Articles, systems, and methods including articles having halogen reservoirs

Abstract

A durable pollution control system, article, and method for removing a plurality of flue gas pollutants. The pollution control system includes an article comprising a sorbent polymer composite (SPC) and a plurality of halogen stores. In some cases, the halogen stores are embedded within the SPC. In some cases, each halogen store has from 5 wt% to 95 wt% of at least one permeation control material and from 5 wt% to 50 wt% of at least one halogen source, based on the average weight of the respective halogen store.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and interest in U.S. Provisional Patent Application No. 63 / 113,047, filed November 12, 2020, entitled “Article comprising a plurality of halogen storage bodies, and systems and methods comprising the same,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of pollution control systems and methods for removing compounds and fine particulate matter from airflow. Background Technology

[0004] Coal-fired power plants, municipal solid waste incinerators, and oil refineries generate large quantities of flue gas containing a wide range of environmental pollutants, such as sulfur oxides (SO2 and SO3), nitrogen oxides (NO, NO2), mercury (Hg) vapor, and particulate matter (PM). In the United States alone, burning coal produces approximately 27 million tons of SO2 and 45 tons of Hg annually. Therefore, there is a need to improve control systems and methods for removing sulfur oxides, mercury vapor, and fine particulate matter from industrial flue gas, such as that from coal-fired power plants. Summary of the Invention

[0005] In some embodiments, an improved durable pollution control system is provided that can simultaneously remove multiple flue gas pollutants. These pollutants may include, but are not limited to, SO₂. x Hg vapor and PM2.5 (particulate matter with a diameter of 2.5 micrometers or smaller). Some embodiments may include a simple pollution control system that can prevent the generation of secondary pollutants. In some embodiments, the pollution control system can provide the required amount of halogen source over a long period of time. In particular, the flue gas treatment device may include a more durable and longer-lasting halogen source in combination with an adsorbent polymer composite substrate. In some embodiments, the adsorbent polymer substrate may not be leached off in the solution formed during the treatment process.

[0006] Some embodiments of this disclosure relate to articles having a layered structure, which may include a halogen source and an SPC. In some embodiments, the articles described herein may allow for delayed release of at least one halogen source from a halogen reservoir, which may form part of the articles described herein.

[0007] In some embodiments, the article of manufacture includes a flue gas treatment apparatus. In some embodiments, the article of manufacture is a flue gas treatment apparatus. In some embodiments, the article of manufacture is part of a flue gas treatment apparatus.

[0008] In some embodiments, the article includes a first SPC layer; a second SPC layer; and a halogen reservoir, wherein the halogen reservoir is disposed between the first SPC layer and the second SPC layer.

[0009] In some embodiments, the article includes or further includes at least one permeation control material.

[0010] In some embodiments of the article of manufacture, the at least one permeation control material is in the form of at least one permeation control layer, wherein the at least one permeation control layer is disposed between the first SPC layer and the halogen reservoir, between the second SPC layer and the halogen reservoir, or both. That is, in some embodiments of the article of manufacture, the at least one permeation control material is in the form of at least one permeation control layer, wherein the at least one permeation control layer is disposed between the first SPC layer and the halogen reservoir, and also between the second SPC layer and the halogen reservoir.

[0011] In some embodiments of the product, the at least one permeation control layer includes a first layer of the at least one permeation control material, wherein the first layer is disposed between the first SPC layer and the halogen reservoir; and a second layer of the at least one permeation control material, wherein the second layer is disposed between the second SPC layer and the halogen reservoir.

[0012] In some embodiments, the article includes an adsorbent polymer complex (SPC); and a plurality of halogen reservoirs embedded within the SPC, wherein each of the plurality of halogen reservoirs comprises, based on the average weight of each halogen reservoir, at least 5% to 95% by weight of at least one permeation control material, and at least 5% to 50% by weight of at least one halogen source based on the average weight of each halogen reservoir.

[0013] In some embodiments of the article of manufacture, the SPC comprises a polymer material.

[0014] In some embodiments of the article, the polymer material includes at least one of the following: polyvinylidene fluoride propylene (PFEP); perfluoroacrylate (PPFA); polyvinylidene fluoride (PVDF); a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV); polyvinyl chloride trifluoroethylene (PCFE); poly(ethylene-co-tetrafluoroethylene) (ETFE); ultra-high molecular weight polyethylene (UHMWPE); polyethylene; poly(p-xylene) (PPX); polylactic acid (PLLA); polyethylene (PE); expanded polyethylene (ePE); polytetrafluoroethylene (PTFE); expanded polytetrafluoroethylene (ePTFE); or any combination thereof.

[0015] In some embodiments of the article of manufacture, the polymer material includes PVDF.

[0016] In some embodiments of the article, PVDF is a PVDF homopolymer.

[0017] In some embodiments of the article, PVDF is a PVDF copolymer.

[0018] In some embodiments of the article, the PVDF copolymer is a copolymer of PVDF and hexafluoropropylene (HFP).

[0019] In some embodiments of the article of manufacture, the polymeric material includes PTFE.

[0020] In some embodiments of the article of manufacture, the polymeric material includes ePTFE.

[0021] In some embodiments of the article of manufacture, the polymer material includes fibrils and nodes, wherein the polymer material becomes porous when stretched, thereby creating voids between the fibrils and nodes.

[0022] In some embodiments of the article of manufacture, at least one halogen source includes at least one metal halide, ammonium halide, elemental halogen, or any combination thereof.

[0023] In some embodiments of the article, at least one halogen source includes at least sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, or any combination thereof.

[0024] In some embodiments of the article, at least one halogen source includes at least one ammonium halide.

[0025] In some embodiments of the article, at least one halogen source includes at least tetramethylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium triiodide, tetrabutylammonium tribromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, or any combination thereof.

[0026] In some embodiments of the article of manufacture, at least one halogen source includes at least one elemental halogen.

[0027] In some embodiments of the article, the elemental halogen is at least one of elemental iodine (I2), elemental chlorine (Cl2) or elemental bromine (Br2).

[0028] In some embodiments of the article, at least one halogen source includes tetrabutylammonium iodide (TBAI).

[0029] In some embodiments of the product, at least one halogen source includes potassium iodide (KI).

[0030] In some embodiments of the article of manufacture, at least one halogen source includes at least one phosphorus halide.

[0031] In some embodiments of the article of manufacture, at least one phosphonium halide comprises tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof. In some embodiments, the at least one phosphonium halide is selected from the group consisting of tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof.

[0032] In some embodiments of the article of manufacture, at least one phosphonium halide is ETPPI.

[0033] In some embodiments of the article, the article comprises a sufficient quantity of multiple halogen reservoirs such that, under conditions where a flue gas stream flows over at least one surface of the article for at least 90 days, the release rate of total halogens from the article is no more than 0.5% of the total halogens in the article per day; wherein the flue gas stream has a temperature of at least 50°C and a relative humidity of at least 95%, and wherein the gas stream contains at least one SO₂ at a concentration of at least 20 ppm. x Compounds, and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0034] In some embodiments of the article, the article comprises a sufficient number of multiple halogen reservoirs such that, under conditions where a flue gas stream flows over at least one surface of the article for at least 90 days, the release rate of total halogens from the article is no more than 2% of the total halogens in the article per day; wherein the flue gas stream has a temperature of at least 20°C and a relative humidity of at least 95%, and wherein the gas stream contains at least one SO₂ at a concentration of at least 1 ppm. x Compounds, and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0035] In some embodiments of the article of manufacture, at least one of the plurality of halogen reservoirs is in the form of an encapsulated bead, wherein the encapsulated bead includes a core and at least one halogen source, wherein the at least one halogen source is present at least on the surface of the core; and a permeation control material, wherein the permeation control material encapsulates the core.

[0036] In some embodiments of the article, the core includes activated carbon.

[0037] In some embodiments of the article of manufacture, at least one of the plurality of halogen reservoirs is in the form of reservoir particles, wherein the reservoir particles comprise a permeation control material, wherein the permeation control material is in the form of permeation control particles; and at least one halogen source, wherein the at least one halogen source is present at least on the surface of the permeation control particles.

[0038] In some embodiments of the article, the permeation control material includes polystyrene, cross-linked polystyrene-divinylbenzene (PS-DVB), or a combination thereof.

[0039] In some embodiments of the product, the storage particles further include a second permeation control material, wherein the second permeation control material surrounds at least one halogen source on the surface of the permeation control particles.

[0040] In some embodiments of the article of manufacture, the plurality of halogen reservoirs take the form of a plurality of reservoir clusters, wherein each reservoir cluster includes at least one halogen source; and a permeation control material.

[0041] In some embodiments of the product, the multiple storage clusters take the form of multiple halogen storage fragments embedded throughout the SPC.

[0042] In some embodiments of the product, the multiple storage clusters take the form of multiple halogen storage aggregates mixed with SPC.

[0043] In some embodiments of the article, based on the total weight of the article, the amount of the plurality of halogen reservoirs is 5% to 75% by weight of the plurality of halogen reservoirs.

[0044] In some embodiments of the article, based on the total weight of the article, the sufficient amount of the plurality of halogen reservoirs is 5% to 50% by weight of the plurality of halogen reservoirs.

[0045] In some embodiments, a method includes obtaining an adsorbent polymer complex (SPC); and obtaining a plurality of halogen reservoirs, wherein each of the plurality of halogen reservoirs comprises: 5% to 95% by weight of at least one permeation control material and 5% to 50% by weight of at least one halogen source based on the average weight of the respective halogen reservoir; and forming particles having the plurality of halogen reservoirs embedded within the SPC.

[0046] In some embodiments of the method, at least one of the plurality of halogen reservoirs is in the form of an encapsulated bead, wherein the method further includes forming the encapsulated bead by: obtaining at least one core-forming particle; depositing at least one halogen source onto the surface of at least one particle; and encapsulating the core with at least one permeation control material to form the encapsulated bead.

[0047] In some embodiments of the method, at least one halogen source is deposited as a solution on the surface of at least one particle.

[0048] In some embodiments of the method, at least one halogen source is deposited as a vapor phase on the surface of at least one particle.

[0049] In some embodiments of the method, at least one particle is a carbon particle.

[0050] In some embodiments of the method, at least one of the plurality of halogen reservoirs is in the form of reservoir particles, wherein the reservoir particles are formed by obtaining a permeation control material in the form of at least one permeation control particle; and by depositing at least one halogen source onto the surface of the permeation control particle.

[0051] In some embodiments, the method further includes depositing a second permeation control material on at least a portion of the storage particles after depositing at least one halogen source onto the surface of the permeation control particles to form a second permeation control layer surrounding at least one halogen source.

[0052] In some embodiments of the method, the plurality of halogen reservoirs are in the form of a plurality of reservoir clusters, wherein the method further includes forming each of the plurality of reservoir clusters by: mixing a plurality of particles with at least one halogen source and at least one permeation control material to form a mixture; forming the mixture into a membrane or fragment; forming the membrane or fragment into a halogen reservoir fragment; and embedding the halogen reservoir fragment into an SPC.

[0053] In some embodiments of the method, the plurality of halogen reservoirs are in the form of a plurality of reservoir clusters, wherein the method further includes forming each of the plurality of reservoir clusters by: obtaining an SPC agglomerate; mixing a plurality of particles with at least one halogen source and at least one permeation control material to form a reservoir agglomerate; and mixing the SPC agglomerate with the reservoir agglomerate to form an article.

[0054] In some embodiments, the method further includes flowing a flue gas stream to contact the article, wherein the flue gas stream has a temperature of at least 50°C and a relative humidity of at least 95%, and wherein, based on the total volume of the flue gas stream, the flue gas stream contains at least one SO42-containing compound at a concentration of at least 20 ppm. x Compounds, and concentrations of at least 1 μg / m 3 Mercury vapor, wherein the release rate of total halogens from the product is no more than 0.5% of the total halogens in the product per day. Attached Figure Description

[0055] Referring now to the accompanying drawings, some embodiments of the present invention will be described by way of example. It will be emphasized that the illustrated embodiments are exemplary and intended for illustrative purposes regarding embodiments of this disclosure. In this regard, how to implement embodiments of this disclosure will be apparent to those skilled in the art from the description in conjunction with the accompanying drawings.

[0056] Figure 1A A non-limiting embodiment of the adsorbent polymer complex (SPC) described herein is depicted in cross-sectional view.

[0057] Figure 1B Further non-limiting embodiments of the adsorbent polymer complex (SPC) described herein are depicted.

[0058] Figures 2A-2F Non-limiting embodiments of halogen reservoirs according to some embodiments of the present disclosure are described, in which a permeation control material is encapsulated and incorporated into an adsorbent polymer complex (SPC).

[0059] Figure 3A This is an electronic image depicting a plurality of halogen storage particles in the form of coated iodine-loaded particles according to some non-limiting embodiments of the present disclosure.

[0060] Figure 3B This is an electronic image depicting an adsorbent polymer complex (SPC) comprising multiple storage particles coated in the form of iodine-loaded particles, according to some non-limiting embodiments of the present disclosure.

[0061] Figure 4A and 4B This is an electronic image depicting an adsorbent polymer complex (SPC) with one or more halogen storage particles embedded according to some non-limiting embodiments of the present disclosure.

[0062] Figure 5A Encapsulation beads according to some non-limiting embodiments of the present disclosure are depicted.

[0063] Figure 5B This is an electronic image of a collection of encapsulated beads according to some embodiments of the present disclosure.

[0064] Figure 6A and Figure 6B These are photographs of a group of halogen storage clusters according to some non-limiting embodiments of this disclosure.

[0065] Figure 7 This is a graph showing the relationship between the relative iodine content of some samples and time according to some embodiments of this disclosure.

[0066] Figure 8This is a graph showing the relationship between the relative iodine content of some samples and time according to some embodiments of this disclosure.

[0067] Figure 9 The graph shows the relationship between the relative iodine content and time for some comparative samples.

[0068] Figure 10 The graph shows the relationship between the relative iodine content and time for some comparative samples.

[0069] Figure 11 Non-limiting embodiments of a pollution control system having any of one or more of the articles described herein are depicted.

[0070] Figure 12 Non-limiting embodiments are depicted, illustrating non-limiting embodiments of flue gas flowing through one or more articles described herein. Detailed Implementation

[0071] Among the benefits and improvements already disclosed, other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Specific embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely examples of this disclosure that may be embodied in various forms. Furthermore, the various embodiments given with respect to this disclosure are intended to be illustrative and not restrictive.

[0072] Throughout the specification and claims, unless the context clearly indicates otherwise, the following terms have the meaning explicitly associated with this document. Although the phrases “in one embodiment,” “in one embodiment,” and “in some embodiments” as used herein may refer to the same embodiment, they do not necessarily refer to the same embodiment. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein may refer to different embodiments, but do not necessarily refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0073] As used herein, the term "between" does not necessarily require direct adjacency with other elements. Typically, the term refers to a configuration in which something is sandwiched between two or more other things. At the same time, the term "between" can describe things directly adjacent to two opposing things. Therefore, in any one or more embodiments disclosed herein, a particular structural component disposed between two other structural elements can be:

[0074] It is positioned directly between two other structural elements, so that the specific structural component is in direct contact with both other structural elements;

[0075] It is positioned directly next to one of the two other structural elements, such that the particular structural component is in direct contact with only one of the two other structural elements;

[0076] It is indirectly placed next to one of the two other structural elements, such that the particular structural element is not in direct contact with only one of the two other structural elements, and there is another element that juxtaposes the particular structural element with one of the two other structural elements;

[0077] Indirectly positioned between two other structural elements, so that a specific structural component does not directly contact the two other structural elements, and other features can be positioned between them; or

[0078] Any one or more of them.

[0079] As used herein, the term "based on" is not exclusive and allows for basing on other factors not described unless the context clearly indicates otherwise. Furthermore, throughout the specification, the meanings of "an," "a," and "the" include plural references. The meaning of "in" includes both "in" and "above."

[0080] All existing patents and publications cited in this article are included in this article in their entirety by reference.

[0081] Adsorbent polymer complexes (SPCs) have proven particularly effective in removing unwanted components from flue gas streams. Such unwanted components may include, but are not limited to, at least one SO₂. x Compounds and mercury vapor.

[0082] Using at least one halogen source can improve the removal efficiency of SPC. However, in some cases, the at least one halogen source may not be durable enough to keep the SPC (and systems including it, such as, but not limited to, fixed-bed absorption systems) running for many years. In some cases, this may happen because the added at least one halogen source may be released from the adsorbent.

[0083] Therefore, some embodiments of this disclosure provide an exemplary solution in which multiple halogen reservoirs can release at least one halogen source over time. Compared to an SPC that does not include multiple halogen reservoirs, multiple halogen reservoirs can allow the SPC (and systems including it, such as, but not limited to, fixed-bed absorption systems) to operate (e.g., be in service) for a longer period of time.

[0084] As used herein, the term "adsorbent" refers to a substance that has the property of collecting molecules of another substance by absorbing, adsorbing, or at least a combination thereof. Adsorbent polymer composite materials include at least one of activated carbon, coal-derived carbon, lignite-derived carbon, wood-derived carbon, coconut-derived carbon, silica gel, zeolite, or any combination thereof.

[0085] As used herein, the term "complex" refers to a material comprising two or more constituent materials with different physical or chemical properties, wherein the combination of the two or more constituent materials produces a material having characteristics different from those of the individual components.

[0086] As used herein, an "adsorbent polymer complex" (SPC) is a complex comprising an adsorbent and a polymer. In embodiments, the adsorbent polymer complex may include adsorbent particles incorporated into the microstructure of the polymer.

[0087] The adsorbent polymer composite material also includes a halogen source. In some embodiments, the halogen source can be incorporated into the adsorbent polymer composite material using any suitable technique, including but not limited to absorption, impregnating, adsorption, mixing, spraying, coating, dipping, painting, coating, ion exchange, or other methods of applying the halogen source to the adsorbent polymer composite material. In some embodiments, the halogen source can be located within the adsorbent polymer composite material, for example, within any pores of the adsorbent polymer composite material. In some embodiments, the halogen source can be provided in a solution that can contact the adsorbent polymer composite material in situ under system operating conditions. The halogen source of the adsorbent polymer composite is a halogen salt, an elemental halogen, or any combination thereof. In some embodiments, the halogen source is selected from at least one of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetramethylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, elemental iodine (I2), elemental chlorine (Cl2), elemental bromine (Br2), or any combination thereof. Additional configurations of the adsorbent polymer complexes described herein and additional examples of the halogen sources described herein are described in U.S. Patent No. 9,827,551 (1368) to Hardwick et al. and U.S. Patent No. 7,442,352 to Lu et al., each of which is incorporated herein by reference in its entirety.

[0088] As used herein, the term "repository" refers to a repository containing at least one material, wherein the repository is configured to release the at least one material over a period of time. In some non-limiting embodiments, the repository may include a permeation control material.

[0089] As used herein, the term "halogen reservoir" refers to a reservoir comprising at least one halogen source, wherein the at least one halogen source is configured to be released from the reservoir over a period of time.

[0090] As used in this article, "embedded" means that the first material is distributed throughout the second material.

[0091] As used herein, the term "permeation control material" refers to a material configured to release one or more substances from a reservoir at a slower rate than the rate at which substances would be released without a permeation control layer.

[0092] As used herein, the term "halogen source" refers to any compound or elemental halogen containing at least one halide ion. The halogen source for the flue gas treatment device is selected from tetrabutylammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium tribromide, or tetrabutylammonium bromide. In another embodiment, the halogen source is a compound having the formula N(R1R2R3R4)X, where N is nitrogen and X = 1. - ,Br - I3 - ,BrI2 - Br2I - Br3 - R1, R2, R3, and R4 are selected from hydrocarbons having about 1 to about 18 carbon atoms, wherein the hydrocarbon can be a simple alkyl group, including but not limited to straight-chain or branched alkyl groups. The halogen source can include a trihalide, wherein the trihalide is formed by acid treatment of its halide precursor in the presence of an oxidizing agent. In another embodiment, the halogen source is a trihalide, wherein the trihalide is formed by acid treatment of its halide precursor in the presence of an oxidizing agent selected from the group consisting of hydrogen peroxide, alkali metal persulfates, alkali metal monopersulfates, potassium iodate, potassium monopersulfate, oxygen, iron(III) salts, ferric (III) nitrate, ferric (III) sulfate, ferric (III) oxide, and combinations thereof.

[0093] As used in this article, the method for calculating the "average weight of each halogen reservoir" is to add up the weights of each of the multiple halogen reservoirs in a particular product, and then divide the sum of the weights by the total weight of the product.

[0094] As used herein, "total halogen release rate" refers to the rate at which at least one halogen source is released from the article into the external environment in which the article is located. In some non-limiting embodiments, the external environment may be a flue gas stream. In some embodiments, at least one halogen source is released into the external environment only from the adsorbent polymer complex (SPC). In these embodiments, "total halogen release rate" is the release rate from the adsorbent polymer complex (SPC) to the external environment. In some embodiments, at least one halogen source is released into the external environment only from multiple halogen reservoirs. In these embodiments, "total halogen release rate" is the release rate from multiple halogen reservoirs to the external environment. In some embodiments, at least one halogen source is released into the external environment from a combination of the adsorbent polymer complex (SPC) and multiple halogen reservoirs. In these embodiments, "total halogen release rate" is a combined release rate, which includes the release of at least one halogen source from the adsorbent polymer complex (SPC) and multiple halogen reservoirs. In some embodiments, the article includes multiple halogen sources. In these embodiments, "total halogen release rate" is a combined release rate, which includes the release of all multiple halogen sources in the article. The determination of the release rate is explained further below.

[0095] As used herein, the term "flue gas flow" refers to a gas mixture that includes at least one byproduct of a combustion process (e.g., but not limited to, coal combustion). In some embodiments, the flue gas flow may consist entirely of byproducts of the combustion process. In some embodiments, the flue gas flow may include at least one gas with a concentration higher than that produced by the combustion process. For example, in a non-limiting instance, the flue gas flow may undergo a "washing" process in which water vapor may be added to the flue gas flow. Thus, in some such embodiments, the flue gas flow may include water vapor with a concentration higher than that of the initial water vapor concentration due to combustion. Similarly, in some embodiments, the flue gas flow may include at least one gas with a lower concentration than that of the initial gas output from the combustion process. This can occur, for example, by removing at least a portion of the at least one gas after combustion. In some embodiments, the flue gas flow may take the form of a gas mixture of a combination of various combustion process byproducts.

[0096] As used in this article, the term "SO" x "Compound" refers to any sulfur oxide. In some non-limiting embodiments, "SO" x "Compounds" can specifically refer to gaseous oxides of sulfur, which are known as environmental pollutants. SO x Non-limiting examples of compounds include sulfur dioxide (SO2) and sulfur trioxide (SO3). xOther non-limiting examples of compounds include sulfur monoxide (SO), disulfur monoxide (S2O), and disulfur dioxide (S2O2).

[0097] As used herein, the term "mercury vapor" refers to a gaseous compound containing mercury. Non-limiting examples of mercury vapor include elemental mercury vapor and mercury oxide vapor.

[0098] As used herein, the term "mercury oxide vapor" is defined as a gaseous mercury compound comprising positively valent mercury. Non-limiting examples of mercury oxide vapor include mercurous halide and mercury halide.

[0099] Various terms are used herein to describe the forms of halogen reservoirs. These forms generally describe halogen reservoirs of localized volume (i.e., localized volume or localized concentration of halogen). The terms encapsulated beads, particles, clusters, aggregates, and streaks all describe various forms of volume-localized halogen clusters. For example, beads can be substantially spherical with a uniformly smooth outer surface or with a non-uniformly smooth (i.e., uneven) outer surface. The shape or form of beads can be regular or irregular. For example, particles can have irregular shapes or sizes, or irregular shapes and sizes. Particles and fragments are generally non-uniformly spherical or generally have a uniformly smooth surface. Particles and fragments can be irregularly distributed within a substance. In some embodiments, a particular form of volume-localized halogen can be described as any one or more of these forms.

[0100] As used herein, the term "encapsulated bead" refers to a halogen reservoir in bead form, comprising a core and at least one encapsulating agent surrounding the core. At least one halogen source is present on at least one surface of the core. The core may include carbon, such as activated carbon. In some embodiments, the at least one encapsulating agent may include a permeation control material.

[0101] As used herein, the term "reservoir particle" refers to a halogen reservoir in particulate form. In some embodiments, a "reservoir particle" may include at least one permeation control material as described herein and at least one halogen source. Some non-limiting examples of "reservoir particles" include, but are not limited to, embodiments of reservoir fragments, reservoir aggregates, iodine-loaded beads, and encapsulated beads. At least one specific non-limiting embodiment of a reservoir fragment is described in detail in Example 1. At least one specific non-limiting embodiment of a reservoir aggregate is described in detail in Example 1. At least one specific non-limiting embodiment of an encapsulated bead is described in detail in Example 2. At least one specific non-limiting embodiment of an iodine-loaded bead is described in detail in Example 3.

[0102] As used herein, the term "reservoir cluster" refers to a cluster of halogen storage cells in the form of stripes or irregularly shaped clumps.

[0103] As used herein, a “repository aggregate” is a collection or mass of repository clusters. In some implementations, each “repository aggregate” (i.e., each collection or mass of repository clusters) may be located within at least one specific region of the SPC.

[0104] As used in this article, the term "agglomerated mixture" refers to a mixture in which the components of the mixture are aggregated together.

[0105] As used in this article, “carbon particles” refers to any particles that contain carbon.

[0106] As used in this article, "porous carbon particles" refers to carbon particles with pores, excluding carbon particles without pores. In other words, porous carbon particles exclude "non-porous" carbon particles.

[0107] As used herein, the term "permeability control particles" refers to at least one permeability control material in particulate form.

[0108] Some embodiments of this disclosure relate to articles comprising an adsorbent polymer complex (SPC) and a plurality of halogen reservoirs.

[0109] In some embodiments, the adsorbent polymer complex (SPC) may include one or more homopolymers, copolymers or terpolymers containing at least one fluorinated monomer, with or without additional nonfluorinated monomers.

[0110] In some embodiments, the polymer material of the adsorbent polymer complex (SPC) may include at least one of the following: polyvinylidene fluoride propylene (PFEP); perfluoroacrylate (PPFA); polyvinylidene fluoride (PVDF); a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV); polyvinyl chloride trifluoroethylene (PCFE); poly(ethylene-co-tetrafluoroethylene) (ETFE); ultra-high molecular weight polyethylene (UHMWPE); polyethylene; poly(p-xylene) (PPX); polylactic acid (PLLA); polyethylene (PE); expanded polyethylene (ePE); polytetrafluoroethylene (PTFE); expanded polytetrafluoroethylene (ePTFE); or any combination thereof.

[0111] In some embodiments, the polymer material of the adsorbent polymer complex (SPC) may include polyvinylidene fluoride (PVDF). In some embodiments, the PVDF may be a PVDF homopolymer. In some embodiments, the PVDF may be a PVDF copolymer. In some embodiments, the PVDF copolymer is a copolymer of PVDF and hexafluoropropylene (HFP). Non-limiting commercial examples of PVDF homopolymers or copolymers suitable for some embodiments of this disclosure include, but are not limited to, Kynar. and Kynar All of them can be purchased from Arkema.

[0112] In some embodiments, the polymer material of the adsorbent polymer complex (SPC) may include polytetrafluoroethylene (PTFE). In some embodiments, the polymer is expanded polytetrafluoroethylene (ePTFE). In some embodiments, the polymer structure becomes porous upon stretching, allowing voids to form between the fibrils and the polymer nodes.

[0113] In some embodiments, the adsorbent polymer complex (SPC) has a thickness of 0.2 mm to 2 mm, 0.4 mm to 2 mm, 0.8 mm to 2 mm, 1.2 mm to 2 mm, or 1.6 mm to 2 mm. In some embodiments, the adsorbent polymer complex (SPC) has a thickness of 0.2 mm to 1.6 mm, 0.2 mm to 1.2 mm, 0.2 mm to 0.8 mm, or 0.2 mm to 0.4 mm. In some embodiments, the adsorbent polymer complex (SPC) has a thickness of 0.4 mm to 1.6 mm or 0.8 mm to 1.2 mm. In some embodiments, the thickness of the adsorbent polymer complex (SPC) can be measured using a cross-sectional scanning electron microscope.

[0114] In some embodiments, the polymer of the adsorbent polymer complex (SPC) has a surface energy of less than 31 dynes / cm, less than 30 dynes / cm, less than 25 dynes / cm, less than 20 dynes / cm, or less than 15 dynes / cm.

[0115] In some embodiments, the polymer of the adsorbent polymer complex (SPC) has a surface energy of 15 dynes / cm to 31 dynes / cm, 20 dynes / cm to 31 dynes / cm, 25 dynes / cm to 31 dynes / cm, 30 dynes / cm to 31 dynes / cm, 15 dynes / cm to 30 dynes / cm, 15 dynes / cm to 25 dynes / cm, or 15 dynes / cm to 20 dynes / cm.

[0116] In some embodiments, the polymer of the adsorbent polymer complex (SPC) has a surface energy of 20 dynes / cm to 25 dynes / cm.

[0117] In some embodiments, the SPC includes an adsorbent. In some embodiments, the adsorbent of the SPC includes activated carbon. In some embodiments, the adsorbent includes activated carbon derived from coal, lignite, wood, coconut shell, other carbonaceous materials, or any combination thereof. In some embodiments, the adsorbent may include silica gel, zeolite, or any combination thereof.

[0118] In some embodiments, the adsorbent polymer complex (SPC) has an adsorbent with a molecular weight exceeding 400 m. 2 / g, exceeding 600m 2 / g, exceeding 800m 2 / g, exceeding 1000m 2 / g, exceeding 1200m 2 / g, exceeding 1400m 2 / g, exceeding 1600m 2 / g, exceeding 1800m 2 / g or more than 2000m 2 / g of surface area.

[0119] In some embodiments, the adsorbent polymer complex (SPC) has an adsorbent with a concentration of 400 m. 2 / g to 2000m 2 / g、600m 2 / g to 2000m 2 / g、800m 2 / g to 2000m 2 / g, 1000m 2 / g to 2000m 2 / g、1200m 2 / g to 2000m 2 / g, 1400m 2 / g to 2000m 2 / g, 1600m 2 / g to 2000m 2 / g, or 1800m 2 / g to 2000m 2 / g of surface area.

[0120] In some embodiments, the adsorbent polymer complex (SPC) has an adsorbent with a concentration of 400 m. 2 / g to 1800m 2 / g、400m 2 / g to 1600m 2 / g、400m 2 / g to 1400m 2 / g、400m 2 / g to 1200m 2 / g、400m 2 / g to 1000m 2 / g、400m 2 / g to 800m 2 / g, or 400m 2 / g to 600m 2 / g of surface area.

[0121] In some embodiments, the adsorbent polymer complex (SPC) has an adsorbent with a concentration of 600 m. 2 / g to 1800m 2 / g、800m 2 / g to 1600m 2 / g, or 1000m 2 / g to 1400m 2 / g of surface area.

[0122] In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) comprises a metal halide, ammonium halide, elemental halogen, or any combination thereof. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) comprises a metal halide. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is selected from at least one of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, or potassium iodide. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) comprises an ammonium halide. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is selected from at least one of tetramethylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium triiodide, tetrabutylammonium tribromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, or tetrabutylammonium chloride. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) includes an elemental halogen. In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is selected from at least one of elemental iodine (I2), elemental chlorine (Cl2), or elemental bromine (Br2).

[0123] In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is elemental iodine (I₂). In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is tetrabutylammonium iodide (TBAI). In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) is potassium iodide (KI).

[0124] In some embodiments, at least one halogen source of the adsorbent polymer complex (SPC) includes at least one phosphonium halide.

[0125] In some embodiments, at least one phosphonium halide comprises tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof. In some embodiments, the at least one phosphonium halide is selected from the group consisting of tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof.

[0126] In some embodiments, at least one phosphonium halide comprises tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), or any combination thereof. In some embodiments, at least one phosphonium halide is selected from the group consisting of tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), or any combination thereof.

[0127] In some embodiments, at least one phosphonium halide is ethyltriphenylphosphonium iodide (ETPPI).

[0128] In some embodiments, at least one halogen source can be incorporated into the adsorbent polymer complex (SPC) using any suitable technique, including but not limited to absorption, impregnation, adsorption, mixing, spraying, coating, impregnation, painting, coating, ion exchange, or other methods of applying at least one halogen source to the adsorbent polymer complex (SPC). In some embodiments, at least one halogen source can be located within the adsorbent polymer complex (SPC), for example, within any pores of the adsorbent polymer complex (SPC). In some embodiments, at least one halogen source can be provided in a solution that can contact the adsorbent polymer complex (SPC) in situ under system operating conditions.

[0129] Figure 1AA non-limiting embodiment of the adsorbent polymer complex (SPC) 100 described herein is illustrated in cross-sectional view. In this non-limiting embodiment, the adsorbent polymer complex (SPC) 100 includes an adsorbent 102 that partially or completely covers the polymer 101. In some non-limiting embodiments, at least one halogen source 103 (as described herein) may partially or completely cover a portion of the adsorbent 102. In some embodiments, the at least one halogen source 103 may be absorbed into the pores of the adsorbent 102.

[0130] Figure 1B Further non-limiting embodiments of the adsorbent polymer complex (SPC) 100 described herein are illustrated. As shown, the adsorbent polymer complex (SPC) 100 may include adsorbent particles 206 incorporated into a polymer microstructure 205. In some embodiments, particles 206 may be activated carbon particles. In some embodiments, the polymer microstructure 205 may include fibrils. In some embodiments, the polymer may be expanded PTFE.

[0131] In some embodiments, each of the plurality of halogen reservoirs is embedded within an adsorbent polymer complex (SPC). Figures 2A-2F This is a simplified illustration of a halogen reservoir incorporated in an adsorbent polymer complex (SPC) according to some non-limiting embodiments of the present disclosure. Figures 2A to 2F In a non-limiting embodiment, article 200 may include an adsorbent polymer composite (SPC) 201 and may further include a plurality of halogen reservoirs 202 embedded within the adsorbent polymer composite (SPC) 201. As further shown, as described herein, the plurality of halogen reservoirs 202 may include at least one halogen source 203 and at least one permeation control material 204. Figures 2A to 2F As further shown, the plurality of halogen storage cells 202 can take the form of a plurality of halogen storage cell clusters.

[0132] For example, such as Figure 2A As shown in the non-limiting embodiments, the plurality of halogen stores 202 in the form of multiple store clusters may take the form of “rectangular store fragments” made of, for example, halogen store films or segments, as further described in Example 1.

[0133] For example, such as Figure 2B As shown in the non-limiting embodiment, the plurality of halogen storage cells 202 in the form of a plurality of storage cell clusters can take the form of “elliptical storage cell fragments”.

[0134] For example, such as Figure 2CAs shown in the non-limiting embodiment, the plurality of halogen storage cells 202 in the form of multiple storage cell clusters can take the form of "irregular storage cell fragments".

[0135] For example, such as Figure 2D As shown in the non-limiting embodiment, the plurality of halogen storage cells 202 in the form of multiple storage cell clusters can take the form of "nodular storage cell fragments".

[0136] like Figure 2E As shown in the non-limiting embodiments, the article 200 according to some embodiments of the present disclosure may include an SPC 201. The SPC 201 may further include a plurality of halogen reservoirs 202 embedded within the SPC 201. As further shown, the plurality of halogen reservoirs 202 may include a mixture of at least one halogen source 203 as described herein and at least one permeation control material 204. As further shown, the plurality of halogen reservoirs 202 may take the form of a plurality of reservoir clusters.

[0137] In some implementations, storage clusters can coalesce to take the form of streaks, for example in... Figure 6B In the unrestricted instances.

[0138] In some implementations, such as Figure 2E As shown in a non-limiting embodiment, multiple halogen reservoirs 202 in the form of multiple reservoir agglomerates can cover the entire thickness of the article. In some embodiments, the thickness of the multiple reservoir agglomerates can be equal to the thickness of SPC 201.

[0139] like Figure 2F As shown in the non-limiting embodiment, the plurality of halogen storage cells 202 in the form of a plurality of storage cell clusters can take the form of "circular storage cell particles".

[0140] In some embodiments, the storage cluster has at least one dimension ranging from 0.1 mm to 100 mm. For example, in some embodiments, the at least one dimension may refer to length, width, height, at least one radius, perimeter, arc length, profile length, or any combination thereof.

[0141] In some embodiments, the storage cluster has at least one dimension of 0.1 mm, at least one dimension of 0.2 mm, at least one dimension of 0.3 mm, at least one dimension of 0.4 mm, at least one dimension of 0.5 mm, at least one dimension of 0.6 mm, at least one dimension of 0.7 mm, at least one dimension of 0.8 mm, at least one dimension of 0.9 mm, at least one dimension of 1 mm, at least one dimension of 5 mm, at least one dimension of 10 mm, at least one dimension of 15 mm, at least one dimension of 20 mm, at least one dimension of 25 mm, at least one dimension of 30 mm, at least one dimension of 35 mm, at least one dimension of 40 mm, at least one dimension of 45 mm, at least one dimension of 50 mm, at least one dimension of 55 mm, at least one dimension of 60 mm, at least one dimension of 65 mm, at least one dimension of 70 mm, at least one dimension of 75 mm, at least one dimension of 80 mm, at least one dimension of 85 mm, at least one dimension of 90 mm, at least one dimension of 95 mm, or at least one dimension of 100 mm.

[0142] In some embodiments, the storage clusters have diameters of 0.2 mm to 100 mm, 0.3 mm to 100 mm, 0.4 mm to 100 mm, 0.5 mm to 100 mm, 0.6 mm to 100 mm, 0.7 mm to 100 mm, 0.8 mm to 100 mm, 0.9 mm to 100 mm, 1 mm to 100 mm, 5 mm to 100 mm, 10 mm to 100 mm, 15 mm to 100 mm, 20 mm to 100 mm, and 25 mm to 100 mm. At least one dimension of 100mm, 30mm to 100mm, 35mm to 100mm, 40mm to 100mm, 45mm to 100mm, 50mm to 100mm, 55mm to 100mm, 60mm to 100mm, 65mm to 100mm, 70mm to 100mm, 75mm to 100mm, 80mm to 100mm, 85mm to 100mm, 90mm to 100mm, or 95mm to 100mm.

[0143] In some embodiments, the storage cluster has at least one dimension of 0.1 mm to 95 mm, 0.1 mm to 90 mm, 0.1 mm to 85 mm, 0.1 mm to 80 mm, 0.1 mm to 75 mm, 0.1 mm to 70 mm, 0.1 mm to 65 mm, 0.1 mm to 60 mm, 0.1 mm to 55 mm, 0.1 mm to 50 mm, 0.1 mm to 45 mm, 0.1 mm to 40 mm, 0.1 mm to 35 mm, 0.1 mm to 30 mm, 0.1 mm to 25 mm, 0.1 mm to 20 mm, 0.1 mm to 15 mm, 0.1 mm to 10 mm, 0.1 mm to 5 mm, or 0.1 mm to 1 mm. In some embodiments, the storage cluster has at least one dimension of 0.1 mm to 0.9 mm, 0.1 mm to 0.8 mm, 0.1 mm to 0.7 mm, 0.1 mm to 0.6 mm, 0.1 mm to 0.5 mm, 0.1 mm to 0.4 mm, 0.1 mm to 0.3 mm, or 0.1 mm to 0.2 mm.

[0144] In some embodiments, each of the plurality of halogen reservoirs comprises at least one permeation control material. In some embodiments, the permeation control material includes polycarbonate (PC), ethyl cellulose (EC), polystyrene (PS), polystyrene-divinylbenzene (PS-DVB), at least one polyolefin, at least one polyvinylidene fluoride (PVDF) homopolymer or copolymer, or any combination thereof.

[0145] In some embodiments, the PVDF copolymer is a copolymer of PVDF and hexafluoropropylene (HFP). Non-limiting commercial examples of PVDF homopolymers or copolymers applicable to some embodiments of this disclosure include, but are not limited to, Kynar. and Kynar All of them can be purchased from Arkema.

[0146] In some embodiments, the permeation control material includes polyethylene wax. In some embodiments, the permeation control material includes polypropylene wax.

[0147] In some embodiments, each of the plurality of halogen reservoirs comprises 5% to 95% by weight of at least one permeation control material, based on the average weight of the individual halogen reservoirs.

[0148] In some embodiments, based on the average weight of the individual halogen reservoirs, each of the plurality of halogen reservoirs includes 5% by weight of at least one permeation control material. In some embodiments, based on the average weight of the individual halogen reservoirs, each of the plurality of halogen reservoirs includes 10% by weight of at least one permeation control material, 15% by weight of at least one permeation control material, 20% by weight of at least one permeation control material, 25% by weight of at least one permeation control material, 30% by weight of at least one permeation control material, 35% by weight of at least one permeation control material, 40% by weight of at least one permeation control material, 45% by weight of at least one permeation control material, 50% by weight of at least one permeation control material, 55% by weight of at least one permeation control material, 60% by weight of at least one permeation control material, 65% by weight of at least one permeation control material, 70% by weight of at least one permeation control material, 75% by weight of at least one permeation control material, 80% by weight of at least one permeation control material, 85% by weight of at least one permeation control material, 90% by weight of at least one permeation control material, and 95% by weight of at least one permeation control material.

[0149] In some embodiments, based on the average weight of each halogen reservoir, each of the plurality of halogen reservoirs includes 10 wt% to 95 wt% of at least one permeation control material, 15 wt% to 95 wt% of at least one permeation control material, 20 wt% to 95 wt% of at least one permeation control material, 25 wt% to 95 wt% of at least one permeation control material, 30 wt% to 95 wt% of at least one permeation control material, 35 wt% to 95 wt% of at least one permeation control material, 40 wt% to 95 wt% of at least one permeation control material, and 45 wt% to 95 wt% of at least one permeation control material. The material comprises at least one permeation control material, 50% to 95% of at least one permeation control material, 55% to 95% of at least one permeation control material, 60% to 95% of at least one permeation control material, 65% to 95% of at least one permeation control material, 70% to 95% of at least one permeation control material, 75% to 95% of at least one permeation control material, 80% to 95% of at least one permeation control material, 85% to 95% of at least one permeation control material, or 90% to 95% of at least one permeation control material.

[0150] In some embodiments, based on the average weight of each halogen reservoir, each of the plurality of halogen reservoirs includes 5 wt% to 10 wt% of at least one permeation control material, 5 wt% to 15 wt% of at least one permeation control material, 5 wt% to 20 wt% of at least one permeation control material, 5 wt% to 25 wt% of at least one permeation control material, 5 wt% to 30 wt% of at least one permeation control material, 5 wt% to 35 wt% of at least one permeation control material, 5 wt% to 40 wt% of at least one permeation control material, and 5 wt% to 45 wt% of at least one permeation control material. The material comprises at least one permeation control material, 5% to 50% by weight of at least one permeation control material, 5% to 55% by weight of at least one permeation control material, 5% to 60% by weight of at least one permeation control material, 5% to 65% by weight of at least one permeation control material, 5% to 70% by weight of at least one permeation control material, 5% to 75% by weight of at least one permeation control material, 5% to 80% by weight of at least one permeation control material, 5% to 85% by weight of at least one permeation control material, or 5% to 90% by weight of at least one permeation control material.

[0151] In some embodiments, each of the plurality of halogen reservoirs includes at least one halogen source based on the average weight of the individual halogen reservoirs. In some embodiments, each of the plurality of halogen reservoirs includes 5% to 50% by weight of at least one halogen source based on the average weight of the individual halogen reservoirs.

[0152] In some embodiments, based on the average weight of each halogen reservoir, each of the plurality of halogen reservoirs includes 5% by weight of at least one halogen source, 10% by weight of at least one halogen source, 15% by weight of at least one halogen source, 20% by weight of at least one halogen source, 25% by weight of at least one halogen source, 30% by weight of at least one halogen source, 35% by weight of at least one halogen source, 40% by weight of at least one halogen source, 45% by weight of at least one halogen source, or 50% by weight of at least one halogen source.

[0153] In some embodiments, each of the plurality of halogen reservoirs includes 10 wt% to 50 wt% of at least one halogen source, based on the average weight of the individual halogen reservoirs. In some embodiments, each of the plurality of halogen reservoirs includes 15 wt% to 50 wt% of at least one halogen source, 20 wt% to 50 wt% of at least one halogen source, 25 wt% to 50 wt% of at least one halogen source, 30 wt% to 50 wt% of at least one halogen source, 35 wt% to 50 wt% of at least one halogen source, 40 wt% to 50 wt% of at least one halogen source, or 45 wt% to 50 wt% of at least one halogen source, based on the average weight of the individual halogen reservoirs.

[0154] In some embodiments, based on the average weight of the individual halogen reservoirs, each of the plurality of halogen reservoirs includes 5 wt% to 45 wt% of at least one halogen source. In some embodiments, based on the average weight of the individual halogen reservoirs, each of the plurality of halogen reservoirs includes 5 wt% to 40 wt% of at least one halogen source, 5 wt% to 35 wt% of at least one halogen source, 5 wt% to 30 wt% of at least one halogen source, 5 wt% to 25 wt% of at least one halogen source, 5 wt% to 20 wt% of at least one halogen source, 5 wt% to 15 wt% of at least one halogen source, or 5 wt% to 10 wt% of at least one halogen source.

[0155] In some embodiments, at least one halogen source in the plurality of halogen reservoirs can be any halogen source described herein. In some embodiments, at least one halogen source in the plurality of halogen reservoirs is the same as at least one halogen source of the adsorbent polymer complex (SPC). In some embodiments, at least one halogen source in the plurality of halogen reservoirs is not the same as at least one halogen source of the adsorbent polymer complex (SPC).

[0156] In some embodiments, the article includes a sufficient number of multiple halogen reservoirs to ensure that the rate of release of total halogens from the article is no more than a specified amount of total halogens per day, provided that flue gas flows over at least one surface of the article for a period of at least 90 days.

[0157] As described herein, % per day refers to the amount of halogen relative to the total halogen content present at that time (not relative to the initial content), not relative to the weight of the SPC. In some embodiments, the decrease in iodine content (or release rate) is exponential (i.e., the decrease can be described as exponential decay), for example, as... Figures 7 to 10 As shown in A, and further discussed in this paper. Therefore, the constant “k” can be used to describe this situation, where “k” can be called the “release rate constant”, the “decay constant”, or the “exponential decay constant”.

[0158] In some embodiments, over a period of at least 90 days during which flue gas flows over at least one surface of the article, the rate of release of total halogens from the article is no more than 0.1% of total halogens per day, no more than 0.2% of total halogens per day, no more than 0.3% of total halogens per day, no more than 0.4% of total halogens per day, no more than 0.5% of total halogens per day, no more than 0.6% of total halogens per day, no more than 0.7% of total halogens per day, no more than 0.8% of total halogens per day, no more than 0.9% of total halogens per day, no more than 1% of total halogens per day, no more than 1.5% of total halogens per day, no more than 2% of total halogens per day, no more than 2.5% of total halogens per day, no more than 3% of total halogens per day, no more than 4% of total halogens per day, and no more than 5% of total halogens per day.

[0159] In some embodiments, the rate of total halogen release from the article is 0.1% to 2% of total halogen per day when the flue gas flows over at least one surface of the article for at least 90 days. In some embodiments, the rate of total halogen release from the article is 0.2% to 2% of total halogen per day, 0.3% to 2% of total halogen per day, 0.4% to 2% of total halogen per day, 0.5% to 2% of total halogen per day, 0.6% to 2% of total halogen per day, 0.7% to 2% of total halogen per day, 0.8% to 1% of total halogen per day, 0.9% to 2% of total halogen per day, 1% to 2% of total halogen per day, or 1.5% to 2% of total halogen per day during the period of at least 90 days when the flue gas flows over at least one surface of the article.

[0160] In some embodiments, the rate of total halogen release from the article is from 0.1% to 1.5% of total halogens per day when the flue gas flows over at least one surface of the article for at least 90 days. In some embodiments, the rate of total halogen release from the article is from 0.1% to 1% of total halogens per day, 0.1% to 0.9% of total halogens per day, 0.1% to 0.8% of total halogens per day, 0.1% to 0.7% of total halogens per day, 0.1% to 0.6% of total halogens per day, 0.1% to 0.5% of total halogens per day, 0.1% to 0.4% of total halogens per day, 0.1% to 0.3% of total halogens per day, or 0.1% to 0.2% of total halogens per day.

[0161] In some embodiments, the rate of total halogen release from the article is 0.2% to 0.9% of the total halogen per day when the flue gas flows over at least one surface of the article for at least 90 days. In some embodiments, the rate of total halogen release from the article is 0.3% to 0.8% of the total halogen per day, 0.4% to 0.7% of the total halogen per day, or 0.5% to 0.6% of the total halogen per day when the flue gas flows over at least one surface of the article for at least 90 days.

[0162] In some embodiments, the flue gas stream has a temperature of at least 20°C and a relative humidity of at least 95%. In some embodiments, the flue gas stream contains at least one SO₂ at a concentration of at least 1 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0163] In some embodiments, the flue gas stream has a temperature of at least 50°C and a relative humidity of at least 95%. In some embodiments, the flue gas stream contains at least one SO₂ at a concentration of at least 20 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0164] In some embodiments, the flue gas flow has a temperature greater than 20°C, greater than 30°C, greater than 40°C, greater than 50°C, greater than 60°C, greater than 70°C, greater than 75°C, greater than 80°C, greater than 85°C, or greater than 90°C.

[0165] In some embodiments, the flue gas flow has a temperature of less than 20°C, less than 30°C, less than 40°C, less than 50°C, less than 60°C, less than 70°C, less than 75°C, less than 80°C, less than 85°C, or less than 90°C.

[0166] In some embodiments, the flue gas flow has a temperature of 20°C to 80°C, 30°C to 80°C, 40°C to 80°C, 50°C to 80°C, 60°C to 80°C, or 70°C to 80°C.

[0167] In some embodiments, the flue gas flow has a temperature of 20°C to 70°C, 20°C to 60°C, 20°C to 50°C, 20°C to 40°C, or 20°C to 30°C.

[0168] In some embodiments, the flue gas flow has a temperature of 30°C to 70°C. In some embodiments, the flue gas flow has a temperature of 40°C to 60°C.

[0169] In some embodiments, the flue gas flow has a temperature of 50°C to 70°C, 60°C to 70°C, 55°C to 70°C, or 55°C to 60°C.

[0170] In some embodiments, the flue gas flow has a temperature of 65°C to 70°C, 70°C to 75°C, 75°C to 80°C, 80°C to 85°C, or 85°C to 90°C.

[0171] In some embodiments, the flue gas flow has a temperature of 65°C to 90°C, 70°C to 90°C, 75°C to 90°C, 80°C to 90°C, or 85°C to 90°C.

[0172] In some embodiments, the flue gas flow has a temperature of 65°C to 75°C, 65°C to 80°C, 65°C to 85°C, or 65°C to 90°C.

[0173] In some embodiments, the flue gas stream has a relative humidity of at least 95%. In some embodiments, the flue gas stream has a relative humidity of at least 96%, at least 97%, at least 98%, or at least 99%. In some embodiments, the flue gas stream has a relative humidity of 100%.

[0174] In some embodiments, the flue gas stream has a relative humidity of 95% to 100%. In some embodiments, the flue gas stream has a relative humidity of 96% to 100%, 97% to 100%, 98% to 100%, or 99% to 100%.

[0175] In some embodiments, the flue gas stream has a relative humidity of 95% to 96%, 95% to 97%, 95% to 98%, 95% to 99%, or 95% to 100%.

[0176] In some embodiments, the flue gas stream does not contain at least one SO. x Compounds. In some embodiments, the flue gas stream contains at least one SO. x The compound having a concentration of at least 1 ppm, at least 5 ppm, at least 10 ppm, at least 20 ppm, at least 25 ppm, at least 30 ppm, at least 35 ppm, at least 40 ppm, at least 45 ppm, at least 50 ppm, at least 100 ppm, at least 500 ppm, or at least 1000 ppm.

[0177] In some embodiments, the flue gas stream contains at least one SO x The compound, at a concentration of 1 ppm to 200 ppm, 5 ppm to 200 ppm, 10 ppm to 200 ppm, 50 ppm to 200 ppm, or 100 ppm to 200 ppm.

[0178] In some embodiments, the flue gas stream contains at least one SO xThe compound, at a concentration of 20 ppm to 100 ppm, 25 ppm to 100 ppm, 30 ppm to 100 ppm, 35 ppm to 100 ppm, 40 ppm to 100 ppm, 45 ppm to 100 ppm, 50 ppm to 100 ppm, 55 ppm to 100 ppm, 60 ppm to 100 ppm, 65 ppm to 100 ppm, 70 ppm to 100 ppm, 75 ppm to 100 ppm, 80 ppm to 100 ppm, 85 ppm to 100 ppm, 90 ppm to 100 ppm, or 95 ppm to 100 ppm.

[0179] In some embodiments, the flue gas stream contains at least one SO x The compound, at a concentration of 20 ppm to 25 ppm, 20 ppm to 30 ppm, 20 ppm to 35 ppm, 20 ppm to 40 ppm, 20 ppm to 45 ppm, 20 ppm to 50 ppm, 20 ppm to 55 ppm, 20 ppm to 60 ppm, 20 ppm to 65 ppm, 20 ppm to 70 ppm, 20 ppm to 75 ppm, 20 ppm to 80 ppm, 20 ppm to 85 ppm, 20 ppm to 90 ppm, 20 ppm to 95 ppm, or 20 ppm to 100 ppm.

[0180] In some embodiments, the flue gas stream contains at least one SO x The compound, in concentrations of 1 ppm to 90 ppm, 1 ppm to 80 ppm, 1 ppm to 70 ppm, 1 ppm to 60 ppm, 1 ppm to 50 ppm, 1 ppm to 40 ppm, 1 ppm to 30 ppm, 1 ppm to 20 ppm, 1 ppm to 10 ppm, or 1 ppm to 5 ppm.

[0181] In some embodiments, the flue gas stream does not contain mercury vapor. In some embodiments, the flue gas stream contains mercury vapor at a concentration of at least 1 μg / m³. 3 flue gas flow, at least 2 μg / m 3 flue gas flow, at least 3 μg / m 3 flue gas flow, at least 4 μg / m 3 flue gas flow, at least 5 μg / m 3 flue gas flow, at least 6 μg / m 3 flue gas flow, at least 7 μg / m 3 flue gas flow, at least 8 μg / m 3 flue gas flow, at least 9 μg / m 3 flue gas flow, at least 10 μg / m 3 flue gas flow, at least 15 μg / m 3 flue gas flow, at least 20 μg / m3 flue gas flow, or at least 50 μg / m 3 Smoke flow.

[0182] In some embodiments, the flue gas contains a concentration of 1 μg / m³. 3 Flue gas flow up to 50 μg / m 3 Mercury vapor in the flue gas stream. In some embodiments, the flue gas stream contains mercury vapor at a concentration of 5 μg / m³. 3 Flue gas flow up to 50 μg / m 3 flue gas flow, 10 μg / m 3 Flue gas flow up to 50 μg / m 3 flue gas flow, 20 μg / m 3 Flue gas flow up to 50 μg / m 3 flue gas flow or 40 μg / m 3 Flue gas flow up to 50 μg / m 3 Smoke flow.

[0183] In some embodiments, the flue gas contains a concentration of 1 μg / m³. 3 Flue gas flow up to 10 μg / m 3 Mercury vapor in the flue gas stream. In some embodiments, the flue gas stream contains mercury vapor at a concentration of 2 μg / m³. 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 3μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 4μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 5 μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 6 μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 7μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow, 8μg / m 3 Flue gas flow up to 10 μg / m 3 flue gas flow or 9μg / m 3 Flue gas flow up to 10 μg / m 3 Smoke flow.

[0184] In some embodiments, the flue gas stream contains mercury vapor at a concentration of 1 μg / m³. 3 Flue gas flow up to 2μg / m 3 flue gas flow, 1 μg / m 3 Flue gas flow up to 3 μg / m 3 flue gas flow, 1 μg / m 3 Flue gas flow up to 4 μg / m 3 flue gas flow, 1 μg / m3 Flue gas flow up to 5 μg / m 3 flue gas flow, 1 μg / m 3 Flue gas flow up to 6 μg / m 3 flue gas flow, 1 μg / m 3 Flue gas flow up to 7 μg / m 3 flue gas flow, 1 μg / m 3 Flue gas flow up to 8 μg / m 3 flue gas flow or 1μg / m 3 Flue gas flow up to 9 μg / m 3 Smoke flow.

[0185] In some embodiments, the flue gas flows over at least one surface of the article for a period of at least 100 days. In some embodiments, the flue gas flows over at least one surface of the article for a period of at least 200 days, at least 300 days, at least 400 days, at least 500 days, at least 600 days, at least 700 days, at least 800 days, at least 900 days, at least 1000 days, at least 2000 days, at least 3000 days, at least 4000 days, or at least 5000 days.

[0186] In some embodiments, the flue gas flows over at least one surface of the article for a period of 100 to 10,000 days. In some embodiments, the flue gas flows over at least one surface of the article for a period of 500 to 10,000 days, 1,000 to 10,000 days, or 5,000 to 10,000 days.

[0187] In some embodiments, the flue gas flows over at least one surface of the article for a period of 100 to 5000 days, 100 to 1000 days, or 100 to 500 days.

[0188] In some embodiments, the flue gas flows over at least one surface of the article for a period of 500 to 10,000 days or 1,000 to 5,000 days.

[0189] In some embodiments, at least one of the plurality of halogen reservoirs is in the form of reservoir particles, wherein the reservoir particles include a first permeation control material and at least one halogen source, wherein the first permeation control material is in the form of permeation control particles, and wherein at least one halogen source is present at least on the surface of the permeation control particles.

[0190] In some embodiments, the storage particles further include a second permeation control material, wherein the second permeation control material surrounds at least one halogen source on the surface of the permeation control particles. In some embodiments, the first permeation control material and the second permeation control material comprise the same material. In some embodiments, the first permeation control material and the second permeation control material comprise different materials.

[0191] In some embodiments, the plurality of halogen reservoirs take the form of a plurality of reservoir clusters, wherein each reservoir cluster includes a mixture of at least one halogen source and a permeation control material.

[0192] Figure 3A An electronic image depicting a collection 302 of halogen storage particles 301 according to some non-limiting embodiments of the present disclosure is shown. Figure 3B Describing includes Figure 3A An electronic image of a cross-section of the adsorbent polymer complex (SPC) 303 of the halogen storage particles. According to some non-limiting embodiments of the present disclosure, halogen storage particles 305 having a permeation control material 304 are embedded within the adsorbent polymer complex (SPC) 303.

[0193] Figure 4A A magnified electronic image of article 400 is depicted, showing a cross section of an adsorbent polymer complex (SPC) 430 according to some non-limiting embodiments of the present disclosure, the SPC 430 including a halogen reservoir 410 in the form of halogen reservoir particles embedded within the SPC 430.

[0194] Figure 4B An electronic image depicting one embodiment of article 400 shows a cross-section of an adsorbent polymer complex (SPC) 430 comprising a halogen reservoir including reservoir particles 410 embedded within the SPC 430.

[0195] In some embodiments, at least one of the plurality of halogen reservoirs takes the form of an encapsulated bead, wherein the encapsulated bead includes a core. In some embodiments, at least one halogen source is present at least on the surface of the core, wherein a permeation control material encapsulates the core to form the encapsulated bead.

[0196] The core may include any suitable material. For example, in some embodiments, the core may include carbon, activated carbon derived from coal, lignite, wood, coconut shell, other carbonaceous materials, silica gel, zeolite, or any combination thereof.

[0197] In some embodiments, the core includes at least one carbon particle. In some embodiments, the at least one carbon particle may include any type of carbon particle listed herein. In some embodiments, the core includes at least one carbon particle or multiple carbon particles.

[0198] In some embodiments, at least one or more carbon particles comprise activated carbon. In some embodiments, activated carbon is incorporated into the encapsulating beads in an amount of 25% to 50% by weight.

[0199] In some embodiments, the activated carbon incorporated into the encapsulated beads is present in amounts of 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight of the encapsulated beads.

[0200] In some embodiments, the activated carbon incorporated into the encapsulated beads is present in an amount of 25% to 30% by weight, 25% to 35% by weight, 25% to 40% by weight, or 25% to 45% by weight of the encapsulated beads.

[0201] In some embodiments, the activated carbon incorporated into the encapsulated beads is present in an amount of 30% to 50% by weight, 35% to 50% by weight, 40% to 50% by weight, or 45% to 50% by weight of the encapsulated beads.

[0202] In some embodiments, the encapsulating beads include at least one permeation control material. In some embodiments, the permeation control material of the encapsulating beads includes at least one polyvinylidene ethylene (PVDF) homopolymer or copolymer, at least one polyolefin, polycarbonate (PC), polystyrene (PS), ethyl cellulose (EC), or any combination thereof.

[0203] In some embodiments, the permeation control material for the encapsulating beads includes polyethylene wax. In some embodiments, the permeation control material for the encapsulating beads includes polypropylene wax.

[0204] In some embodiments, the encapsulated beads include at least one halogen source, wherein the at least one halogen source is present on the surface of at least one carbon particle.

[0205] In some embodiments, the encapsulated beads comprise a size range of 20 micrometers to 500 micrometers. In some embodiments, the halogen release rate increases as the size of the encapsulated beads decreases. In some embodiments, the encapsulated beads comprise a size range of 25 micrometers to 50 micrometers.

[0206] In some embodiments, the encapsulated beads include sizes of 20 micrometers; 25 micrometers; 30 micrometers; 35 micrometers; 40 micrometers; 45 micrometers; 50 micrometers; 100 micrometers; 150 micrometers; 200 micrometers; 250 micrometers; 300 micrometers; 350 micrometers; 400 micrometers; 450 micrometers; or 500 micrometers.

[0207] In some embodiments, the encapsulated beads include sizes ranging from 20 to 25 micrometers; 20 to 30 micrometers; 20 to 35 micrometers; 20 to 40 micrometers; 20 to 45 micrometers; 20 to 50 micrometers; 20 to 100 micrometers; 20 to 150 micrometers; 20 to 200 micrometers; 20 to 250 micrometers; 20 to 300 micrometers; 20 to 350 micrometers; 20 to 400 micrometers; 20 to 450 micrometers; or 20 to 500 micrometers.

[0208] In some embodiments, the encapsulated beads include a size range of 25 micrometers to 500 micrometers. In some embodiments, the encapsulated beads include a size range of 30 micrometers to 500 micrometers; 35 micrometers to 500 micrometers; 40 micrometers to 500 micrometers; 45 micrometers to 500 micrometers; 50 micrometers to 500 micrometers; 100 micrometers to 500 micrometers; 150 micrometers to 500 micrometers; 200 micrometers to 500 micrometers; 250 micrometers to 500 micrometers; 300 micrometers to 500 micrometers; 350 micrometers to 500 micrometers; 400 micrometers to 500 micrometers; or 450 micrometers to 500 micrometers.

[0209] In some embodiments, the encapsulated beads can be prepared by any method known to those skilled in the art. In some embodiments, the encapsulated beads can be prepared by spray drying, spray condensation, co-extrusion, coating, or coacervation.

[0210] In some embodiments, the encapsulated beads can be prepared by spray drying. In some embodiments, the spray drying method includes suspending carbon particles in a solution of a halogen source and a permeation control material, atomizing the suspension through a nozzle, evaporating the solvent to produce encapsulated beads, and collecting an aggregate of encapsulated beads. In some embodiments, the at least one halogen source can be dissolved in solution or pre-adsorbed onto activated carbon.

[0211] In some embodiments, the solvent used for spray drying can be any low-boiling-point solvent.

[0212] In some embodiments, the boiling point of the solvent used for spray drying may be below 100°C. In some embodiments, the boiling point of the solvent used for spray drying may be below 75°C. In some embodiments, the boiling point of the solvent used for spray drying may be below 50°C.

[0213] In some embodiments, the boiling point of the solvent used for spray drying can be from 50°C to 100°C. In some embodiments, the boiling point of the solvent used for spray drying can be from 75°C to 100°C. In some embodiments, the boiling point of the solvent used for spray drying can be from 50°C to 75°C.

[0214] In some embodiments, the solvent used for spray drying can be any solvent that has the necessary solubility for the desired permeation control material.

[0215] In some embodiments, the solvent used for spray drying can be any solvent having a solubility of at least 5% by weight in the desired permeation control material. In some embodiments, the solvent used for spray drying can be any solvent having a solubility of at least 25%, at least 50%, or at least 75% by weight in the desired permeation control material.

[0216] In some embodiments, the solvent used for spray drying can be any solvent that does not react with at least one halogen source.

[0217] In some embodiments, the solvent may be dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), acetone, toluene, or any combination thereof.

[0218] In some embodiments, the encapsulated beads can be prepared by spray condensation. In some embodiments, at least one halogen source can be pre-adsorbed onto carbon particles. In some embodiments, the carbon particles are activated carbon. In some embodiments, the at least one halogen source pre-adsorbed onto the carbon particles can be mixed in molten wax, atomized through a nozzle, solidified upon cooling, and then the encapsulated beads are collected.

[0219] In some embodiments, encapsulated beads can be incorporated into the adsorbent polymer complex (SPC) using any method for preparing the adsorbent polymer complex (SPC).

[0220] In some embodiments, the encapsulating bead content in the adsorbent polymer complex (SPC) includes 5% by weight; 10% by weight; 20% by weight; or 25% by weight.

[0221] In some embodiments, the encapsulating bead content in the adsorbent polymer complex (SPC) ranges from 10% to 30% by weight. In some embodiments, the encapsulating bead content in the adsorbent polymer complex (SPC) ranges from 15% to 30% by weight; 20% to 30% by weight; or 25% to 30% by weight.

[0222] In some embodiments, the encapsulating bead content in the adsorbent polymer complex (SPC) includes 10% to 25% by weight; 10% to 20% by weight; or 10% to 15% by weight.

[0223] In some embodiments, the amount of encapsulating beads in the adsorbent polymer complex (SPC) can be determined based on the desired total halogen source content in the SPC and the total halogen source content in the encapsulating beads. In some embodiments, the encapsulating beads comprise at least one halogen source in an amount ranging from 1% to 50% by weight.

[0224] In some embodiments, the encapsulating beads include at least one halogen source in a content of at least 1% by weight; at least 5% by weight; at least 10% by weight; at least 15% by weight; at least 20% by weight; at least 25% by weight; at least 30% by weight; at least 35% by weight; at least 40% by weight; at least 45% by weight; or about 50% by weight.

[0225] In some embodiments, the encapsulating beads include at least one halogen source in the following amounts: 5% to 50% by weight; 10% to 50% by weight; 15% to 50% by weight; 20% to 50% by weight; 25% to 50% by weight; 30% to 50% by weight; 35% to 50% by weight; 40% to 50% by weight; or 45% to 50% by weight.

[0226] In some embodiments, the encapsulating beads include at least one halogen source in the following amounts: 1% to 5% by weight; 1% to 10% by weight; 1% to 15% by weight; 1% to 20% by weight; 1% to 25% by weight; 1% to 30% by weight; 1% to 35% by weight; 1% to 40% by weight; or 1% to 45% by weight.

[0227] Figure 5AA halogen storage device in the form of an encapsulated bead 500 according to some non-limiting embodiments of the present disclosure is depicted. As shown, the encapsulated bead 500 includes a core 501. In some embodiments, the core 501 includes at least one particle, such as, but not limited to, at least one carbon particle. In some embodiments, at least one halogen source (not shown) is present at least on the surface of the core 501. In some embodiments, the encapsulated bead 500 further includes at least one permeation control material 502. In some embodiments, the permeation control material 502 encapsulates the core 501.

[0228] Figure 5B An electronic image depicting a collection of encapsulating beads 510 according to some embodiments of the present disclosure.

[0229] In some implementations, the multiple storage clusters take the form of multiple discrete membranes embedded throughout the adsorbent polymer complex (SPC).

[0230] Figure 6A and Figure 6B This is a set of two photographs showing various embodiments of halogen reservoirs incorporated into adsorbent polymer complexes (SPCs). Figure 6A A surface image of an article 600 according to some non-limiting embodiments of the present disclosure is depicted, the article 600 comprising a halogen reservoir cluster 620 made of halogen reservoir aggregates embedded within an adsorbent polymer complex (SPC) 610. Figure 6B A surface image of an article 600 according to some non-limiting embodiments of the present disclosure is depicted. The article 600 includes a halogen reservoir 620 embedded within an adsorbent polymer complex (SPC) 610. As shown, the halogen reservoir cluster 620 may take the form of localized regions, for example... Figure 6B The stripes shown. In some embodiments, the localized region can be formed by generating an aggregated mixture of halogen reservoirs and embedding the aggregated mixture throughout the adsorbent polymer complex (SPC) 610.

[0231] In some embodiments, the article comprises a sufficient number of multiple halogen reservoirs such that, when flue gas flows over at least one surface of the article for a period of at least 90 days, the release rate of total halogens from the article is no more than 0.5% of the total halogens per day, wherein the flue gas has a temperature of at least 20°C and a relative humidity of at least 95%, and wherein the flue gas contains at least one SO at a concentration of at least 1 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0232] In some embodiments, the article includes a sufficient number of multiple halogen reservoirs such that, when flue gas flows over at least one surface of the article for a period of at least 90 days, the release rate of total halogens from the article is no more than 2% of the total halogens per day, wherein the flue gas has a temperature of at least 50°C and a relative humidity of at least 95%, and wherein the flue gas contains at least one SO at a concentration of at least 20 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0233] In some embodiments, the sufficient amount of the plurality of halogen stores in the article is 5% to 50% by weight, based on the total weight of the article. In some embodiments, the sufficient amount of the plurality of halogen stores in the article is at least 5% by weight; at least 10% by weight; at least 15% by weight; at least 20% by weight; at least 25% by weight; at least 30% by weight; at least 35% by weight; at least 40% by weight; at least 45% by weight; or at least 50% by weight, based on the total weight of the article.

[0234] In some embodiments, the sufficient amount of the plurality of halogen stores in the article is 10% to 50% by weight, based on the total weight of the article. In some embodiments, the sufficient amount of the plurality of halogen stores in the article is 15% to 50% by weight; 20% to 50% by weight; 25% to 50% by weight; 30% to 50% by weight; 35% to 50% by weight; 40% to 50% by weight; or 45% to 50% by weight, based on the total weight of the article.

[0235] In some embodiments, based on the total weight of the article, the amount of the plurality of halogen reservoirs in the article is 5% to 45% by weight; 5% to 40% by weight; 5% to 35% by weight; 5% to 30% by weight; 5% to 25% by weight; 5% to 20% by weight; 5% to 15% by weight; or 5% to 10% by weight.

[0236] Some embodiments of this disclosure relate to methods for obtaining articles comprising an adsorbent polymer complex (SPC) and a plurality of halogen reservoirs.

[0237] In some implementations, multiple halogen storage cells are embedded within the SPC.

[0238] In some embodiments, each of the plurality of halogen reservoirs includes at least one permeation control material comprising 5% to 95% by weight of the average weight of the halogen reservoir, and at least one halogen source comprising 5% to 50% by weight of the average weight of the halogen reservoir.

[0239] Some such embodiments involve flowing a flue gas over at least one surface of an article for a period of at least 90 days, wherein the gas has a temperature of at least 20°C and a relative humidity of at least 95%, and wherein, based on the total volume of the flue gas, the gas includes at least one SO at a concentration of at least 1 ppm. x Compounds, and concentrations of at least 1 μg / m 3 Mercury vapor.

[0240] In some embodiments, during the flow step, the release rate of total halogens from the article is no more than 0.5% of the total halogens in the article per day. In some embodiments, during the flow step, the release rate of total halogens from the article is no more than 0.6% of the total halogens per day; no more than 0.7% of the total halogens per day; no more than 0.8% of the total halogens per day; no more than 0.9% of the total halogens per day; no more than 1% of the total halogens per day; no more than 1.5% of the total halogens per day; or no more than 2% of the total halogens per day.

[0241] In some embodiments, as described above, at least one of the plurality of halogen reservoirs takes the form of an encapsulated bead. In some such embodiments, the encapsulated bead is formed by obtaining at least one particle to form a core, depositing at least one halogen source on the surface of at least one particle, and encapsulating the core with at least one permeation control material. In some embodiments, at least one particle of the core comprises at least one carbon particle.

[0242] In some embodiments, the at least one halogen source is deposited as a solution on at least the surface of the core. In some embodiments, the at least one halogen source is deposited as a solution on at least one carbon particle surface of the core.

[0243] In some embodiments, at least one halogen source is deposited in the gas phase on at least one surface of the core. In some embodiments, at least one halogen source is deposited in the gas phase on at least one carbon particle surface of the core.

[0244] In some embodiments, as described above, at least one of the plurality of halogen reservoirs is in the form of reservoir particles. In some embodiments, reservoir particles are formed by obtaining a permeation control material in the form of permeation control particles and depositing at least one halogen source onto at least the surface of the permeation control particles.

[0245] In some embodiments, the method further includes depositing a second permeation control material on at least a portion of the reservoir particles after depositing at least one halogen source onto the surface of the permeation control particles to form a second permeation control layer surrounding the at least one halogen source. In some embodiments, the first permeation control material and the second permeation control material comprise the same material. In some embodiments, the first permeation control material and the second permeation control material comprise different materials.

[0246] In some embodiments, the plurality of halogen reservoirs are in the form of a plurality of reservoir clusters, wherein each of the plurality of reservoir clusters is formed by mixing a plurality of carbon particles with at least one halogen source and at least one permeation control material to form a mixture, and embedding the mixture in an SPC.

[0247] In some embodiments, the method further includes agglomerating the mixture to form an agglomerated mixture and embedding the agglomerated mixture in an SPC.

[0248] In some embodiments, the method further includes forming the agglomerated mixture into a plurality of discrete membranes and embedding the discrete membranes throughout the SPC.

[0249] Some embodiments of this disclosure relate to systems that include embodiments of any exemplary articles of manufacture and / or articles of manufacture disclosed herein. In some embodiments, the system includes a channel configured to allow airflow through it. In some embodiments, the article of manufacture is housed within the channel. In some embodiments, at least a portion of the article of manufacture is configured to contact the flue gas flow.

[0250] Figure 11 A non-limiting embodiment of a pollution control system 1100 having at least one of the articles described herein is depicted. Some non-limiting uses of the pollution control system 1100 include controlling air pollutant emissions to comply with various air pollutant emission standards. The pollution control system 1100 can be configured to capture elemental gaseous mercury and oxidized gaseous mercury from industrial flue gas. The pollution control system 1100 may include discrete stackable modules 1102 that can be installed downstream of a particulate collection system. In some embodiments, the module 1102 may be configured with one or more embodiments of the article 1104 described herein (in... Figure 11 (Seen in a magnified close-up view).

[0251] In some embodiments, the system may include several articles formed as multiple channels. In such embodiments, the gas flow can flow between the channels such that the gas flow is in direct contact with at least a portion of the SPC, but not with the reservoir. In some embodiments, the multiple channels of the device may facilitate the flow of reactants (e.g., gaseous components) on one or more surfaces of the system and facilitate the discharge of at least one liquid product.

[0252] Non-limiting exemplary geometries of systems that may include the embodiments described herein can be found in U.S. Patent No. 9,381,459 to Stark et al., which is incorporated herein by reference in its entirety for all purposes.

[0253] Figure 12 A non-limiting embodiment of a schematic diagram 1200 depicting flue gas flowing over a non-limiting embodiment of the article 1202 described herein is illustrated. When the flue gas flows through (e.g., across or through the material of article 1202), article 1202 can capture elemental mercury and mercury oxide from the flue gas flow. Mercury can be firmly bound within the material of article 1202 by chemisorption. SO2 can also be adsorbed and / or absorbed and catalyzed (by SO2 oxidation catalyst) into liquid sulfuric acid, which can form droplets 1204 and be discharged from article 1202. Droplets 1204 can flow downwards on the surface of article 1202 by gravity.

[0254] Various embodiments and comparative examples of the article of manufacture used in the specific systems and methods described herein have been tested to demonstrate the enhanced properties of the article of manufacture implementations. The results are described in detail below.

[0255] Test methods

[0256] Simulated flue gas durability test

[0257] Simulated flue gas durability testing is a laboratory test. An exemplary test simulating exposure to flue gas is conducted using an apparatus that includes:

[0258] (1) Air supply regulated by a mass flow controller;

[0259] (2) SO2 source supplied by a gas cylinder containing a 1% sulfur dioxide / nitrogen mixture regulated by a mass flow controller;

[0260] (3) A triangular sample cell with a side length of 12 mm, equipped with a bypass, and located in an oven at 65°C; simultaneously

[0261] (4) Maintain a high relative humidity of over 80% using an MH-070 permeation tube humidifier (PermaPure, New Jersey, USA). Expose the sample to a concentration of 300 ppm / m³ in the apparatus described above. 3 For approximately three months, the samples were subjected to a simulated flue gas flow of 1 (-) standard liters per minute with SO2 and 90% humidity. The total halogen (iodine) content of the samples over time was measured by X-ray fluorescence (“XRF”), in weight percent. The total halogen content of the samples was determined by the total iodine content. Therefore, the discussion of halogen content and release rate will be based on the release rate of the total iodine (total halogen) from the samples and the iodine content.

[0262] The relative iodine content over time is tracked using the formula C_iodine / C_iodine_0, where C_iodine / C_iodine_0 refers to the total iodine content in the product at a certain time point relative to the initial total iodine content in the product. The release rate of total halogens is analyzed by tracking the relative iodine content using the exponential release rate (decay) function based on the formula C_iodine / C_iodine_0 = exp(-k * time), where C_iodine is the total iodine content measured over time in each sample, C_iodine_0 is the initial total iodine content, and k is the iodine release rate (content decay) constant, in % / day. The total release rate equals k * C_iodine, and the relative release rate equals k * C_iodine / C_iodine_0.

[0263] The total release rate is equal to the release rate constant (e.g., 0.5% / day) multiplied by the total halogen content in the article. In other words, in this embodiment, the total halogen release rate from the article is 0.5% of the total halogen content in the article per day. The relative release rate and the release rate constant have the same units (% / day) but differ due to the relative iodine content.

[0264] Sometimes, the change of iodine content over time is tracked using the formula C_iodine = C_iodine_0 * exp(-k * time), where C_iodine is the iodine content in the product, C_iodine_0 is the initial iodine content, and k is the same iodine release rate (attenuation) constant as described above, in units of % / day.

[0265] The exponential release rate (decay) model is used to estimate the consumption of halogen sources over a long period of time.

[0266] Flue gas durability test

[0267] The flue gas durability test is a field test. An exemplary test of exposure to actual flue gas flow is conducted by exposing an SPC sample (representing an article of the present disclosure) to a slipstream of wet flue gas flow downstream of a desulfurization absorption unit in a coal-fired power plant. The sample was exposed to the flue gas flow in two configurations.

[0268] In the first configuration, up to six 3.5"×12" (8.89cm x 30.48cm) SPC sheets are mounted into a 3.5"×3.5"×40" (8.89cm×8.89cm×101cm) insulated sample holder. The SPC sheets are supported on rods to allow unobstructed fluid flow through the sheets. A stream of flue gas at approximately 80 ACFM (actual cubic feet per minute) (137 cubic meters per hour) is blown into the sample holder through a series of pipes by a fan to expose the sample.

[0269] In the second configuration, 1.25"×12" (3.175cm×30.48cm) SPC strips are mounted on a 2'×2'×1' (61cm×61cm×30cm) frame fixture, with the top and bottom of the strips secured along the frame's rails, which can accommodate up to 100 strips. The rails are spaced 2 inches (50mm) apart to provide unobstructed flow through the frame. The frame is then fitted into a 2.1'×2.1'×8' (0.66m×0.66m×2.4m) insulated pilot tower unit. Approximately 2880 ACFM (4860m³) is blown in by a fan. 3 The sample is exposed to a flue gas flow rate of (per hour). The sample, according to this disclosure, is tested in either the first configuration, the second configuration, or both. In both configurations, the flow rate and pressure difference through the sample fixing device are monitored. The composition of the slipstream flue gas varies considerably, but a typical composition includes 2 μg / m³. 3 Mercury concentration, SO2 concentration of 20-40 ppm 2 Concentration, 6% O 2 The NO concentration was 200 ppm, and the relative humidity was greater than 95%. The slipstream flue gas temperature was 50-55°C. Samples were taken approximately monthly (every 30 days) and the total halogen (iodine) content (wt%) was analyzed by X-ray fluorescence (“XRF”). The total halogen content of the samples disclosed herein was determined by the total iodine content. Therefore, the discussion of halogen content and release rate will be based on the release rate of the total iodine (total halogen) in the samples and the iodine content.

[0270] The total iodine content of each sample was converted to iodine content relative to the initial iodine content (“relative iodine content”) and tracked over time as described in the table below.

[0271] The total halogen release rate corresponds to the iodine release rate analyzed in the embodiments of the present invention.

[0272] The total iodine release rate is analyzed by using the formula C_iodine / C_iodine_0 = exp(-k * time) to track relative iodine content. Here, C_iodine is the total iodine content in each sample, C_iodine_0 is the initial total iodine content, and k is the iodine release (content decay) constant in % / day. The total release rate equals k * C_iodine, and the relative release rate equals k * C_iodine / C_iodine_0. The exponential release rate (decay) model is used to estimate the consumption of halogen sources over long periods.

[0273] Example 1

[0274] Iodine-loaded carbon

[0275] Iodine-loaded carbon 1A was prepared by mixing 25% iodine with 75% activated carbon (Norit PAC20BF, Cabot Inc., Texas, USA). The mixture was heated to 60°C in a sealed glass container for 4–6 hours to obtain an iodine loading of approximately 25% by weight.

[0276] Iodine-loaded carbon 1B was prepared by adding activated carbon (NUCHAR SA-20, Ingeivity, South Carolina, USA) to a supersaturated solution of potassium iodide (KI) dissolved in water at a ratio of 75% KI solution to 25% carbon, and stirring at 90°C for approximately 10 minutes. The carbon was then dispersed on PTFE sheets and dried in an oven at 120°C for 24 hours.

[0277] Halogen storage fragments

[0278] Halogen storage fragment 1A uses 12% iodine-supported carbon 1A and 18% PVDF ( A halogen reservoir slurry was prepared using Superflex 2501-20 (Arkema Inc., Pennsylvania, USA) and 70% tetrahydrofuran (THF) solvent (I2-carbon:PVDF = 1:1.5). The slurry was then applied to a release liner via a slot die coating head to form a halogen reservoir film. The dried film thickness was 6 mils (0.1524 mm). The halogen reservoir film (e.g., a thin, flat structure) was then shredded into smaller, well-defined fragments using a Fellowes Micro-Cut 16Ms Micro-Shred office shredder (product model 4922002, Fellowes Inc., Illinois, USA). The shredded fragments were rectangular, with an average size of approximately 4 mm × 13 mm (0.156 × 0.5 inches).

[0279] Halogen reservoir fragment 1B was prepared using a mixture of iodine-loaded carbon 1A and PVDF powder (Kynar Superflex 2501-20, Arkema Corporation, Pennsylvania, USA) at a ratio of 33% impregnated carbon to 66% PVDF. This preparation employed the general dry blending method taught in U.S. Patent No. 7791861 and a calendering step at 110°C to produce a 0.75 mm (30 mil) thick semi-continuous film or thin, flat structure. These halogen reservoir films were then shredded into smaller, well-defined fragments using a Vanroth Micro-Cut 16Ms Micro-Shred shredder (commercial model 4922002, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular, with an average size of approximately 4 mm × 13 mm (0.156 × 0.5 inches).

[0280] Halogen reservoir fragment 1C was prepared by mixing iodine-loaded carbon 1B and PVDF powder (Kynar Superflex 2501-20, Arkema Corporation, Pennsylvania, USA) in a 40% impregnation carbon to 60% PVDF ratio. The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 110°C to produce a semi-continuous film 0.75 mm (30 mil) thick. These halogen reservoir films were then shredded into smaller, well-defined fragments using a Vanroth Micro-Cut 16Ms Micro-Shred shredder (commercial model 4922002, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular, with an average size of approximately 4 mm × 13 mm (0.156 × 0.5 inches).

[0281] Halogen reservoir fragments 1D were manufactured under laboratory conditions containing 40% KI (potassium iodide), 10% activated carbon (NUCHAR SA-20, Injevit, South Carolina, USA), and 50% permeation control material PVDF (Kynar Flex2751-00, Arkema, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C (at which the material melts) to produce 3 mm thick halogen reservoir fragments. These fragments were then shredded into smaller, well-defined pieces using a Vanroth Micro-Cut 16Ms Micro-Shred shredder (commercial model 4922002, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular, with an average size of approximately 4 mm × 13 mm (0.156 × 0.5 inches).

[0282] Halogen reservoir fragment 1E was manufactured under laboratory conditions as a halogen reservoir material comprising 31% KI, 6% activated carbon (NUCHAR SA-20, Injevit, South Carolina, USA), 11% PTFE, and 52% permeation control material PVDF (Kynar Flex 2751-00, Arkema, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce 2 mm thick halogen reservoir fragments. These halogen reservoir fragments were then manually crushed into various sizes, from approximately 2 cm × 2 cm fragments to residual powder.

[0283] Halogen reservoir fragments 1F were manufactured under laboratory conditions containing 29% TBAI, 14% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 9% PTFE, and 48% permeation control material PVDF (Kynar Flex2751-00, Arkema Corporation, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce 2 mm thick halogen reservoir fragments. These fragments were then shredded into smaller, well-defined pieces using a Vanroth 18-Sheet Cross-Cut 99Ci Powershred commercial shredder (commodity model 3229901, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular with an average size of approximately 4 mm × 38 mm (0.156 × 1.5 inches).

[0284] Halogen reservoir fragments 1G were manufactured under laboratory conditions containing 27% TBAI, 14% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 14% PTFE, and 45% permeation control material PVDF (KynarFlex 2751-00, Arkema Corporation, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce halogen reservoir fragments approximately 2 mm thick. These fragments were then shredded into smaller pieces using a Vanroth 18-Sheet Cross-Cut 99Ci Powershred commercial shredder (commercial model 3229901, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular with a nominal size of approximately 4 mm × 38 mm (0.156 × 1.5 inches).

[0285] Halogen reservoir fragments 1H were manufactured under laboratory conditions containing 20% ​​TBAI, 20% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 20% PTFE, and 40% permeation control material PVDF (KynarFlex 2751-00, Arkema Corporation, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce halogen reservoir fragments approximately 2 mm thick. These fragments were then shredded into smaller pieces using a Vanroth 18-Sheet Cross-Cut 99Ci Powershred commercial shredder (commodity model 3229901, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular with a nominal size of approximately 4 mm × 38 mm (0.156 × 1.5 inches).

[0286] Halogen reservoir fragments 1I were manufactured under laboratory conditions containing 20% ​​TBAI, 10% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 50% PTFE, and 20% permeation control material PVDF (KynarFlex 2751-00, Arkema Corporation, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce halogen reservoir fragments approximately 2 mm thick. These halogen reservoir fragments were then shredded into smaller pieces using a Vanroth 18-Sheet Cross-Cut 99Ci Powershred commercial shredder (commodity model 3229901, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular with a nominal size of approximately 4 mm × 38 mm (0.156 × 1.5 inches).

[0287] Halogen reservoir fragments 1J were manufactured under laboratory conditions containing 10% TBAI, 5% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 5% PTFE, and 80% permeation control material PVDF (Kynar Flex2751-00, Arkema Corporation, Pennsylvania, USA). The preparation employed the general dry-mixing method taught in U.S. Patent No. 7791861 and used a calendering step at room temperature to produce halogen reservoir fragments approximately 2 mm thick. These fragments were then shredded into smaller pieces using a Vanroth 18-Sheet Cross-Cut 99Ci Powershred commercial shredder (commodity model 3229901, Vanroth Corporation, Illinois, USA). The shredded fragments were rectangular with a nominal size of approximately 4 mm × 38 mm (0.156 × 1.5 inches).

[0288] Halogen storage aggregates

[0289] Halogen reservoir agglomerates 1A are prepared under laboratory conditions as halogen reservoir precursor agglomerates comprising 8% TBAI, 53% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 23% PTFE, and 17% permeation control material PVDF (KynarFlex 2751-00, Arkema Corporation, Pennsylvania, USA). The preparation of these agglomerates utilizes the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0290] Halogen reservoir agglomerates 1B are prepared under laboratory conditions as halogen reservoir precursor agglomerates comprising 10% TBAI, 10% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 15% PTFE, and 65% permeation control material PVDF (Kynar Flex2751-00, Arkema Corporation, Pennsylvania, USA). The preparation of these agglomerates utilizes the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0291] Adsorbent polymer complex (SPC) aggregates

[0292] SPC agglomerates 1A. Precursor agglomerates comprising 67% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) and 33% PTFE were prepared under laboratory conditions using the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0293] SPC agglomerates 1B. Precursor agglomerates comprising 64% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 31% PTFE and 5% sulfur were prepared under laboratory conditions using the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0294] SPC agglomerates 1C. Precursor agglomerates comprising 70% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) and 30% PTFE were prepared under laboratory conditions using the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0295] SPC agglomerates 1D. Precursor agglomerates comprising 76% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) and 24% PTFE were prepared under laboratory conditions using the general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0296] SPC agglomerates 1E. Precursor agglomerates comprising 63% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 27% PTFE, 4% TBAI, 4% sulfur, and 2% PVDF powder (Kynar Flex 2751-00, Arkema Corporation, Pennsylvania, USA) were prepared under laboratory conditions using a general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0297] SPC agglomerates 1F were prepared under laboratory conditions comprising 68% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 29% PTFE, and 3% PVDF (Kynar Flex 2751-00, Arkema Corporation, Pennsylvania, USA) using a general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0298] SPC agglomerates 1G. Precursor agglomerates comprising 62% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 27% PTFE, 4% sulfur, 4% TBAI, and 3% PVDF (Kynar Flex 2751-00, Arkema Corporation, Pennsylvania, USA) were prepared under laboratory conditions using a general dry-mixing method taught in U.S. Patent No. 7791861 to produce loose agglomerates.

[0299] SPC agglomerates 1H were prepared under laboratory conditions comprising 64% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 27% PTFE, and 4% sulfur (Sigma Aldrich) and 4% TBAI, using a general dry-mixing method taught in U.S. Patent No. 7,791,861 to produce loose agglomerates.

[0300] Sample 1A - an article comprising an SPC containing halogen storage fragments 1A. The SPC aggregates 1A and halogen storage fragments 1A are lightly mixed by hand in a ratio of 83% SPC aggregates and 17% halogen storage fragments to form a well-distributed mixture. The preparation is carried out using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 110°C to produce an adsorbent polymer composite (SPC) of approximately 0.9 mm thickness.

[0301] Sample 1B - an article containing SPC with halogen storage fragments 1B, wherein the SPC aggregates 1B and halogen storage fragments 1B are loosely tumbled in a closed container in a ratio of 80% SPC aggregates and 20% halogen storage fragments to form a well-distributed mixture, which is then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and using a calendering step at 140°C to produce an adsorbent polymer composite (SPC) of about 1 mm thickness.

[0302] Sample 1C – an article comprising an SPC containing halogen storage fragments 1C – is prepared by loosely tumbling SPC aggregates 1B and halogen storage fragments 1C in a closed container to form a well-distributed mixture in a ratio of 80% SPC aggregates and 20% halogen storage fragments. This mixture is then prepared using the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 140°C to produce an adsorbent polymer composite (SPC) approximately 1 mm thick.

[0303] Sample 1D - an article containing SPC with halogen storage fragments 1D - is prepared by loosely tumbling SPC aggregates 1C and halogen storage fragments 1D in a closed container to form a well-distributed mixture, which is then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 0.5 mm thickness.

[0304] Sample 1E – an article comprising an SPC containing halogen storage fragments 1E – is prepared by loosely tumbling SPC aggregates 1C and halogen storage fragments 1E in a closed container to form a well-distributed mixture in a ratio of 70% SPC aggregates and 30% halogen storage fragments. This mixture is then prepared using the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) approximately 1.2 mm thick.

[0305] Sample 1F - an article containing SPC with halogen storage fragments 1F - was prepared by loosely tumbling SPC aggregates 1D and halogen storage fragments 1F in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage fragments. The mixture was then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 1.1 mm thickness.

[0306] Sample 1G – an article containing SPC with halogenated aggregate 1A – was prepared by loosely tumbling SPC aggregate 1E with halogenated reservoir aggregate 1A in a closed container to form a well-distributed mixture in a ratio of 50% SPC aggregate and 50% halogenated reservoir aggregate. This mixture was then prepared using the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) approximately 1.1 mm (44 mil) thick.

[0307] Sample 1H - an article containing SPC with halogen storage fragments 1H. The SPC aggregates 1E and halogen storage fragments 1H were gently mixed by hand in a ratio of 67% SPC aggregates and 33% halogen storage fragments to form a well-distributed mixture, which was then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 1 mm thickness.

[0308] Sample 1I - an article containing SPC with halogen storage fragment 1F, wherein SPC aggregate 1D and halogen storage fragment 1F are loosely tumbled in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage fragments, which is then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) about 1.1 mm (44 mils) thick.

[0309] Sample 1J - an article containing SPC with halogen storage fragments 1G - was prepared by loosely tumbling SPC aggregates 1F and halogen storage fragments 1G in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage fragments. The mixture was then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 1 mm (40 mils) thickness.

[0310] Sample 1K - an article containing SPC with halogen storage fragments 1H - was prepared by loosely tumbling SPC aggregates 1C and halogen storage fragments 1H in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage fragments. The mixture was then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 0.9 mm thickness.

[0311] Sample 1L - an article containing SPC with halogen storage fragment 1I - was prepared by loosely tumbling SPC aggregate 1C with halogen storage fragment 1I in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage fragments. The mixture was then prepared using the general dry mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) of about 1 mm thickness.

[0312] Sample 1M – an article containing SPC with halogenated aggregate 1B – was prepared by loosely tumbling SPC aggregate 1E and halogenated reservoir aggregate 1B in a closed container for about 10 revolutions to form a well-distributed mixture in a ratio of 33% SPC aggregate and 67% halogenated reservoir aggregate. This mixture was then prepared using the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer composite (SPC) about 1 mm (40 mil) thick.

[0313] Sample 1N – an article comprising a storage complex from halogen storage fragment 1J – was prepared by loosely tumbling SPC aggregate 1H and halogen storage aggregate 1C in a closed container to form a well-distributed mixture in a ratio of 67% SPC aggregates and 33% halogen storage aggregates. This mixture was then prepared using the general dry-mixing method taught in U.S. Patent No. 7791861 and a calendering step at 145°C to produce an adsorbent polymer complex (SPC) of approximately 1 mm thickness.

[0314] Flue gas durability testing was performed on samples 1A, 1G, and 1I-1L as described above, and the total iodine content was measured over time. The total iodine content was converted to relative iodine content, as shown in Table 1 and... Figure 7 As described in [the text].

[0315] The release rate constant (iodine content decay constant k) of sample 1A was 0.17% / day, sample 1I was 0.17% / day, sample 1J was 0.34% / day, sample 1G was 0.38% / day, sample 1K was 0.23% / day, and sample 1L was 0.42% / day.

[0316] Table 1: Flue gas durability test

[0317]

[0318]

[0319] When using an exponential release rate model to extrapolate flue gas durability data (e.g.) Figure 7 (As shown by the corresponding dashed line in the figure), samples 1J, 1G, and 1L show iodine release over nearly 2 years (approximately 550 to 700 days) before reaching nearly 90% consumption (as shown by the horizontal line L). Extrapolation of samples 1A, 1I, and 1K shows good iodine release over 3 years (1095 days) before reaching 90% consumption.

[0320] Example 2

[0321] Encapsulated beads (Figure 5)

[0322] Iodine-PVDF-activated carbon (1:2:1) encapsulated beads 2A: Sample preparation was performed using a spinning discatomization process. 40 g of PVDF (Kynar Flex 2751-00, Arkema Corporation, Pennsylvania, USA) was dissolved in 1695 g of tetrahydrofuran (THF). Then, 20 g of activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) and 20 g of iodine (I) were mixed to form a homogeneous suspension. The suspension was then poured onto a 7.6 cm diameter disc at approximately 100–120 g / min. The disc was rotated at approximately 7000 rpm to atomize the slurry into a 0.1 m³ conical-bottom container heated to approximately 29 °C. The dried powder was conveyed by air through a cyclone separator for collection. 53.4 g of encapsulated beads were recovered. The obtained beads had a nominal particle size of 20-30 micrometers. X-ray fluorescence ("XRF") analysis of a portion of the beads revealed that they contained approximately 20.7% by weight of iodine. This result indicates that the formulation of activated carbon and iodine achieved iodine retention in the final encapsulated beads during the spray drying process.

[0323] Iodine-PVDF-activated carbon (1:1:2) encapsulated beads 2B: Sample preparation using a rotary disc atomization method. 143 g (g) of PVDF (Kynar Flex 2751-00, Arkema Corporation, Pennsylvania, USA) was dissolved in 2500 g of tetrahydrofuran (THF). 143 g of iodine (I) followed by 286 g of activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) was dissolved in this solution to form a homogeneous suspension. The suspension was then poured onto a 7.6 cm diameter disc at approximately 100–120 g / min. The disc was rotated at approximately 7000 rpm to atomize the slurry into a 0.1 m³ conical-bottom jar heated to approximately 29 °C. The dried powder was conveyed by air through a cyclone separator for collection. 544 g of microencapsulated beads were recovered after sieving through a 212 μm sieve. The resulting beads had a nominal particle size of 20-30 micrometers. X-ray fluorescence ("XRF") analysis of a portion of the beads revealed that they contained approximately 26.4% by weight of iodine. Based on the aforementioned formulation, the theoretical maximum iodine content in this mixture is 25% by weight. Increasing the ratio of activated carbon to polymer to 2:1 ensured that almost all of the iodine added to the formulation was incorporated into the final encapsulated beads.

[0324] Iodine-polycarbonate-activated carbon (1:2:1) encapsulated beads 2C: Sample preparation using a rotary disc atomization method. 20 g (g) of polycarbonate (catalog #954, MW 36000, Scientific Polymer Products Inc., NY, USA) was dissolved in 250 g of dichloromethane (DCM). 10 g of iodine (I) followed by 10 g of activated carbon (Norit PAC20BF, Cabot Corporation, TD, USA) was dissolved in this solution to form a homogeneous suspension. The suspension was then poured onto a 7.6 cm diameter disc at a rate of approximately 100–120 g / min. The disc was rotated at approximately 7000 rpm to atomize the slurry into a 0.1 m³ cubic conical-bottom jar heated to approximately 40 °C. The dried powder was collected by air conveying through a cyclone separator. 33.2 g of encapsulated beads were recovered after sieving through a 212 μm sieve. The nominal particle size of the obtained beads was 20-30 μm. X-ray fluorescence ("XRF") analysis of a portion of the obtained beads showed that they contained approximately 21.3% by weight iodine. Based on the above formulation, the theoretical maximum iodine content in this mixture is 25% by weight.

[0325] Iodine-ethyl cellulose-activated carbon (1:2:1) encapsulated beads 2D: Sample preparation using a rotary disc atomization method. 20 g of ethyl cellulose (Ethocel Standard 4, DuPont deNemours Inc., Delaware, USA) was dissolved in 330 g of methanol (MeOH). 10 g of iodine (I) followed by 10 g of activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA) was dissolved in this solution to form a homogeneous suspension. The suspension was then poured onto a 7.6-inch diameter disc at approximately 100–120 g / min. The disc was rotated at approximately 7000 rpm to atomize the slurry into a 0.1 m³ conical-bottom jar heated to approximately 29°C. The dried powder was conveyed by air through a cyclone separator for collection. 36 g of encapsulated beads were recovered after sieving through a 212 μm sieve. The obtained beads had a nominal particle size of 20-30 micrometers. X-ray fluorescence ("XRF") analysis of a portion of the beads revealed that they contained approximately 23.3% by weight of iodine. Based on the above formulation, the theoretical maximum iodine content in this mixture is 25% by weight.

[0326] Adsorbent polymer complexes for encapsulated bead samples 2A-2C: Adsorbent polymer complexes comprising 67% activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 22% PTFE, and 11% encapsulated beads were prepared under laboratory conditions using the general dry-mixing method taught in U.S. Patent No. 7791861 to form the complex samples. Adsorbent polymer complex (SPC) samples 2A-2C were formulated using the encapsulated beads described in Examples 2B-2D, as summarized in Table 2. A subset of the SPC samples were analyzed by X-ray fluorescence (“XRF”) to confirm the retention of iodine during processing. The results are shown in Table 2:

[0327] Table 2: Non-limiting embodiments of encapsulated beads

[0328]

[0329] To provide sufficient stiffness for field testing, two (2) 3.5" × 12" strips of each material were laminated together in a belt laminator using a 2-mil PVDF membrane (SOLEF PVDF 9009, Solvay Specialty Polymers LLC, Delaware, USA) at approximately 170°C and approximately 60-80 psig.

[0330] Flue gas durability test: Samples 2A-I, 2A-II, 2B, and 2C underwent the flue gas durability test as described above, and the total iodine content was measured over time. The total iodine content was converted to iodine content relative to the initial iodine content, as shown in Table 3.

[0331] As shown in Table 3 and Figure 8 As shown, the halogen release rate constant k (iodine decay rate) for sample 2A-I was determined to be 0.58% / day, for sample 2A-II it was 0.49%, for sample 2B it was 0.75% / day, and for sample 2C it was 0.76%. When using an exponential release rate model to extrapolate flue gas durability data (e.g.) Figure 8 As shown by the corresponding dashed lines in the figure, sample 2A-I reached 90% iodine consumption in about 450 days (as shown by the horizontal line L), sample 2A-II reached 90% iodine consumption in about 400 days, while samples 2B and 2C reached 90% iodine consumption after about 300 days.

[0332] Table 3: Results of Iodine Durability Test

[0333]

[0334]

[0335] Example 3

[0336] Iodine storage particles

[0337] Iodine-loaded storage particles 3A were prepared by mixing 20% ​​iodine with 80% polystyrene (PS) beads (Poly-Fil Micro Beads, Part #PFMB, Fairfield Processing Corp., Connecticut, USA) by shaking the mixture container several times for one hour. The mixture was then heated to 80°C in a sealed container for 20 hours. X-ray fluorescence (“XRF”) analysis of a portion of the sample revealed a iodine content of approximately 20.2%.

[0338] Iodine-loaded storage particles 3B were prepared by dispersing cross-linked polystyrene-divinylbenzene (PS-DVB) beads (Amberlite XAD4, Sigma-Aldrich, Missouri, USA) in a glass drying tray and placing them in an oven at 120°C until completely dry. The dried beads were then mixed with iodine at a ratio of 75% to 25% by shaking the container several times for one hour. The mixture was then heated to 80°C in a sealed container for 16 hours. X-ray fluorescence (“XRF”) analysis of a portion of the sample revealed that it contained approximately 24.3% iodine.

[0339] Iodine-loaded storage particles, specifically 3C cross-linked polystyrene-divinylbenzene (PS-DVB) beads (Amberlite XAD4, Sigma-Aldrich, Missouri, USA), were repeatedly washed to remove impurities that could affect mercury removal performance. 500 mL of deionized water and 200 g of PS-DVB beads were added to a 1000 mL beaker, stirred, and then vacuum filtered. This washing process was repeated three times. The washed beads were then dispersed in a glass drying tray and placed in an oven at 120°C until completely dry. The dried beads were mixed with iodine at a 75% to 25% ratio by shaking the mixture container several times for one hour. The mixture was then heated to 80°C in a sealed container for 16 hours. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 24.5% by weight of iodine.

[0340] Permeation control materials

[0341] Solution 3A. Preparation of a solution of 1.5 wt% PVDF (Kynar Superflex 2501-20, Arkema, Pennsylvania, USA) in tetrahydrofuran (THF) solvent.

[0342] Solution 3B. Preparation of a solution of 4.0 wt% PVDF (Kynar Superflex 2501-20, Arkema, Pennsylvania, USA) in acetone (ACE) solvent.

[0343] Iodine-loaded particles and permeation control materials

[0344] The coated storage particles 3A can be coated with a polymer layer by any method known to those skilled in the art. One such method is fluidized bed coating. Solution 3A is coated onto iodine-loaded storage particles 3B using a fluid air feasibility processor (a laboratory-scale fluidized bed coater using a 1L chamber with a bottom spray). The apparatus is initially loaded with 100g of iodine-loaded beads 3B. The inlet temperature of the fluidized bed coater is set to 35°C, resulting in an outlet temperature of 25.3 to 29.1°C and a product temperature of 24.8 to 28.1°C. The inlet air flow rate is set to 25-30 standard cubic feet per hour (SCFH), the atomizing air is set to 12 psig, and the filter pressure is set to 98 psig. The permeation control material solution 3A is pumped into the atomizing nozzle at 2.5g / min during the continuous coating process until approximately 20% PVDF loading is achieved.

[0345] The iodine-loaded storage particles 3B were coated using a fluidic air feasibility processor (a laboratory-scale fluidized bed coater using a 1L chamber with a bottom spray). The apparatus was initially loaded with 75g of iodine-loaded particles 3B. The inlet temperature of the fluidized bed coater was set to 45°C, resulting in an outlet temperature of 36.6–38.3°C and a product temperature of 39.1–40.2°C. The inlet air flow rate was set to 26–28 SCFH, the atomizing air to 12 psig, and the filter pressure to 95 psig. The permeation control material solution 3A was pumped into the atomizing nozzle at 2.1 g / min during the continuous coating process until approximately 50% PVDF loading was achieved.

[0346] Brunauer-Emmett-Teller (BET) surface area

[0347] To ensure adequate coverage of the penetration control material coating, the specific surface area of ​​the particles was measured using nitrogen adsorption (BET). The BET surface area of ​​the iodide PS-DVB particles decreased with increasing coverage of the penetration control material coating. Compared to uncoated particles, the BET surface area was 631.4 μm. 2 Compared to the BET surface area of ​​ / g, the BET surface area of ​​the coated storage particles 3B is 8.8m². 2 / g. The reduction in surface area indicates that the coated reservoir particles 3B are well covered by the permeation control material.

[0348] Iodine stability test

[0349] The stability of iodine-loaded and coated particles was tested by heating the samples in an oven at 60°C for three months. The iodine-loaded and coated particle samples were placed in vials and then sealed with caps. Activated carbon was also included in the vials to capture lost iodine. The iodine content of the iodine-loaded and coated particles before and after the test was determined by XRF. After three months (94–97 days), the iodine loss percentage was 13.0% for iodine-loaded reservoir particle 3B, 6.9% for coated reservoir particle 3A, and 2.1% for coated reservoir particle 3B.

[0350] Samples with storage particles

[0351] Sample 3A – An article containing an SPC with iodine-loaded storage particles 3A – was prepared under laboratory conditions as an adsorbent polymer complex (SPC) consisting of 65 parts activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 20 parts PTFE, and 5 parts iodine-loaded storage particles 3A, using the general dry-mixing method taught in U.S. Patent No. 7,791,861 to form the complex sample. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 1.11% iodine.

[0352] Sample 3B – An article comprising an SPC with iodine-loaded storage particles 3B – was prepared under laboratory conditions as an adsorbent polymer complex (SPC) consisting of 65 parts activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 20 parts PTFE, and 15 parts iodine-loaded storage particles 3B, using the general dry-mixing method taught in U.S. Patent No. 7,791,861 to form the complex sample. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 3.75% by weight iodine.

[0353] Sample 3C – an article of SPC containing coated reservoir particles 3A – was prepared under laboratory conditions as an adsorbent polymer composite (SPC) consisting of 65 parts activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 20 parts PTFE, and 15 parts coated reservoir particles 3A, using the general dry-mixing method taught in U.S. Patent No. 7,791,861 to form the composite sample. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 2.429% by weight iodine.

[0354] Sample 3D – an article of SPC containing coated reservoir particles 3B – was prepared under laboratory conditions as an adsorbent polymer composite (SPC) consisting of 65 parts activated carbon (Norit PAC20BF, Cabot Corporation, Texas, USA), 20 parts PTFE, and 15 parts coated reservoir particles 3B, using the general dry-mixing method taught in U.S. Patent No. 7,791,861 to form the composite sample. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 1.18% iodine.

[0355] Scanning electron microscope Figure 3B The image shows a scanning electron microscope (SEM) image of a cross-section of sample 3C. Figure 3B Two coated iodine-loaded reservoir particles 305 embedded in the SPC material 303 are shown in the cross-section. It can be observed that the particles 305 are intact, and the PVDF permeation control material coating is visible after formation into the SPC.

[0356] Sample 3E – an article containing laminated SPCs with iodine-loaded storage particles 3B – consisted of two layers of SPCs from Sample 3B laid together and laminated on a belt laminator using a pressure of 36–40 psig and 185°C. Analysis of a portion of the sample by X-ray fluorescence (“XRF”) revealed that it contained approximately 3.74% by weight of iodine.

[0357] The simulated flue gas durability test exposed three samples of Sample 3E to the aforementioned simulated flue gas for one month. Iodine content before and after the test was measured by X-ray fluorescence (XRF). The relative iodine contents of the three samples in this test were 0.24, 0.47, and 0.64, respectively.

[0358] The data for the flue gas durability test sample 3E are summarized in Table 5. Table 5 shows the relative iodine content of the SPC with iodide beads after the flue gas durability test under flue gas conditions.

[0359] Table 5: Relative Iodine Content of Adsorbent Polymer Complexes (SPCs)

[0360]

[0361] Comparative Example 1

[0362] SPC Comparative Sample 4A. An adsorbent polymer complex (SPC) was prepared under laboratory conditions comprising 40% activated carbon (NUCHAR SA-20, Ingevity, South Carolina, USA), 50% PTFE, 3% potassium iodide (KI) as a halogen source, and 7% sulfur. The preparation was carried out using the general dry blending method taught in U.S. Patent No. 7,791,861 to form the complex sample, which was then subjected to uniaxial expansion according to the teachings of U.S. Patent No. 3,953,566.

[0363] SPC Comparative Sample 4B. An adsorbent polymer complex (SPC) was prepared under laboratory conditions comprising 50% activated carbon (NUCHAR SA-20, Ingevity, South Carolina, USA), 39% PTFE, 6% tetrabutylammonium iodide (TBAI) as a halogen source, and 5% sulfur. The preparation was carried out using the general dry blending method taught in U.S. Patent No. 7,791,861 to form the complex sample, which was then subjected to uniaxial expansion according to the teachings of U.S. Patent No. 3,953,566.

[0364] Simulated flue gas durability testing. Simulated flue gas durability testing was performed on SPC comparison samples 4A and 4B, and the relative iodine content was tracked over time, as shown in Table 6. Figure 9As shown, for SPC comparison sample 4A, the halogen release rate constant (iodine content decay constant k) was determined to be 17.7% / day, while for SPC comparison sample 4B, the halogen release rate constant was 16.3% / day. Figure 9 The data shows the relative iodine content measured over a 14-day period. When extrapolating flue gas durability data using an exponential release rate (decay) model, such as... Figure 9 As shown by the corresponding dashed line in the figure, SPC comparison samples 4A and 4B showed only about 15 days of iodine release before approaching 90% consumption (shown by the horizontal line L).

[0365] Table 6: Durability of Simulated Flue Gas Flow

[0366]

[0367]

[0368] Flue gas durability testing was conducted on SPC comparative samples 4A and 4B. The relative iodine content was tracked over time, as shown in Table 7. For SPC comparative sample 4A, the halogen release rate constant (iodine content decay constant k) was determined to be 15% / day, while for SPC comparative sample 4B, the halogen release rate constant was 9.0% / day. (See Table 7 and...) Figure 10 As shown, samples 4A and 4B reached 90% iodine consumption in less than 10 days (as indicated by the horizontal line L). Figure 10 The relative iodine content was measured over 24 and 51 days, respectively.

[0369] Table 7: Flue Gas Durability Test

[0370]

[0371] aspect

[0372] The following describes various aspects. It should be understood that any one or more of the features listed in one or more of the following aspects can be combined with any one or more other aspects.

[0373] Aspect 1. An article comprising:

[0374] Adsorbent polymer complex (SPC); and

[0375] Multiple halogen storage cells,

[0376] The plurality of halogen reservoirs are embedded within the SPC.

[0377] Each of the plurality of halogen reservoirs comprises:

[0378] Based on the average weight of each halogen reservoir, at least one permeation control material comprising 5% to 95% by weight, and

[0379] Based on the average weight of each halogen reservoir, at least one halogen source of 5% to 50% by weight.

[0380] Aspect 2. The article of manufacture as described in aspect 1, wherein the SPC comprises a polymeric material.

[0381] Aspect 3. The article of aspect 2, wherein the polymer material comprises at least one of the following: polyvinylidene fluoride propylene (PFEP); perfluoroacrylate (PPFA); polyvinylidene fluoride (PVDF); a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV); polyvinyl chloride trifluoroethylene (PCFE); poly(ethylene-co-tetrafluoroethylene) (ETFE); ultra-high molecular weight polyethylene (UHMWPE); polyethylene; poly(p-xylene) (PPX); polylactic acid (PLLA); polyethylene (PE); expanded polyethylene (ePE); polytetrafluoroethylene (PTFE); expanded polytetrafluoroethylene (ePTFE); or any combination thereof.

[0382] Aspect 4. The article of aspect 3, wherein the polymer material comprises PVDF.

[0383] Aspect 5. The article as described in aspect 4, wherein the PVDF is a PVDF homopolymer.

[0384] Aspect 6. The article of aspect 4, wherein the PVDF is a PVDF copolymer.

[0385] Aspect 7. The article of aspect 6, wherein the PVDF copolymer is a copolymer of PVDF and hexafluoropropylene (HFP).

[0386] Aspect 8. The article of aspect 3, wherein the polymer material comprises PTFE.

[0387] Aspect 9. The article of aspect 3, wherein the polymeric material comprises ePTFE.

[0388] Aspect 10. The article of any one of Aspects 2-9, wherein the polymer material comprises fibrils and nodes, wherein the polymer material becomes porous after stretching, thereby forming voids between the fibrils and nodes.

[0389] Aspect 11. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least one metal halide, ammonium halide, elemental halogen or any combination thereof.

[0390] Aspect 12. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, or any combination thereof.

[0391] Aspect 13. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least one ammonium halide.

[0392] Aspect 14. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least tetramethylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium triiodide, tetrabutylammonium tribromide, tetrabutylammonium trichloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, or any combination thereof.

[0393] Aspect 15. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least one elemental halogen.

[0394] Aspect 16. The article of aspect 15, wherein the elemental halogen is at least one of elemental iodine (I2), elemental chlorine (Cl2) or elemental bromine (Br2).

[0395] Aspect 17. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises tetrabutylammonium iodide (TBAI).

[0396] Aspect 18. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises potassium iodide (KI).

[0397] Aspect 19. The article of any one of Aspects 1-10, wherein the at least one halogen source comprises at least one phosphonium halide.

[0398] Aspect 20. The article of aspect 19, wherein the at least one phosphonium halide comprises tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof. In some embodiments, the at least one phosphonium halide is selected from the group consisting of tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof.

[0399] Aspect 21. The article of manufacture as described in aspect 20, wherein the at least one phosphonium halide is ETPPI.

[0400] Aspect 22. Articles as described in any one of Aspects 1-21,

[0401] The article comprises a sufficient amount of the plurality of halogen reservoirs such that, under conditions where flue gas flows over at least one surface of the article for a period of at least 90 days, the rate of release of total halogens from the article is no more than 2% per day relative to the total halogens of the article.

[0402] The flue gas stream has a temperature of at least 20°C and a relative humidity of at least 95%, and

[0403] The gas flow contains at least one SO at a concentration of at least 1 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0404] Aspect 23. Articles as described in any one of Aspects 1-22,

[0405] At least one of the plurality of halogen reservoirs is in the form of an encapsulated bead.

[0406] The encapsulating beads include:

[0407] core;

[0408] At least one halogen source, wherein the at least one halogen source is present at least on the surface of the core; and

[0409] A permeation control material, wherein the permeation control material encapsulates the core.

[0410] Aspect 24. The article of manufacture as described in aspect 23, wherein the core comprises activated carbon.

[0411] Article 25. The article as described in any one of Articles 1-24,

[0412] At least one of the plurality of halogen reservoirs is in the form of reservoir particles.

[0413] The storage particles include:

[0414] Permeation control material, wherein the permeation control material is in the form of permeation control particles; and

[0415] At least one halogen source, wherein the at least one halogen source is present at least on the surface of the permeation control particles.

[0416] Aspect 26. The article of aspect 25, wherein the permeation control material comprises polystyrene, cross-linked polystyrene-divinylbenzene (PS-DVB), or a combination thereof.

[0417] Aspect 27. The article of any one of Aspect 25 or Aspect 26, wherein the storage particle further comprises a second permeation control material, wherein the second permeation control material surrounds at least one halogen source on the surface of the permeation control particle.

[0418] Aspect 28. The article of any one of Aspects 1-22, wherein the plurality of halogen reservoirs are in the form of a plurality of reservoir clusters, wherein each reservoir cluster comprises:

[0419] The at least one halogen source; and

[0420] The permeation control material.

[0421] Aspect 29. The article of manufacture as described in aspect 28, wherein the plurality of storage cell clusters take the form of a plurality of halogen storage cell fragments embedded throughout the SPC.

[0422] Aspect 30. The article of manufacture as described in aspect 28, wherein the plurality of reservoir clusters take the form of a plurality of halogen reservoir aggregates mixed with the SPC.

[0423] Aspect 31. The article of the invention as described in aspect 22, wherein, based on the total weight of the article, the sufficient amount of the plurality of halogen storage cells is 5% to 75% by weight of the plurality of halogen storage cells.

[0424] Aspect 32. The article of aspect 22, wherein, based on the total weight of the article, the sufficient amount of the plurality of halogen storage cells is 5% to 50% by weight of the plurality of halogen storage cells.

[0425] 33. Articles as described in any one of aspects 1-32,

[0426] The article comprises a sufficient amount of the plurality of halogen reservoirs such that, under conditions where flue gas flows over at least one surface of the article for a period of at least 90 days, the rate of release of total halogens from the article is no more than 0.5% per day relative to the total halogens of the article.

[0427] The flue gas stream has a temperature of at least 50°C and a relative humidity of at least 95%, and

[0428] The gas flow contains at least one SO at a concentration of at least 20 ppm. x Compounds and concentrations of at least 1 μg / m 3 Mercury vapor in flue gas.

[0429] Aspect 34. A method comprising:

[0430] To obtain adsorbent polymer complexes (SPCs); and

[0431] Multiple halogen storage cells were obtained.

[0432] Each of the plurality of halogen reservoirs comprises: 5% to 95% by weight of at least one permeation control material, based on the average weight of the respective halogen reservoir; and

[0433] Based on the average weight of each halogen reservoir, at least one halogen source comprising 5% to 50% by weight; and

[0434] An article is formed having multiple halogen storage bodies embedded in an SPC.

[0435] Aspect 35. The method of aspect 34, wherein at least one of the plurality of halogen reservoirs is in the form of an encapsulated bead, wherein the method further comprises:

[0436] The encapsulating bead is formed through the following steps:

[0437] Obtain at least one particle to form a core;

[0438] Depositing the at least one halogen source onto the surface of the at least one particle; and

[0439] The core is encapsulated with at least one permeation control material to form an encapsulated bead.

[0440] Aspect 36. The method of aspect 35, wherein the at least one halogen source is deposited as a solution on the surface of the at least one particle.

[0441] Aspect 37. The method of aspect 35, wherein the at least one halogen source is deposited as a vapor phase on the surface of the at least one particle.

[0442] Aspect 38. The method of any one of Aspects 35-37, wherein the at least one particle is a carbon particle.

[0443] Aspect 39. The method of aspect 35, wherein at least one of the plurality of halogen reservoirs is in the form of reservoir particles.

[0444] The storage particles are formed by the following steps:

[0445] Obtain at least one permeation control material in the form of permeation control particles; and

[0446] The at least one halogen source is deposited onto the surface of the permeation control particles.

[0447] Aspect 40. The method of aspect 39, further comprising:

[0448] After depositing the at least one halogen source onto the surface of the permeation control particles, a second permeation control material is deposited on at least a portion of the storage particles to form a second permeation control layer surrounding the at least one halogen source.

[0449] Aspect 41. The method of aspect 34, wherein the plurality of halogen stores are in the form of a plurality of store clusters, wherein the method further comprises:

[0450] Each of the plurality of storage clusters is formed through the following steps:

[0451] Multiple particles are mixed with at least one halogen source and at least one permeation control material to form a mixture;

[0452] The mixture is formed into a film or fragment;

[0453] The membrane or fragment is formed into a halogen storage fragment; and

[0454] Halogen storage fragments are embedded in the SPC.

[0455] Aspect 42. The method of aspect 34, wherein the plurality of halogen stores are in the form of a plurality of store clusters, wherein the method further comprises:

[0456] Each of the plurality of storage clusters is formed through the following steps:

[0457] Obtain SPC aggregates;

[0458] Multiple particles are mixed with at least one halogen source and at least one permeation control material to form reservoir aggregates; and

[0459] The SPC aggregates are mixed with the storage aggregates to form the article.

[0460] Aspect 43. The method of any one of Aspects 34-42, further comprising flowing a flue gas stream to contact the article, wherein the flue gas stream has a temperature of at least 50°C and a relative humidity of at least 95%, wherein, based on the total volume of the flue gas stream, the flue gas stream contains at least one SO at a concentration of at least 20 ppm. x Compounds, and concentrations of at least 1 μg / m 3 Mercury vapor, wherein the release rate of total halogens from the article is no more than 0.5% per day relative to the total halogens of the article.

[0461] It should be understood that modifications to details may be made without departing from the scope of this disclosure, particularly in terms of the shape, size, and arrangement of the building materials and components used. This specification and the described embodiments are exemplary, and the true scope and spirit of the disclosure are defined by the appended claims.

Claims

1. An article comprising: a sorbent polymer composite (SPC); and a plurality of halogen stores, wherein the plurality of halogen stores are embedded within the SPC, wherein each halogen store of the plurality of halogen stores comprises: from 5 wt% to 95 wt% of at least one permeation control material, based on the average weight of the individual halogen store, wherein the permeation control material comprises polycarbonate (PC), ethyl cellulose (EC), polystyrene (PS), polystyrene-divinylbenzene (PS-DVB), at least one polyolefin, at least one polyvinylidene fluoride (PVDF) homopolymer or copolymer, or any combination thereof, and from 5 wt% to 50 wt% of at least one halogen source, based on the average weight of the individual halogen store.

2. The article of claim 1, wherein the SPC comprises a polymeric material.

3. The article of claim 2, wherein the polymeric material comprises: polyfluoroethylene propylene (PFEP); polyperfluoropropenoate (PPFA); polyvinylidene fluoride (PVDF); terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV); polychlorotrifluoroethylene (PCFE); poly(ethylene-co-tetrafluoroethylene) (ETFE); polyparaxylylene (PPX); polylactic acid (PLA); polyethylene (PE); polytetrafluoroethylene (PTFE); or any combination thereof.

4. The article of claim 3, wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE).

5. The article of claim 3, wherein the polyethylene is expanded polyethylene (ePE).

6. The article of claim 3, wherein the polytetrafluoroethylene is expanded polytetrafluoroethylene (ePTFE).

7. The article of claim 3, wherein the polymeric material comprises PVDF.

8. The article of claim 7, wherein the PVDF is a PVDF homopolymer.

9. The article of claim 7, wherein the PVDF is a PVDF copolymer.

10. The article of claim 9, wherein the PVDF copolymer is a copolymer of PVDF and hexafluoropropylene (HFP).

11. The article of claim 3, wherein the polymeric material comprises PTFE.

12. The article of any one of claims 2-11, wherein the polymeric material comprises fibrils and nodes, wherein the polymeric material becomes porous after stretching such that voids are formed between the fibrils and nodes.

13. The article of any one of claims 1-11, wherein the at least one halogen source comprises at least a metal halide, an ammonium halide, an elemental halogen, or any combination thereof.

14. The article of any one of claims 1-11, wherein the at least one halogen source comprises at least sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, or any combination thereof.

15. The article of any one of claims 1-11, wherein the at least one halogen source comprises at least one ammonium halide.

16. The article of any one of claims 1-11, wherein, The at least one halogen source comprises at least tetramethylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium triiodide, tetrabutylammonium tribromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, or any combination thereof.

17. The article of any one of claims 1-11, wherein the at least one halogen source comprises at least one elemental halogen.

18. The article of claim 17, wherein the elemental halogen is at least one of I2, CI2, or Br2.

19. The article of any one of claims 1-11, wherein the at least one halogen source comprises tetrabutylammonium iodide (TBAI).

20. The article of any one of claims 1-11, wherein the at least one halogen source comprises potassium iodide (KI).

21. The article of any one of claims 1-11, wherein the at least one halogen source comprises at least one phosphonium halide.

22. The article of claim 21, wherein the at least one phosphonium halide comprises tetrabutylphosphonium iodide (TBPI), ethyltriphenylphosphonium triiodide (ETPPI3), tetrabutylphosphonium bromide (TBPBr), ethyltriphenylphosphonium bromide (ETPPBr), ethyltriphenylphosphonium iodide (ETPPI), or any combination thereof.

23. The article of claim 22, wherein the at least one phosphonium halide is ETPPI.

24. The article of any one of claims 1-11, wherein the article comprises a sufficient amount of the plurality of halogen reservoirs such that a rate of total halogen release from the article is no more than 2% of the total halogen in the article per day under conditions in which a flue gas stream flows over at least one surface of the article for a period of at least 90 days; wherein the flue gas stream has a temperature of at least 20 °C and a relative humidity of at least 95%, and wherein the flue gas stream comprises at least one SOx x compound and mercury vapor at a concentration of at least 1 μg / m 3 3.

25. The article of any one of claims 1-11, wherein at least one of the plurality of halogen reservoirs is in the form of an encapsulated bead, wherein the encapsulated bead comprises: a core; at least one halogen source, wherein the at least one halogen source is present at least on a surface of the core; and a permeation control material, wherein the permeation control material encapsulates the core.

26. The article of claim 25, wherein the core comprises activated carbon.

27. The article of any one of claims 1-11, wherein at least one of the plurality of halogen reservoirs is in the form of a reservoir particle, wherein the reservoir particle comprises: a permeation control material, wherein the permeation control material is in the form of a permeation control particle; and at least one halogen source, wherein the at least one halogen source is present at least on a surface of the permeation control particle.

28. The article of claim 27, wherein the permeation control material comprises polystyrene, polystyrene-divinylbenzene (PS-DVB), or a combination thereof.

29. The article of claim 27, wherein, The reservoir particles further comprise a second permeation control material, wherein the second permeation control material surrounds the at least one halogen source on the surface of the permeation control particle.

30. The article of any one of claims 1-11, wherein, The plurality of halogen reservoirs take the form of a plurality of reservoir clusters, wherein each reservoir cluster comprises: the at least one halogen source; and the permeation control material.

31. The article of claim 30, wherein, The plurality of reservoir clusters take the form of a plurality of halogen reservoir fragments embedded throughout the SPC.

32. The article of claim 30, wherein the plurality of reservoir clusters take the form of a plurality of halogen reservoir agglomerates mixed with the SPC.

33. The article of claim 24, wherein the sufficient amount of the plurality of halogen reservoirs is 5 wt% to 75 wt% of the plurality of halogen reservoirs, based on the total weight of the article.

34. The article of claim 24, wherein the sufficient amount of the plurality of halogen reservoirs is 5 wt% to 50 wt% of the plurality of halogen reservoirs, based on the total weight of the article.

35. The article of any one of claims 1-11, wherein the article comprises a sufficient amount of the plurality of halogen reservoirs such that a rate of total halogen release from the article is no more than 0.5% of the total halogen of the article per day under conditions in which a flue gas stream flows over at least one surface of the article for a period of at least 90 days; wherein the flue gas stream has a temperature of at least 50 °C and a relative humidity of at least 95%, and wherein the flue gas stream comprises at least one SOx at a concentration of at least 20 ppm x compounds and a concentration of at least 1 pg / m 3 of mercury vapor.

36. A method comprising: obtaining a sorbent polymer composite (SPC); and obtaining a plurality of halogen reservoirs, wherein each reservoir of the plurality of halogen reservoirs comprises: 5 wt% to 95 wt% of at least one permeation control material, based on the average weight of the individual halogen reservoir, wherein the permeation control material comprises a polycarbonate (PC), an ethyl cellulose (EC), a polystyrene (PS), a polystyrene-divinylbenzene (PS-DVB), at least one polyolefin, at least one polyvinylidene fluoride (PVDF) homopolymer or copolymer, or any combination thereof, and 5 wt% to 50% of at least one halogen source, based on the average weight of the individual halogen reservoir; and forming an article having the plurality of halogen reservoirs embedded within the SPC.

37. The method of claim 36, wherein at least one of the plurality of halogen reservoirs takes the form of an encapsulated bead, wherein the method further comprises: forming the encapsulated bead by: obtaining at least one particle forming a core; depositing the at least one halogen source onto a surface of the at least one particle; and encapsulating the core with at least one permeation control material to form an encapsulated bead.

38. The method of claim 37, wherein the at least one halogen source is deposited as a solution onto a surface of the at least one particle.

39. The method of claim 37, wherein the at least one halogen source is deposited as a gas phase onto a surface of the at least one particle.

40. The method of any one of claims 37-39, wherein the at least one particle is a carbon particle.

41. The method of claim 37, wherein the plurality of halogen reservoirs is in the form of reservoir particles, wherein the reservoir particles are formed by the steps of: obtaining at least one permeation control material in the form of permeation control particles; and depositing the at least one halogen source onto the surface of the permeation control particles.

42. The method of claim 41, further comprising: depositing a second permeation control material on at least a portion of the reservoir particles after depositing the at least one halogen source onto the surface of the permeation control particles to form a second permeation control layer surrounding the at least one halogen source.

43. The method of claim 36, wherein, the plurality of halogen reservoirs is in the form of a plurality of reservoir clusters, wherein the method further comprises: forming each of the plurality of reservoir clusters by the steps of: mixing a plurality of particles with at least one halogen source and at least one permeation control material to form a mixture; forming the mixture into a film or a segment; forming the film or segment into halogen reservoir fragments; and embedding the halogen reservoir fragments in the SPC.

44. The method of claim 36, wherein, the plurality of halogen reservoirs is in the form of a plurality of reservoir clusters, wherein the method further comprises: forming each of the plurality of reservoir clusters by the steps of: obtaining SPC agglomerates; mixing a plurality of particles with at least one halogen source and at least one permeation control material to form reservoir agglomerates; and mixing the SPC agglomerates with the reservoir agglomerates to form the article.

45. The method of any of claims 36-39, further comprising flowing a stream of smoke to contact the article, wherein the stream of smoke has a temperature of at least 50 °C and a relative humidity of at least 95%, wherein, based on a total volume of the flue gas stream, the flue gas stream comprises at least one SOx x compound, and mercury vapor at a concentration of at least 1 µg / m 3 wherein the article has a release rate of total halogen of no more than 0.5% of the total halogen of the article per day.

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