example, Ni(IO ₃ ) ₂ or Ni(IO ₃ ) ₂ .4H ₂ O), nickel iodide (for example, NiI ₂ ), nickel nitrate (for example, Ni) (NO ₃ ) ₂ .6H ₂ O), nickel oxide (for example, NiO), nickel sulfate (for example, NiSO ₄ , NiSO ₄ .7H ₂ O or NiSO ₄ .6H ₂ O) or a mixture of two or more thereof.

Suitable copper-carrying compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water-soluble or water-insoluble forms of copper-carrying compounds, which Copper compounds include, but are not limited to, metallic copper, copper acetate (eg, Cu(C ₂ H ₃ O ₂ ) ₂ .CuO.6H ₂ O or Cu(C ₂ H ₃ O ₂ ) ₂ .H ₂ O), bromine Copper acid (for example, Cu(BrO ₃ ) ₂ .6H ₂ O), copper bromide (for example, CuBr, Cu ₂ Br ₂ or CuBr ₂ ), copper trioxide (for example, CuBr ₂ .3Cu(OH) ₂ ), copper carbonate or basic copper carbonate _{(e.g., Cu 2 CO 3, CuCO 3} .Cu (OH) 2 or _{2CuCO 3 .Cu (OH) 2)} , copper chloride _{(e.g., CuCl, Cu 2 Cl 2,} CuCl ₂ or CuCl ₂ .2H ₂ O), copper chloride (for example, CuF, Cu ₂ F ₂ , CuF ₂ or CuF ₂ .2H ₂ O), copper hydroxide (for example, Cu(OH) ₂ ), copper iodate (for example, Cu(IO ₃ ) ₂ or Cu ₃ (IO ₃ ) ₆ .2H ₂ O), copper iodide (for example, Cul or Cu ₂ I ₂ ), copper nitrate (for example, Cu(NO ₃ ) ₂ .H ₂ O or Cu(NO ₃ ) ₂ .3H ₂ O), copper oxide (for example, Cu ₂ O, CuO, CuO ₂ .H ₂ O or Cu ₄ O), copper sulfate (for example, Cu ₂ SO ₄ , CuSO _{4 )} Or CuSO ₄ .5H ₂ O) or a mixture of two or more thereof. Suitable zinc-bearing compounds include, but are not limited to, powdered, solid, aqueous (which may be aqueous or aqueous emulsions) and/or water-soluble or water-insoluble forms of the compound carrying zinc, which Compounds of zinc include, but are not limited to, zinc metal, zinc acetate (eg, Zn(C ₂ H ₃ O ₂ ) ₂ or Zn(C ₂ H ₃ O ₂ ) ₂ .2H ₂ O), zinc bromate (eg, Zn) (BrO ₃ ) ₂ .6H ₂ O), zinc bromide (for example, ZnBr ₂ ), zinc carbonate (for example, ZnCO ₃ ), zinc chloride (for example, ZnCl ₂ ), zinc ferrite (for example, ZnFe ₂ O _{4 )} ), zinc fluoride (for example, ZnF ₂ or ZnF ₂ .4H ₂ O), zinc hydroxide (for example, Zn(OH) ₂ ), zinc iodate (for example, Zn(IO ₃ ) ₂ or Zn(IO ₃ ) ₂ .2H ₂ O), zinc iodide (for example, ZnI ₂ ), zinc nitrate (for example, Zn(NO ₃ ) ₂ .3H ₂ O or Zn(NO ₃ ) ₂ .6H ₂ O), zinc oxide (for example, ZnO or ZnO ₂ .1⁄2H ₂ O), zinc sulfate (for example, ZnSO ₄ , ZnSO ₄ .6H ₂ O or ZnSO ₄ .7H ₂ O) or a mixture of two or more thereof.

It should be noted that although various different hydrated forms of the metal-bearing compound are listed herein, the invention is not limited to the above listed hydrated forms. Rather, any corresponding anhydrous form of the metal-carrying compound listed above may also be used in conjunction with the present invention, if possible. In this case, when a metal-bearing compound is mentioned herein, whether or not the chemical formula is given "Water", which should all be interpreted to include hydrated or anhydrous forms.

In another embodiment, the invention may mean that at least one kaolin-carrying compound is used to control the gas phase sodium and potassium compounds as described in U.S. Patent No. 8,303,919, the entire disclosure of which is incorporated herein by reference. Into this article.

In the above case, in one embodiment, the invention relates to a gas phase selenium in one or more emission control devices/equipment that enables control of a boiler, heater, kiln or other flue gas or combustion gas generating device Or a method and/or equipment for one or both of the aqueous selenium. While not wishing to be bound by any theory, it is generally believed that the addition of one or more metal-carrying compounds allows selenium to be captured in the gas phase and/or aqueous phase via modified selenium species formation, resulting in low solubility in water or other aqueous solutions. The selenium compound produced by the one or more metal-carrying compounds of the present invention is not added. As described above, the present invention is applicable to both WFGD and DFGD systems, and allows control, slowing, and/or reduction of selenium in, for example, WFGD effluent, WFGD slurry solution, particulate matter formed from DFGD, and the like. While not wishing to be bound by any theory, in one embodiment of the invention, selenium species in the gas phase and/or liquid phase/aqueous phase are modified to have low solubility (defined herein as being in water under SATP) Less than about 0.1 g/100 mL, less than about 0.01 g/100 mL, less than about 0.001 g/100 mL, less than about 0.0001 g/100 mL, less than about 1 x 10 ^-5 g/100 mL, or less than about 1 x. 10 ^-6 g / 100 mL solubility); substantially no solubility (defined herein as less than about 1 x 10 ^-7 g / 100 mL in SATP in water, less than about 1 x 10 ^-8 g / 100 mL, Or at least about 1 x 10 ^-9 g / 100 mL of solubility); or even 0 solubility especially in water or a stream solution (defined herein as less than about 1 x 10 ^-10 in water at SATP) g/100 mL, or less than about 1 x 10 ^-11 g / 100 mL, or less than about 1 x 10 ^-12 g / 100 mL, less than about 1 x 10 ^{- 13} g / 100 mL, or less than about 1 x 10 ^- An oxidation state and/or a selenium compound of ¹⁴ grams per 100 mL, or less than about 1 x 10 ^-15 grams per 100 mL, or even less than about 1 x 10 ^-16 grams per 100 mL of solubility (for example including but not limited to Insoluble selenite compounds and/or insoluble selenide compounds, etc.) To be "discharged" and / or "leaching" into the surrounding environment (such as rivers, lakes, groundwater, etc.) of the lower amounts of selenium. As defined herein, SATP is known as "standard ambient temperature and pressure" and is defined herein as a temperature equal to 298.15 K (ie, 25 ° C or 77 ° F) and an absolute pressure of 100 kPa (ie, 14.504 psi or 0.986 atm). . Here, as well as elsewhere in the specification and claims, individual values may be combined to form additional ranges and/or non-disclosed ranges.

In yet another embodiment, the selenium control of the present invention may or may not be achieved using one or more of the following: (i) controlling mercury in the flue gas via any applicable mercury control technique mercury oxidation and capture discussed herein. (ii) controlling one or more gas phase sodium and/or gas phase sodium compounds; and/or (iii) controlling one or more gas phase potassium and/or gas phase potassium compounds. In yet another embodiment, the present invention utilizes at least one iron-carrying compound to simultaneously control the gas phase phosphorus and the gas phase and/or aqueous selenium as described above. In this additional embodiment of the invention, the amount of iron-carrying compound supplied in any of the ways previously discussed and at any location may be the same amount as discussed above with respect to control of vapor phase phosphorus. In other embodiments, according to this embodiment of the present invention, the carrying Iron compounds or other metal-carrying compounds are not limited to any amount.

In one embodiment, as is known to those skilled in the art, an excess stoichiometric ratio can be used when determining the selenium content of the coal to be combusted via a suitable known method. In one embodiment, the excess stoichiometric ratio of metal to iron (eg, via one or more metal-carrying compounds, iron, aluminum, nickel, zinc, and/or copper) is between about 2.5:1 and about 10:1. Or from about 3:1 to about 9:1, or from about 3.5:1 to about 8:1, or from about 4:1 to about 7.5:1, or from about 5:1 to about 7:1, or It is from about 5.5:1 to about 6.5:1, or even about 6:1. The individual range values may be combined herein to form additional ranges and/or non-disclosed ranges, and elsewhere in the specification and claims. It will be appreciated that in embodiments of the invention in which an iron-bearing compound is used, since in some embodiments the amount of the iron-carrying compound used to control the gas phase phosphorus is sufficient to control the selenium species formation properties, It is not necessary to add any additional iron-carrying compounds to control, reduce and/or slow the amount of unwanted selenium species formation and/or selenium compounds in the flue gas and/or water/water solution.

While the invention has been shown and described with respect to the embodiments of the embodiments of the present invention, it is understood that the invention is not limited thereto, and the invention may be embodied otherwise without departing from the principles. In some embodiments of the invention, certain features of the invention may be used to obtain a benefit without necessarily corresponding to other features. Accordingly, all such changes and embodiments are intended to fall within the scope of the appended claims.

Claims (51)

A method for controlling the formation of selenium species in a flue gas and/or a gas phase of at least one component of an emission control device, the method comprising the steps of: (a) providing at least one coal-based fuel to a furnace or boiler; (b) subjecting at least one coal-based fuel to a staged combustion process, wherein the staged combustion process produces gaseous mercury; (c) providing at least one metal-carrying compound to the furnace or boiler before the flue gas enters the SCR a combustion zone or flue gas stream; and (d) allowing the at least one metal-carrying compound to be present in the combustion zone, the flue gas, and/or any selenium in the gas phase and at least one component of the emission control device And/or a selenium compound reaction, wherein the at least one metal-carrying compound is provided in an amount to allow control of one or more combustion zones, flue gas, and/or one or more present in at least one component of the emission control device The selenium species in the gas phase is formed, thereby causing the combustion zone, the flue gas, and/or any one or more gas phase emissions present in at least one component of the emission control device or contained therein of (VI) ions to reduce the amount or concentration. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of at least one inorganic compound carrying iron. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of metallic iron, one or more iron oxides, iron carbonate, iron (II) acetate, iron (II) nitrate, and ferric nitrate ( III), a mixture of iron (II) sulfate, iron (III) sulfate or two or more thereof. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of iron (III) oxide, iron (II) carbonate, iron (II) oxide, iron (II) acetate or two or more thereof. a mixture. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of an organic compound carrying iron. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of aluminum metal, aluminum acetate, aluminum bromate, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum hydroxide, aluminum iodide, Aluminum nitrate, aluminum oxide, aluminum sulfate or a mixture of two or more thereof. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of organic compounds bearing aluminum. The method of claim 1, wherein the compound carrying the metal is selected from the group consisting of nickel metal, nickel acetate, nickel bromate, nickel bromide, nickel carbonate, basic nickel carbonate, nickel chloride, nickel fluoride, hydrogen. A mixture of nickel oxide, nickel iodate, nickel iodide, nickel nitrate, nickel oxide, nickel sulfate or two or more thereof. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of organic compounds carrying nickel. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of copper metal, copper acetate, copper bromate, copper bromide, copper trioxygen bromide, copper carbonate, basic copper carbonate, and chlorination. Copper, copper fluoride, copper hydroxide, copper iodate, copper iodide, copper nitrate, copper oxide, copper sulfate or a mixture of two or more thereof. For example, the method of claim 1 of the patent scope, wherein the metal is carried The compound is selected from the group consisting of organic compounds carrying copper. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of metal zinc, zinc acetate, zinc bromate, zinc bromide, zinc carbonate, zinc chloride, zinc ferrite, zinc fluoride, and hydrogen. Zinc oxide, zinc iodate, zinc iodide, zinc nitrate, zinc oxide, zinc sulfate or a mixture of two or more thereof. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of organic compounds carrying zinc. The method of claim 1, wherein the metal-carrying compound is selected from the group consisting of one or more compounds carrying iron, one or more compounds carrying aluminum, one or more carrying nickel a compound, one or more compounds carrying copper, one or more compounds bearing zinc, or a mixture of any two or more thereof. The method of claim 1, wherein the at least one metal-carrying compound is supplied to the combustion zone via addition to the pulverized coal. The method of claim 1, wherein the at least one metal-carrying compound is supplied to the combustion zone via a dedicated supply line. The method of claim 1, wherein at least one component of the emission control device is a WFGD unit. The method of claim 1, wherein at least one component of the emission control device is a DFGD unit. A method for simultaneously increasing the active life of an SCR catalyst and controlling the formation of selenium species in a gas phase in at least one component of a selenium species formation and/or emission control device in a flue gas and/or gas phase, the method comprising Show Step: (A) providing at least one coal-based fuel to the furnace or boiler; (B) subjecting the at least one coal-based fuel to a staged combustion method, wherein the staged combustion method produces gaseous mercury; (C) entering the flue gas Prior to SCR, at least one iron-bearing compound is provided to the combustion zone or flue gas stream of the furnace or boiler; and (D) at least one iron-bearing compound is present and present before the flue gas enters the SCR Any of the gaseous phosphorus compounds or phosphorus-containing compounds in the combustion zone or flue gas and any selenium and/or selenium present in the combustion zone, flue gas, and/or gas phase of at least one component of the emission control device Compound reaction wherein the process achieves at least about 10% increase in catalytic activity and/or catalytic lifetime at an operating time of at least about 2,000 hours while allowing control in one or more gas phases and/or emissions The selenium species in the at least one component of the control device is formed, resulting in a reduction in selenium emissions in the flue gas and/or from one or more components of the emission control device. The method of claim 19, wherein the compound carrying iron is selected from the group consisting of at least one inorganic compound carrying iron. The method of claim 19, wherein the compound carrying iron is selected from the group consisting of metallic iron, one or more iron oxides, iron carbonate, iron (II) acetate, iron (II) nitrate, and ferric nitrate ( III), a mixture of iron (II) sulfate, iron (III) sulfate or two or more thereof. The method of claim 19, wherein the compound carrying iron is selected from the group consisting of iron (III) oxide, iron (II) carbonate, iron (II) oxide, and Iron iron (II) or a mixture of two or more thereof. The method of claim 19, wherein the compound carrying iron is selected from the group consisting of organic compounds carrying iron. The method of claim 19, wherein the method further comprises adding at least one compound selected from the group consisting of one or more aluminum-carrying compounds, one or more compounds carrying nickel, one or more copper-carrying An additional metal-carrying compound of one or more compounds bearing zinc or a mixture of two or more thereof. The method of claim 19, wherein the at least one iron-carrying compound is supplied to the combustion zone via addition to the pulverized coal. The method of claim 19, wherein the at least one iron-carrying compound is supplied to the combustion zone via a dedicated supply line. The method of claim 19, wherein at least one component of the emission control device is a WFGD unit. The method of claim 19, wherein at least one component of the emission control device is a DFGD unit. The method of claim 19, wherein the at least one iron-carrying compound is provided in an excess stoichiometric ratio of iron to phosphorus in the range of from about 2.5:1 to about 10:1. The method of claim 19, wherein the at least one iron-carrying compound is provided in an excess stoichiometric ratio of iron to phosphorus in the range of from about 3.5:1 to about 8:1. For example, the method of claim 19, wherein the method is another Externally includes the step of controlling the oxidation of mercury via the addition of at least one compound carrying a halide. The method of claim 31, wherein the method further comprises controlling one or more of the gas phase sodium, the gas phase sodium compound, the gas phase potassium, and/or the gas phase potassium compound by adding at least one compound carrying kaolin. More steps. The method of claim 19, wherein the method further comprises controlling one or more of the gas phase sodium, the gas phase sodium compound, the gas phase potassium, and/or the gas phase potassium compound by adding at least one compound carrying kaolin. More steps. A method for controlling selenium species formation in a flue gas and/or gas phase in at least one component of an emission control device and in conjunction with a post-combustion CO ₂ capture procedure, the method comprising the steps of: (I) providing at least one a coal-based fuel to a furnace or a boiler; (II) a staged combustion method for the at least one coal-based fuel, wherein the staged combustion method produces gaseous mercury; (III) at least one of the flue gases before the SCR enters the SCR a metal compound is provided to the combustion zone or flue gas stream of the furnace or boiler; and (IV) allows the at least one metal-carrying compound to be present in the combustion zone, flue gas, and/or at least one component of the emission control device Or reacting any selenium and/or selenium compound in the gas phase, wherein the at least one metal-carrying compound provides an amount to allow control of one or more combustion zones, flue gases present in at least one component of the emission control device And/or the selenium species in the one or more gas phases are formed, resulting in the combustion zone, the flue gas, and/or any or from the at least one component of the emission control device Reduce or selenium contained within a plurality of exhaust gas (VI) amount or concentration of ions and / or post-combustion CO ₂ capture with the program and with the at least one amine compound to reduce selenium (VI) ion amount or concentration. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of at least one inorganic compound carrying iron. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of metallic iron, one or more iron oxides, iron carbonate, iron (II) acetate, iron (II) nitrate, and ferric nitrate ( III), a mixture of iron (II) sulfate, iron (III) sulfate or two or more thereof. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of iron (III) oxide, iron (II) carbonate, iron (II) oxide, iron (II) acetate or two or more thereof. a mixture. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of organic compounds carrying iron. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of aluminum metal, aluminum acetate, aluminum bromate, aluminum bromide, aluminum chloride, aluminum fluoride, aluminum hydroxide, aluminum iodide, Aluminum nitrate, aluminum oxide, aluminum sulfate or a mixture of two or more thereof. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of organic compounds bearing aluminum. The method of claim 34, wherein the compound carrying the metal is selected from the group consisting of nickel metal, nickel acetate, nickel bromate, nickel bromide, and carbonic acid. Nickel, basic nickel carbonate, nickel chloride, nickel fluoride, nickel hydroxide, nickel iodate, nickel iodide, nickel nitrate, nickel oxide, nickel sulfate or a mixture of two or more thereof. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of organic compounds carrying nickel. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of copper metal, copper acetate, copper bromate, copper bromide, copper trioxygen bromide, copper carbonate, basic copper carbonate, and chlorination. Copper, copper fluoride, copper hydroxide, copper iodate, copper iodide, copper nitrate, copper oxide, copper sulfate or a mixture of two or more thereof. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of organic compounds carrying copper. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of metal zinc, zinc acetate, zinc bromate, zinc bromide, zinc carbonate, zinc chloride, zinc ferrite, zinc fluoride, and hydrogen. Zinc oxide, zinc iodate, zinc iodide, zinc nitrate, zinc oxide, zinc sulfate or a mixture of two or more thereof. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of organic compounds bearing zinc. The method of claim 34, wherein the metal-carrying compound is selected from the group consisting of one or more compounds carrying iron, one or more compounds carrying aluminum, one or more carrying nickel a compound, one or more compounds carrying copper, one or more compounds bearing zinc, or a mixture of any two or more thereof. The method of claim 34, wherein the at least one metal-carrying compound is supplied to the combustion zone via addition to the pulverized coal. The method of claim 34, wherein the at least one metal-carrying compound is supplied to the combustion zone via a dedicated supply line. The method of claim 34, wherein at least one component of the emission control device is a WFGD unit. The method of claim 34, wherein at least one component of the emission control device is a DFGD unit.