Patent Grant
10828596
Mercury (Hg) emissions have become a health and environmental concern because of their toxicity and ability to bioaccumulate. The U.S. Environmental Protection Agency (EPA) has issued regulations for the control of mercury emissions from waste-to-energy, cement production, and coal-fired power plants. Mercury in flue gas from industrial sources (e.g., power plants) can be captured by sorbents such as activated carbon, which can then be removed by particulate separation devices. The amount of standard sorbents (e.g., activated carbon) needed to serve the market is large. Standard sorbents are not always effective and become more expensive as larger amounts are used.
Inhibition of mercury capture from gas streams by active carbon sorbents can occur when sulfur(VI) (e.g. SO3, H2SO4) is present in the gas stream, with increasing inhibition at higher concentrations. Low sulfur coals when burned can produce SO3 concentrations in the flue gas from 1-5 ppm, whereas high sulfur coals when burned can produce SO3 concentrations in the flue gas in excess of 30 ppm. Additionally, many utilities desire to operate SO3 injection systems at a minimum of about 5-6 ppm to improve ash collectability. Mercury capture above sulfur(VI) concentrations of 3 ppm by mole is limited. Sulfur(VI) concentration of about 6 ppm can diminish elemental mercury capture by about 25%-50% or more. With this reduction, it becomes difficult, if not impossible, to economically achieve desired mercury emission levels. The scientific understanding of why a severe inhibition of mercury sorption exists when sulfur(VI) concentrations increase by such a small amount is limited.
In various embodiments, the present invention provides a method for separating mercury from a mercury-containing gas stream. The method includes contacting a mercury-containing gas stream with an activated carbon sorbent including promoted ammonium salt-protected activated carbon sorbent particles, to form a mercury-sorbent composition. The method also includes separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas.
In various embodiments, the present invention provides a method for separating mercury from a mercury-containing gas stream. The method includes contacting a mercury-containing gas stream with an activated carbon sorbent including HBr-promoted ammonium sulfate-protected activated carbon sorbent particles, to form a mercury-sorbent composition. The method also includes separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas.
In various embodiments, the present invention provides ammonium salt-protected activated carbon sorbent particles including ammonia, an ammonium salt, or a combination thereof.
In various embodiments, the present invention provides a method of making the promoted ammonium salt-protected activated carbon particles. The method includes subjecting a mixture including a precursor activated carbon sorbent and an ammonium salt to heating (e.g., in hot flue gas or in hot air), microwaving, irradiation, or a combination thereof, to form an activated carbon sorbent including promoted ammonium salt-protected activated carbon sorbent particles.
In various embodiments, the present invention provides a method for separating mercury from a mercury-containing gas stream. The method includes contacting a mercury-containing gas stream with an activated carbon sorbent comprising promoted or non-promoted activated carbon sorbent particles and ammonia, to form a mercury-sorbent composition. The method includes separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas.
In various embodiments, the present invention provides certain advantages over other mercury sorbents and methods of using the same, at least some of which are unexpected. For example, in some embodiments, the promoted ammonium salt-protected activated carbon sorbent particles provide significantly more effective and economical mercury sorbents for effluent gases, advantageously applicable to treating gas streams from fired equipment and gasification systems. In some embodiments, ammonia formed from the ammonium salt-protection/decomposition adsorbed or complexed on the sorbent surface or in the gas phase that (e.g., owing to its basic character) can react with SO2 or SO3 in the mercury-containing gas stream and can prevent their interference with the sorption of mercury in or near active sites on the activated carbon. In some embodiments, the promoted ammonium salt-protected activated carbon sorbent particles can separate mercury from a gas stream more effectively than other sorbents, such as in the presence of SO3. In various embodiments, mercury removal efficiencies of promoted ammonium salt-protected activated carbon sorbent particles exceeds or matches that of conventional methods with added benefits such as reduced costs. The method and materials of various embodiments of the present invention can operate more efficiently than other methods of mercury removal. In some embodiments, the method and materials of various embodiments can remove a given amount of mercury for a smaller amount of financial expenditure, as compared to other methods. For example, the method and materials of various embodiments can remove a larger amount of mercury for a given mass of carbon, as compared to other methods of removing mercury, including as compared to other methods of removing mercury that include a carbon sorbent.
In some embodiments, in-flight preparation (e.g., in the furnace, in the mercury-containing gas, in the injection/transport system, or a combination thereof) of the promoted ammonium salt-protected carbon sorbent on location produces certain advantages. For example, the treatment system can be combined with the carbon (or sorbent) injection system at the end-use site. With this technique, the halogen/halide is introduced to the carbon-air (or other gas, such as a combustion or gasification gas) mixture in a transport line (or other part of the sorbent storage and injection system), or prepared in-flight in the mercury-containing gas. In some embodiments, this can provide the following benefits over current conventional concepts for treating sorbents off-site: capital equipment costs at a treatment facility are eliminated; costs to operate the treatment facility are eliminated; there are no costs for transporting carbon and additive to a treatment facility; the inventive process uses existing hardware and operation procedures; the inventive technology ensures that the sorbent is always fresh, and thus, more reactive; no new handling concerns are introduced; there are no costs for removing carbon from treatment system; the inventive process allows rapid on-site tailoring of additive-sorbent ratios in order to match the requirements of flue gas changes, such as may be needed when changing fuels or reducing loads, thus further optimizing the economics; the inventive technology reduces the amount of spent sorbents that are disposed; or a combination thereof.
In various embodiment, another advantage of the present invention relates to the use of a feedback system to more efficiently utilize certain aspects of the invention. Where possible and desirable, the mercury control technology of the present invention may utilize continuous measurement of mercury emissions as feedback to assist in control of the sorbent injection rate. Tighter control on the sorbent and optional component(s) levels can be achieved in this way, which will ensure mercury removal requirements are met with minimal material requirements, thus minimizing the associated costs. In some embodiments, the mercury emissions are continuously measured downstream of the injection location, such as in the exhaust gas at the stack.
In some embodiments, the promoted ammonium salt-protected activated carbon sorbent particles can be regenerated and reused, reducing disposal of spent sorbents and decreasing the cost of mercury removal. In some embodiments, preparation or promotion of the promoted ammonium salt-protected activated carbon sorbent particles can advantageously occur on-site. On-site preparation and promotion can have advantages including, for example: reduction or elimination of equipment costs and operating costs of a separate preparation facility or location, reduction or elimination of transportation costs, fresher and more reactive sorbent, reduction of handling, on-site tailoring of composition (such as when changing fuels or reducing loads).
The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present invention.
Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.
Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.
In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.
In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.
The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of” as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that the composition is about 0 wt % to about 5 wt % of the material, or about 0 wt % to about 1 wt %, or about 5 wt % or less, or less than, equal to, or greater than about 4.5 wt %, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt % or less.
The term “solvent” as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
The term “air” as used herein refers to a mixture of gases with a composition approximately identical to the native composition of gases taken from the atmosphere, generally at ground level. In some examples, air is taken from the ambient surroundings. Air has a composition that includes approximately 78% nitrogen, 21% oxygen, 1% argon, and 0.04% carbon dioxide, as well as small amounts of other gases.
The term “room temperature” as used herein refers to a temperature of about 15° C. to 28° C.
As used herein, “mineral” refers to a naturally occurring solid chemical substance formed through biogeochemical processes, having, for example, characteristic chemical composition, highly ordered atomic structure, and specific physical properties.
Method for Separating Mercury from a Mercury-Containing Gas Stream.
In various embodiments, the present invention provides a method for separating mercury from a mercury-containing gas stream. The method includes contacting a mercury-containing gas stream with an activated carbon sorbent including promoted ammonium salt-protected activated carbon sorbent particles, to form a mercury-sorbent composition. The method includes separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas.
The mercury-containing gas stream can have any suitable source. In some embodiments, the method includes combusting coal to form the mercury-containing gas stream. The mercury-containing gas stream can include any suitable concentration of sulfur(VI), such as about 1 ppm to about 2000 ppm, or about 1 ppm or less, or less than, equal to, or greater than about 2 ppm, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 200, 250, 300, 400, 500, 750, 1,000, 1,250, 1,500, 1,750, or about 2,000 or more. The activated carbon sorbent can have any suitable location within the mercury-containing gas stream, such as in a fixed bed, in a moving bed, in a scrubber (e.g., in scrubber slurry), in a filter (e.g., fixed or travelling), suspended in the mercury-containing gas stream, or a combination thereof. The mercury-containing gas stream can include a concentration of sulfur(VI) that is greater than about 0 ppm by mole, such as greater than about 1 ppm or about 3 ppm by mole (e.g., any suitable concentration described herein) and the activated carbon sorbent can form a mercury-sorbent composition at a higher absorption rate relative to a corresponding activated carbon sorbent including less or substantially no ammonium salt-protection. The mercury-containing gas stream can further include a concentration of sulfur(VI) that is greater than about 0 ppm by mole, such as greater than about 1 ppm or about 3 ppm by mole (e.g., any suitable concentration described herein) and the activated carbon sorbent can form a mercury-sorbent composition at a higher absorption rate relative to a corresponding activated carbon sorbent including at least one of a) less or substantially no halide- or halogen-promotion, wherein the activated carbon sorbent including the activated carbon sorbent particles is promoted (e.g., halide- or halogen-promoted), and b) less or substantially no ammonium salt-protection.
The activated carbon sorbent combines with at least some of the mercury in the mercury-containing gas stream to form the mercury-sorbent composition, such as about 0.001 wt % to about 100 wt % of mercury in the mercury-containing gas stream, such as about 70 wt % to about 100 wt %, or such as less than, equal to, or greater than about 0.001 wt %, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more.
The method can include injecting a sorbent into the mercury-containing gas stream. The injected sorbent can be the activated carbon sorbent including the promoted ammonium salt-protected activated carbon sorbent particles. The precursor can be a promoted non-ammonium salt-protected activated carbon sorbent, wherein the ammonium salt-protection occurs after injection of the precursor into the mercury-containing gas stream. The precursor can be an ammonium salt-protected non-promoted activated carbon sorbent, wherein the halide-promotion occurs after injection of the precursor into the mercury-containing gas stream. The precursor can be a non-promoted non-ammonium salt-protected activated carbon sorbent, wherein halide-promotion and ammonium salt-protection occurs after injection of the precursor in the mercury-containing gas stream.
The activated carbon sorbent and the promoted ammonium salt-protected activated carbon sorbent particles have any suitable particle size, such as a particle size of about 0.1 μm to about 1000 μm, about 0.1 μm to about 10 μm, or about 0.1 μm or less, or less than, equal to, or greater than about 0.5 μm, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or about 1000 μm or more. The promoted ammonium salt-protected activated carbon sorbent particles can be 100 wt % of the activated carbon sorbent, or the activated carbon sorbent can include 0.001 wt % to about 99.999 wt % of the promoted ammonium salt-protected activated carbon sorbent particles, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more.
The activated carbon sorbent can include an alkaline component, such as an alkaline component chosen from alkali elements, alkaline earth elements, alkali salts, alkaline earth salts, and combinations thereof. For example, the alkali salts or alkaline earth salts can be an oxide, a hydroxide, a carbonate, or a phosphate. The activated carbon sorbent can include a mercury-stabilizing reagent selected from the group consisting of S, Se, H2S, SO2, H2Se, SeO2, CS2, P2S5, and combinations thereof. The activated carbon sorbent can optionally include a substrate including at least one of diatomaceous earth, a clay (e.g., bentonite), a zeolite, or a mineral (e.g., lime). For example, the activated carbon sorbent can optionally include a substrate including at least one of mica, talc, phyllosilicates, feldspars, bentonite, dolomite, kaolin, kaolinite, montmorillonite, smectite, illite, chlorite, or a combination thereof.
The activated carbon sorbent can include a product of subjecting a mixture including a carbonaceous material and the substrate to heating, microwaving, irradiating, or a combination thereof; comprises a material derived from the product via one or more of halide-promotion and ammonium salt-protection; or a combination thereof. The heating can be performed in hot gas or hot air, or any other suitable method of heating. The heating can include heating to about 100° C. to about 1200° C., or about 100° C. or less, or less than, equal to, or greater than about 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900, 1,000, 1,100, or about 1,200° C. or more. The heating of the mixture including the carbonaceous material and the substrate to form the product thereof can be performed prior to contacting the activated sorbent and the mercury-containing gas stream. The heating of the mixture including the carbonaceous material and the substrate to form the product thereof can be performed in the mercury-containing gas stream. In some embodiments, the activated carbon sorbent includes a carbon nanocomposite sorbent.
The promoted ammonium salt-protected activated carbon sorbent particles can include promoted ammonium salt-protected powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, any carbonaceous material described herein or a material derived via pyrolysis or devolatization thereof, or a combination thereof. The promoted ammonium salt-protected activated carbon sorbent particles, non-promoted ammonium salt-protected activated carbon sorbent particles, promoted non-ammonium salt-protected activated carbon sorbent particles, or non-promoted non-ammonium salt-protected activated carbon sorbent particles, can have any suitable particle size (e.g., longest dimension of the particle) such as a particle size of about 0.1 μm to about 1000 μm, about 0.1 μm to about 30 μm, or about 0.1 μm or less, or less than, equal to, or greater than about 0.5 μm, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or about 1000 μm or more.
The promoted ammonium salt-protected activated carbon sorbent particles include a product of subjecting a mixture including a carbonaceous material and a nitrogenous material to heating, microwaving, irradiating, or a combination thereof; including a material derived from the product via one or more of halide-promotion and ammonium salt-protection; or a combination thereof. The promoted ammonium salt-protected activated carbon sorbent particles can include a product of acid or base treatment of the product of subjecting a mixture including a carbonaceous material and a nitrogenous material to heating (e.g., by hot gas, hot air, or via any suitable heating method), microwaving, irradiating, or a combination thereof. The carbonaceous material can include powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, brown sugar, barley sugar, caramel, cane sugar, corn syrup, starch, molasses, a glucan, a galactan, a xylan, a sugar waste product, or a combination thereof.
The nitrogenous material can include a nitrogen-containing organic or inorganic material. The nitrogenous material can include a nitrogen heterocycle, a nitrogen-containing polymer or copolymer, a nitrile, a carbamate, an amino acid, nitrobenzene, hydroxylamine, urea, hydrazine, sulfamic acid, an ammonium salt, or a combination thereof. The nitrogenous material can include indole, quinoxaline, carbazole, isoquinoline, nitrobenzene, urea, sulfamic acid, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, vinylpyrrolidone-acrylic acid copolymer, vinylpyrrolidone-maleic acid copolymer, polyethylenimine, alanine, piperazine, quinolone, quinoxaline, diazabicyclooctane, an amino acid, an ammonium salt, or a combination thereof.
The promoted ammonium salt-protected activated carbon sorbent particles can include nitrogen atoms in at least a surface layer thereof, such as nitrogen atoms resulting from the nitrogenous material from heating of a carbonaceous material and a nitrogenous material prior to promotion and ammonium protection/decomposition, or nitrogen atoms resulting from ammonia produced from ammonium salt protection, or a combination thereof. The surface layer can be a continuous or discontinuous layer. The surface layer can have any suitable thickness, such as about 0.001% to about 99% of a radius of the particles (e.g. wherein the radius is half of the longest dimension), 0.001% to about 50%, or 0.001% or less, or less than, equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, or about 50% or more. Any suitable proportion of the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles can be nitrogen atoms, such as about 0.001 wt % to about 99 wt % nitrogen, 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or about 99 wt % or more. The promoted ammonium salt-protected activated carbon sorbent particles can have any suitable overall nitrogen atom concentration, such as about 0.001 wt % to about 50 wt %, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, or about 50 wt % or more.
In some embodiments, a concentration of nitrogen atoms in the surface layer can be greater than a concentration of nitrogen atoms in a core of the promoted ammonium salt-protected activated carbon sorbent particles. The core of the promoted ammonium salt-protected activated carbon sorbent particles can be about 0 wt % to about 99 wt % nitrogen atoms, about 1 wt % to about 6 wt % nitrogen atoms, or about 1 wt % or less, or less than, equal to, or greater than about 2 wt %, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99 wt % or more. The surface layer of the promoted ammonium salt-protected activated carbon sorbent particles can include about 0.001 wt % to about 99 wt % nitrogen atoms, about 5 wt % to about 80 wt % nitrogen atoms, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99 wt % or more.
In some embodiments, nitrogen atoms are substantially homogeneously distributed throughout the promoted ammonium salt-protected activated carbon sorbent particles, with a substantially equal concentration in the core and the surface layer.
The nitrogen atoms in the surface layer (e.g., the ammonia, or nitrogen atoms from other sources) can decrease neutralization of carbocations in the promoted ammonium salt-protected activated carbon sorbent particles by at least one of SO3, H2SO4, and HSO41−, as compared to corresponding promoted ammonium salt-protected activated carbon sorbent particles including less or substantially no nitrogen in a corresponding particle surface layer. The nitrogen atoms in the surface layer can at least partially block carbocations in the promoted ammonium salt-protected activated carbon sorbent particles from at least one of SO3, H2SO4, and HSO41−, as compared to a corresponding promoted ammonium salt-protected activated carbon sorbent particles including less or substantially no nitrogen in a corresponding particle surface layer.
The separating at least some of the mercury-sorbent composition from the mercury-containing gas stream can includes separating in a particulate separator. The particulate separator can include an electrostatic precipitator (ESP), a baghouse, a wet scrubber, a filter, cyclone, fabric separator, or any combination thereof. The contacting, the separating, or a combination thereof, can occur in an aqueous scrubber. The scrubber can include an aqueous slurry that includes the activated carbon sorbent.
The method can further include regenerating the mercury-sorbent composition to give a regenerated activated carbon sorbent.
In some embodiments, the present invention provides a method for separating mercury from a mercury-containing gas stream. The method can include contacting a mercury-containing gas stream with an activated carbon sorbent comprising promoted activated carbon sorbent particles and ammonia, to form a mercury-sorbent composition. The method can include separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas. In various embodiments, the ammonia can be injected into the mercury-containing gas stream (or an ammonium precursor such as urea can be injected, which generates ammonia), such as along with or separately from the sorbent or a precursor thereof.
Promotion.
The promoted ammonium salt-protected activated carbon can include a halide, a hydrogen halide, or a combination thereof, such as complexed with the activated carbon. The promotion of the mercury oxidizing capability of the activated carbon can be effected by addition of several classes of Lewis and Bronstead acids to the carbene site on the precursor activated carbon. The halide, hydrogen halide, or combination thereof, is the promoter, and the complexing of the same with the activated carbon results in promotion of the oxidative reactivity of the activated carbon sorbent precursor with elemental mercury. The halide, hydrogen halide, or combination thereof is about 0.001 wt % to about 30 wt % of the promoted ammonium salt-protected activated carbon, about 1 wt % to about 15 wt %, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more.
The promoted ammonium salt-protected activated carbon sorbent particles can be promoted prior to addition to the mercury-containing gas stream. The method can further include promoting precursor activated carbon sorbent particles (e.g. activated carbon that has received ammonium salt protection or that is free of ammonium salt protection) with a promoter (e.g., halide promoter) to form promoted activated carbon sorbent particles. Promoting precursor activated carbon sorbent particles with the promoter can include chemically reacting carbene species edge sites in the activated carbon sorbent particles with the promoter. Promoting precursor activated carbon sorbent particles with the promoter can include subjecting a mixture including the precursor activated carbon sorbent particles and the promoter to heating (e.g., in hot air or gas, or via any suitable heating method), microwaving, irradiating, or a combination thereof. During the promoting the promoter can be substantially in vapor or gaseous form. The promoting can occur at any suitable time; for example, the promoting of the precursor activated carbon sorbent particles can occur in-flight in the mercury-containing gas stream, or can occur prior to addition of the activated carbon sorbent particles to the mercury-containing gas stream. In some embodiments, the promoting can occur in an aqueous scrubber, wherein the scrubber includes an aqueous slurry that includes the promoter.
The method can include combusting coal that includes the promoter (e.g., halide promoter), a promoter precursor, or a combination thereof (e.g., coal to which the promoter precursor has been added). The promoter precursor can transform into the promoter during or after the combustion. The promoter can combine with an injected activated carbon sorbent downstream of the combustion to form a promoted activated carbon sorbent. The method can include adding the promoter, promoter precursor, or a combination thereof, to the coal prior to the combustion thereof. The promoter, promoter precursor, or a combination thereof, can be added to the coal in any suitable way, for example, as a solid, liquid, gas, or in an organic solvent, such as a hydrocarbon, a chlorinated hydrocarbon, supercritical carbon dioxide, or a combination thereof.
The method can include injecting into the mercury-containing gas stream the promoter, a promoter precursor, or a combination thereof. For example, the promoter, the promoter precursor, or a combination thereof, can be injected (e.g., as a solid, liquid, gas, or combination thereof) into the furnace, into the flue gas, or into any suitable location that allows the promoter to combine with the activated carbon sorbent to form a promoted activated carbon sorbent. In some embodiments, the promoter, promoter precursor, or a combination thereof, is added together with the precursor activated carbon sorbent particles into the mercury-containing gas stream. The promoter, promoter precursor, or a combination thereof, can be added into the mercury-containing gas stream separately from addition of the precursor activated carbon sorbent particles into the mercury-containing gas stream.
The method can include adding the promoter or promoter precursor within (e.g., to) the coal/gas combustion zone, or gasification zone. The promoter precursor can transform into the promoter during or after the combustion, or gasification. The promoter can combine with an injected activated carbon sorbent downstream of the combustion to form a promoted activated carbon sorbent.
The promoter can be any suitable promoter that forms a promoted activated carbon sorbent as described herein. For example, the promoter can be a halide promoter such as HCl, HBr, HI, Br2, Cl2, I2, BrCl, IBr, ICl, ClF, PBr3, PCl5, SCl2, CuCl2, CuBr2, Al2Br6, FeIx (x=1, 2, 3, or 4), FeBry (y=1, 2, 3, or 4), FeClz (z=1, 2, 3, or 4), MnBr2, MnCl2, NiBr2, NiCl2, NiI2, ZnBr2, ZnCl2, ZnI2, NHBr, NH4Cl, NHsI, NH4F, or a combination thereof. The promoter precursor can be a metal halide or a nonmetal halide. The promoter can be HBr.
The method can include forming the promoter form a promoter precursor, such as during combustion with the coal or downstream of the coal combustion in the flue gas. The promoter precursor can be any suitable material that can transform into a suitable promoter, such as an elemental halogen, a Group V halide, a Group VI halide, a hydrohalide, an ammonium halide, a metal halide, a nonmetal halide, an alkali earth metal halide, an alkaline earth metal halide, or a combination thereof. The promoter precursor can be NaBr, NaCl, NaI, Br−, Cl−, I−, KI, KCl, LiCl, LiBr, CuCl2, CuBr2, AgCl, AgBr, CHI3, CH3Br, AuBr, FeIx (x=1, 2, 3, or 4), FeBry (y=1, 2, 3, or 4), FeClz (z=1, 2, 3, or 4), MgBr2, MgCl2, MnBr2, MnCl2, NiBr2, NiCl2, NiI2, ZnBr2, ZnCl2, ZnI2, CaI2, CaBr2, CaCl2, or a combination thereof. The promoter precursor can have any suitable particle size, such as a particle size of about 0.1 μm to about 1000 μm, or about 0.1 μm or less, or less than, equal to, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or about 1000 μm or more.
Ammonium Salt Protection.
The promoted ammonium salt-protected activated carbon can include ammonia (e.g., ammonia that forms from thermal decomposition of the ammonium salt), the ammonium salt, or a combination thereof. The ammonia can result from the ammonium salt protection of the activated carbon sorbent precursor (e.g., of a promoted activated carbon sorbent or a non-promoted activated carbon sorbent). The ammonia or ammonium salt can be any suitable proportion of the promoted ammonium salt-protected activated carbon, such as about 0.001 wt % to about 30 wt %, about 0.01 wt % to about 15 wt %, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more. The released ammonia can collect in the pore structures of the carbon sorbent or release into the gas phase in close proximity to the sorbent particle. In either space the ammonia can reacts with and neutralize Sulfur(VI) species in the gas phase, removing them from the gas phase and preventing their interference with the active site on the carbon surface. Some ammonia can also bind to deposits of ammonium salt surrounding the active site, and can react with sulfur VI species before they neutralize the carbon active site.
In some embodiments, the promoted ammonium salt-protected activated carbon can include an anionic counterion of the ammonium salt. The anionic counterion can result from the ammonium salt protection of the activated carbon sorbent precursor (e.g., of a promoted activated carbon sorbent or a non-promoted activated carbon sorbent). The anionic counterion of the ammonium salt can be any suitable proportion about 0.001 wt % to about 30 wt % of the promoted ammonium salt-protected activated carbon, 0.01 wt % to about 15 wt %, or about 0.001 wt % or less, or less than, equal to, or greater than about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more.
The method can further include protecting a precursor activated carbon sorbent with an ammonium salt to form the promoted ammonium salt-protected activated carbon sorbent particles. The precursor activated carbon sorbent can be a promoted activated carbon sorbent, or an activated carbon sorbent that is free of halide-promotion. The protecting of the promoted or non-promoted activated carbon sorbent particles with the ammonium salt can include subjecting a mixture including the activated carbon sorbent particles and the ammonium salt to heating, microwaving, irradiating, or a combination thereof. The mixture including the activated carbon sorbent particles and the ammonium salt can have any suitable ratio of the activated carbon sorbent particles (e.g., either promoted or unpromoted) to the ammonium salt, such as about 1:100 to about 100:1, about 1:1 to about 1:5, or about 1:100 or less, or less than, equal to, or greater than about 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, or about 100:1 or more.
The promoted ammonium salt-protected activated carbon sorbent particles can be ammonium salt-protected prior to addition to the mercury-containing gas stream, wherein the ammonium salt-protection of the promoted activated carbon sorbent particles or of precursor activated carbon sorbent particles occurs prior to addition of the promoted activated carbon sorbent particles to the mercury-containing gas stream. The ammonium salt-protection of the promoted activated carbon sorbent particles or of precursor activated carbon sorbent particles (e.g., activated carbon sorbent particles free of promotion) can occur in-flight in the mercury-containing gas stream.
The ammonium salt can be added to a coal-burning power plant at any suitable location. The method can include injecting the ammonium salt into the mercury-containing gas stream, such as into the flue gas, such as at any location within the combustion zone or downstream of the combustion zone. The ammonium salt can be added together with the promoted activated carbon sorbent particles or precursor activated carbon sorbent particles (e.g., activated carbon sorbent particles free of halide-promotion) into the mercury-containing gas stream. The ammonium salt can be added into the mercury-containing gas stream separately from addition of the promoted activated carbon sorbent particles or precursor activated carbon sorbent particles into the mercury-containing gas stream.
The ammonium salt can be any suitable ammonium salt that can form an ammonium salt-protected activated carbon sorbent as described herein. The ammonium salt can be an ammonium halide that is also used as a promoter precursor in the method, wherein addition of the promoter precursor and the ammonium salt can occur simultaneously as the same step in the method, advantageously producing ammonia and promoting the activated carbon. The ammonium salt can be an ammonium halide, a methylammonium halide, an ammonium salt of an oxyacid of a Group VI element, an ammonium salt of an oxyacid of a Group V element, or a combination thereof. The counterion of the ammonium salt can be an anion of a halogen or Group VI element, an oxyanion of a Group VI element such as sulfate, sulfite, thiosulfate, dithionite, or an oxyanion of a Group V element such as nitrate, nitrite, phosphate, phosphite, thiophosphate, or carbonate. The ammonium salt can be ammonium bromide, ammonium iodide, ammonium chloride, an organic halide with a formula of CH3NH3X (wherein X is Cl, Br or I), ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, ammonium persulfate, ammonium pyrosulfate, ammonium thiosulphate, ammonium dithionite, ammonium aluminium sulfate, ammonium iron sulfate, ammonium sulfamate, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium thiophosate, ammonium nitrate, ammonium nitrite, ammonium carbonate, ammonium thiocyanate, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium chlorate, ammonium chromate, ammonium fluoride, ammonium formate, ammonium hydroxide, ammonium perchlorate, or a combination thereof. The ammonium salt can be ammonium sulfate. The ammonium salt can have any suitable particle size, such as a particle size of about 0.1 μm to about 1000 μm, about 0.1 μm to about 10 μm, or about 0.1 μm or less, or less than, equal to, or greater than about 0.5 μm, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or about 1000 μm or more.
Sorption of Mercury.
Referring now to
It has now been found that the formation of the new halide (e.g., bromide) compound with carbon increases their reactivity toward mercury and other pollutants. Additionally, the resulting halide compound is uniquely suited to facilitate oxidation of the mercury. The effectiveness of the oxidation can result from the promotion effect of the halide, exerted on the developing positive charge on the mercury during the oxidation, known in the chemical art as a specific catalytic effect. Thus, as the mercury electrons are drawn toward the positive carbon, the halide anion electrons are pushing in from the other side, protecting the positive charge developing on the mercury and lowering the energy requirement for the oxidation process. Bromide is especially reactive, owing to the highly polarizable electrons in the outer 4p orbitals of the ion. Thus, adding HBr or Br2 (or a precursor that forms one or both of these) to the carbon forms a similar carbenium bromide, in which the positive carbon oxidizes the mercury with the assistance of the bromide ion. Iodide is an even more nucleophilic species, hence lowers the energy requirement even more, giving higher reaction rates. Chlorine is less effective, but still facilitates oxidation.
A mechanistic model showing the promotion, as well as mercury oxidation and capture, and protection when using ammonium salts is illustrated in
(NH4)2SO4→NH3+NH4SO4H(ammonium bisulfate)
2(NH4)2SO4→2NH3+(NH4)2S2O7(ammonium pyrosulfate) Reaction 1:
In the model described in
Other similar ammonium salts will similarly donate hydrogen ion to the zig-zag carbon from the ammonium ion to form a carbenium ion which is subsequently converted by hydrogen halides in the gas stream to the carbenium halide ion pair in the promotion mechanism as shown for ammonium sulfate.
Ammonia formed on the surface and residing on the carbon surface (and near capture sites) as well as the sulfuric acid generated are capable of intercepting SO3 from the gas phase as shown in Reactions 3 and 4, preventing their reaction with the active carbon site, thereby protecting the site from deactivation and allowing mercury capture to occur. Thus the embodiments that utilize ammonium salt as the optional component are highly effective in protecting sorbent sites from flue gas contaminants (e.g. SO2, SO3, NOx, selenates, and the like), in particular SO3.
NH3+SO3→NH3SO3(sulfamic acid) Reaction 3:
H2SO4+SO3→H2S2O7(pyrosulfuric acid)+NH3
H2S2O7+NH3→(NH4)2S2O7(ammonium pyrosulfate) Reaction 4:
With other anionic species derived from the ammonium salt, there may be some additional subsequent reactions of the byproducts of the reactions. Or there may be decomposition reactions of the salts that produce secondary components valuable for the capture of mercury. For example, when ammonium thiosulfate is used, the reaction proceeds with formation of the carbenium ion. Subsequently, the thiosulfate reacts with mercury halide to form more stable mercury sulfide.
Contacting the mercury-containing gas stream with the activated carbon sorbent including promoted ammonium salt-protected activated carbon sorbent particles to form the mercury-sorbent composition can include chemically reacting the mercury in the mercury-containing gas stream with the promoted ammonium salt-protected activated carbon sorbent. The promoted ammonium salt-protected activated carbon sorbent particles can include active sites, wherein the active sites include halide anions bound to the sorbent particles, such as carbocations bound to halide anions. The carbocations in the promoted ammonium salt-protected activated carbon sorbent particles can accept electrons from mercury atoms of the mercury-sorbent particulate.
In the promoted ammonium salt-protected activated carbon sorbent particles ammonia or an anionic ammonium counterion derived from the ammonium salt can intercepts SO2, SO3, NOx, selenates, or a combination thereof, in the mercury-containing gas stream, preventing reaction thereof with active carbon sites in the promoted ammonium salt-protected activated carbon.
Coal-Fired Power Plant Mercury-Removal System.
Referring now to
Reservoirs 110, 120, 130, and 180 connect through their respective flow control devices and via associated piping, to transport line 115. Optional alkali (or ammonium salt) component reservoir 180 may also connect, through respective flow control devices and via associated piping, to transport line 118. A source of air, nitrogen, or other transport gas(es) is provided by gas source 170 to transport line 115 for the purpose of entraining materials discharged from reservoirs 110, 120, 130, and 180 and injecting such materials, via injection point 116, into contaminated flue gas stream 15. A source of air, nitrogen, or other transport gas(es) may be provided by gas source 171 to transport line 118 for the purpose of entraining materials discharged from reservoirs 180 and injecting such materials, via injection point 119, into flue gas stream 15. Reservoirs 110, 120, 130, and 180 may be the same or different, as desired. Gas sources 170 and 171 may be the same or different, as desired. Alternatively, transport gas(es) may be provided to both transport lines 115 and 118 by gas source 170 (connection from source 170 to line 118 not shown). Although gas sources 170 and 171 are shown in
For clarity, single injection points 116 or 119 are shown in
Downstream from injection point 116 and 119 is provided particulate separator 140. By way of illustration and not limitation, particulate separator 140 may comprise one or more fabric filters, one or more electrostatic precipitators (hereinafter “ESP”), one or more scrubbers, or other particulate removal devices as are known in the art. It should be further noted that more than one particulate separator 140 may exist, sequentially or in parallel, and that injection point 116 and 119 may be at a location upstream and/or downstream of 140 when parallel, sequential, or combinations thereof exist. Particulate separator 140 produces at least a predominantly gaseous (“clean”) stream 142, and a stream 141 comprising separated solid materials. A sorbent/ash separator 150 separates stream 141 into a largely ash stream 152, and a largely sorbent stream 151. Stream 151 may then be passed to an optional sorbent regenerator 160, which yields a regenerated sorbent stream 161 and a waste stream 162.
An optional Continuous Emission Monitor (hereinafter “CEM”) 205 for mercury is provided in exhaust gas stream 35, to provide electrical signals representative of the mercury concentration in exhaust stream 35 as a function of time. The optional mercury CEM 205 and flow controllers 201, 202, 203, 208, and 209 are electrically connected via optional lines 207 (or wirelessly) to an optional digital computer (or controller) 206, which receives and processes signals and controls the preparation and injection of promoted carbon sorbent into contaminated flue gas stream 15.
In operation, promoted ammonium salt-protected carbon sorbent (or precursor) and/or an optional alkali (or ammonium salt) component (or precursor) is injected into contaminated flue gas stream 15. After contacting the injected material with the contaminated flue gas stream 15, the injected promoted ammonium salt-protected carbon sorbent, or precursors that then form the promoted ammonium salt-protected carbon sorbent, reduces the mercury concentration, transforming contaminated flue gas into reduced mercury flue gas, 25. The injected material is removed from the flue gas 25, by separator 140, disposed of or further separated by optional separator 150, and disposed of or regenerated by an optional regenerator 160, respectively. The reduced mercury “clean” flue gas stream 42 (or 35) is then monitored for mercury content by an optional CEM 205, which provides corresponding signals to an optional computer/controller 206. Logic and optimization signals from 206 then adjust flow controllers 201, 202, 203, 208, 209 to maintain the mercury concentration in exhaust stream 35 within desired limits, according to control algorithms well known in the art. Flow controllers 201, 202, 203, 208, 209 can also be adjusted manually or be some other automated means to maintain the mercury concentration in exhaust stream 35 within desired limits, according to control algorithms well known in the art.
Referring still to
Similarly, the optional ammonium salt may be contacted and react directly in transport line 115 via line 131, or optionally as described above with respect to the halogen/halide, via lines 131b and 131c, or added in reservoir 110 (in which case 110 and 130 are same reservoir) and injected via. lines 111 and 115, or injected directly into stream 115 to form the promoted ammonium salt-protected carbon sorbent, either in line 115 or stream 15.
Similarly, the optional alkali and/or ammonium salt component (s) from 180 may either be added to reservoir 110 (in which case 110 and 180 are same reservoir) and injected via. lines 111 and 115, or injected in transport line 115 directly, or may be injected separately by transport line 118, combining in 115, or in flue gas stream 15 for synergistic effects with activated carbon, promoted carbon, or optional secondary components. Being able to vary the amount of the optional alkali and/or ammonium salt component (s) relative to activated carbon, promoted carbon, or optional secondary components is a key feature to overcome and optimize for site-specific operating and flue gas conditions.
Ammonium Salt-Protected Activated Carbon Sorbent Particles.
In various embodiments, the present invention provides ammonium salt-protected activated carbon sorbent particles, such as any embodiment of the promoted or unpromoted ammonium salt-protected activated carbon sorbent particles described herein or that can perform an embodiment of the method for mercury removal described herein. The ammonium salt-protected activated carbon sorbent particles can include ammonia, an ammonium salt, or a combination thereof in at least a surface layer thereof.
In some embodiments, the ammonium salt-protected activated carbon sorbent particles are promoted ammonium salt-protected activated carbon sorbent particles. For example, the promoted ammonium salt-protected activated carbon sorbent particles can include active sites that bind with mercury atoms. The active sites can include carbocations bound to promoter anions (e.g, halides).
The ammonium salt-protected activated carbon sorbent particles can further include an anionic counterion. The anionic counterion can be derived from the ammonium salt or precursor thereof.
Method of Making the Ammonium Salt-Protected Activated Carbon Particles.
In various embodiments, the present invention provides a method of making ammonium salt-protected activated carbon particles, such as any embodiment of the promoted or unpromoted ammonium salt-protected activated carbon sorbent particles described herein or that can perform an embodiment of the method for mercury removal described herein. For example, the method of making the ammonium salt-protected activated carbon particles can include subjecting a mixture including a precursor activated carbon sorbent and an ammonium salt to heating (e.g., in hot flue gas, hot air, or any suitable heating method), microwaving, irradiation, or a combination thereof, to form an activated carbon sorbent including promoted ammonium salt-protected activated carbon sorbent particles. The precursor activated carbon sorbent can be a promoted activated carbon sorbent, or an unpromoted activated carbon sorbent. The method can further include promoting an activated carbon with a promoter (e.g., which can optionally be formed from a promoter precursor) to provide the precursor activated carbon sorbent.
Various embodiments of the present invention can be better understood by reference to the following Examples which are offered by way of illustration. The present invention is not limited to the Examples given herein.
Part I (Include 3338.005 Examples and Figures).
Finely powdered activated carbon (such as NORIT Darco FGD, NORIT Americas, Inc., Marshall, Tex. (USA), although others are suitable, as will be recognized by those skilled in the art), was placed in a rotating plastic barrel with side blades (a 5 ft3 (0.14 m3) cement mixer) fitted with a tight plastic lid to prevent loss of the fine powder during the preparation. In a separate vessel, gas phase bromine was generated by passing a nitrogen stream over a weighed amount of liquid bromine that is warmed to about 40°-50° C. The vapor pressure of the bromine was such that a dark red gas is generated and passed out of the generator. The outlet from the gaseous bromine generator is connected via a ¼ inch (0.64 cm) plastic hose to a stationary metal tube inserted through a flange in the center of the plastic lid and passing into the center of the barrel. The flange is not air tight so that the excess of nitrogen is released after the bromine is transferred to the tumbling carbon. Thus, the bromine gas stream continuously passed into the rotating barrel where it contacted the tumbling carbon. The unit is then operated until the desired amount of bromine has combined with the carbon. Typically, this is 0.4 to 1 kg of bromine to 20 kg of carbon (2-5 wt. %). When the reaction is completed, the carbon is weighed. The treated carbon is odorless and does not cause skin irritation since the bromine has completely reacted with the carbon to produce the brominated carbon.
XPS spectra demonstrate that the brominated carbon contains both covalent carbon-bound (organic) bromide as well as anionic bromide. The product contains the same moisture originally present in the activated carbon (5-17 wt %), but does not require further drying for use. The moisture is driven out at higher temperatures (>150° C.), and the bromine was not released until very high temperatures.
Bench-Scale Testing of Mercury Oxidation and Capture Efficiency.
A bench-scale apparatus and procedure based on the above description was used to test the initial activities and capacities of several promoted activated carbon sorbents using powdered carbon, including bromine-containing activated carbons prepared from a variety of carbons, including commercially available sorbents, aerogel film sorbents, and the original precursor carbons for comparison.
A detailed description of the apparatus and its operation is provided in Dunham, G. E.; Miller, S. J., Chang, R.; Bergman, P. Environmental Progress 1998, 17, 203, which is incorporated herein by reference in its entirety. The bench scale mercury sorbent tests in the flue gas compositions were performed with finely (−400 mesh) powdered sorbents (37 mg) mixed with 113 mg sand and loaded on a quartz filter (2.5 inch (6.35 cm)). The loaded filter and holder were heated in an oven (125° C.) in the simulated flue gas stream (30 SCFH (standard cubic feet/hr) or 0.79 NCMH (normal cubic meters per hour)) containing the following: 0 2 (6%), CO2 (12%), SO2 (600 ppm), NO (120 ppm), NO2 (6 ppm), HCl (1 ppm), Hg0 (11 μg/m), H2O (15%), and N2 (balance). Elemental mercury was provided by a standard permeation tube source placed in a double jacketed glass condenser, and heated to the desired temperature. Mercury concentrations in the gas streams were determined with a continuous mercury emission monitor (Sir Galahad mercury CEM mfr. P.S. Analytical Deerfield Beach Fla. USA), and a SnCh cell was used to convert oxidized species to elemental, so that both elemental and oxidized mercury concentration data could be obtained for both the influent and the effluent concentrations from the sorbent bed. Mercury concentrations were calibrated for the flow rates used. Spent sorbents were analyzed for mercury to determine the mass balance.
Referring now to
A bed of activated carbon supported in a vertical tube by a plug of glass wool was fluidized by a nitrogen stream. The top of the fluidized bed tube was connected to a catching trap for carbon fines that blow out the top of the tube. The bromine gas generator as described in Example 1-1 was attached to the fluidized carbon bed and the desired amount of gaseous bromine was passed into the bed. The contents of the trap were then mixed with the material in the bed and weighed. The resulting brominated carbon exhibited properties similar to the brominated carbon of Example 1-1.
A 5% solution of bromine in water was prepared by carefully adding 50 g of bromine to 1 liter of cold water. One kg of activated carbon was added to the bromine solution in a large metal can. The resulting slurry was stirred with a large paddle during the addition and for a short time afterwards until all the bromine had reacted with the carbon, as indicated by the disappearance of the red color. The slurry was then filtered using a Buchner funnel under vacuum. The moist carbon that was collected on the filter was dried in an oven at 110° C. for several hours to constant weight. As in Example 1-1, some moisture remains in the carbon, however. The dried carbon was then tumbled in the rotating barrel with metal pieces to break up and fluff the carbon.
Brominated carbon was produced by solution phase bromination similar to that described with reference to Example 1-3. However, before filtration, a solution of hydriodic acid (HI) was added to the slurry in an amount equal to 10% of the bromine amount. The slurry was stirred to complete the reaction and then filtered and dried as described in Example 1-3.
A solution of phosphorus tribromide (500 g) in ligroin (10 liters) was stirred in a large metal can and 10 kg of activated carbon was added. The resulting slurry was stirred with a large paddle at ambient temperature to complete the reaction. The slurry was filtered under vacuum on a large Buchner funnel in several batches. The wet filter cake was dried at 110° C. in an oven to constant weight. The dried product was fluffed in the rotating barrel as described in Example 1-3.
Tests were conducted on a pilot-scale combustor while firing a subbituminous coal, to evaluate mercury control by injecting larger-than-normal sized treated activated carbon. Standard AC sorbents generally are of fine size with a mean particle diameter of less than 20 micrometers, which is also typical of the flyash that is generated from pulverized coal combustion. Consequently, because the sizes of standard AC and flyash are similar, separation of the two is difficult. Injection of larger sized AC is generally not considered because the sorbent effectiveness decreases with size.
In a scheme to recycle the injected carbon, the carbon is separated from the flyash. A separation based on size fractionation requires a treated larger particle sorbent. To test this concept, a treated larger sized (>60 μm) sorbent was developed, prepared, and tested.
Treatment—Gas Phase Halogenation.
Granular activated carbon (Calgon F400) was ground and sieved through conventional mesh screens. The mesh size fraction −170 to +240 (corresponding to about 60 to about 88 micrometers) was collected and placed in a rotating vessel as described in Example 1-1 above. In a separate vessel, gas phase bromine was generated by passing a nitrogen stream over a weighed amount of liquid bromine that was warmed to about 40°-50° C., and the outlet from this gaseous bromine generator was connected via a ¼ inch (6.35 mm) plastic hose to a stationary metal tube inserted through a flange in the center of the lid and passing into the center of the rotating vessel, also as described in Example 1-1. The unit was operated until the desired amount of bromine had combined with the carbon, in this case 0.05 kg of bromine to 1 kg of carbon (5 wt. %). When the reaction was completed, the carbon was weighed. The treated carbon was odorless as has been described above.
PTC Apparatus.
The pilot-scale combustor, known as the “Particulate Test Combustor” (hereinafter “PTC”), is a 550,000-Btu/hr (about 161 kW) pulverized coal (“PC”)-fired unit, designed to generate combustion flue gas properties and fly ash that are representative of those produced in a full-scale utility boiler. The combustor is oriented vertically to minimize wall deposits. A refractory lining helps to ensure adequate flame temperature for complete combustion and prevents rapid quenching of the coalescing or condensing fly ash. Based on the superficial gas velocity, the mean residence time of a particle in the combustor is approximately 3 seconds. The coal nozzle of the PTC fires axially upward from the bottom of the combustor, and secondary air is introduced concentrically to the primary air with turbulent mixing. Coal is introduced to the primary air stream via a screw feeder and eductor. An electric air preheater is used for precise control of the combustion air temperature. Originally, the PTC used cold-water annular heat exchangers to provide flue gas temperature control to the baghouse (also referred to as a “fabric filter”) or electrostatic precipitator (ESP). However, analysis of ash deposits collected from the heat exchangers indicated that some mercury was collected on the duct walls. To minimize this effect, the heat exchangers were modified to provide for higher duct wall temperatures.
The PTC instrumentation permits system temperatures, pressures, flow rates, flue gas constituent concentrations, and particulate control device (baghouse, Advanced Hybrid Particle Collector/AHPC™, and/or electrostatic precipitator/ESP) operating data to be monitored continuously and recorded on a data logger.
PTC Procedure.
Flue gas samples were taken at combinations of two of the three available system sample points: the furnace exit, the particulate control device inlet, and the particulate control device outlet. After passing through sample conditioners to remove moisture, the flue gas was typically analyzed for O2, CO, CO2, SO2, and NOx. Each constituent was normally analyzed at both the furnace exit and the outlet of the particulate control device simultaneously, using two analyzers. The concentration values from all of the instruments were recorded continuously. In addition, data were manually recorded at set time intervals. NOx was determined using a pair of Rosemount Analytical NOx chemiluminescent analyzers. SO2 was measured using a pair of Ametek Instruments photometric gas analyzers. The remaining gases were measured by a pair of Rosemount Analytical multi-gas continuous emissions monitors. Each of these analyzers was regularly calibrated and maintained to provide accurate flue gas concentration measurements.
The baghouse vessel was a 20 inch (50.8 cm) (ID) chamber that is heat-traced and insulated, with the flue gas introduced near the bottom. The combustor produced about 200 ACFM (actual cubic feet per minute; about 5.7 actual m3/min) of flue gas at 300° F. (about 150° C.), therefore three 13-ft by 5-inch (3.96 m by 12.7 cm) bags provided an air-to-cloth ratio of 4 ft/min (1.22 m/min). Each bag was cleaned separately in operation with its own diaphragm pulse valve. In order to quantify differences in pressure drop for different test conditions, the bags were cleaned on a time basis, rather than with the cleaning cycle initiated by pressure drop. Once bag cleaning was initiated, all three bags were pulsed in rapid succession on-line.
Tests were also conducted with a single-wire, tubular ESP replacing the fabric filter. The ESP unit was designed to provide a specific collection area of 125 at 300° F. (150° C.). Since the flue gas flow rate for the PTC is 130 SCFM (standard cubic feet per minute; about 3.7 NCMM (normal m3/min)), the gas velocity through the ESP is 5 ft/min (about 1.52 m/min). The plate spacing for the ESP unit is 11 in (27.9 cm). The ESP was designed to facilitate thorough cleaning between tests so that all tests can begin on the same basis.
PTC Results.
Results are illustrated in
Referring now to
A 5% solution of bromine in ligroin was prepared by carefully adding 50 g of bromine to 1 liter of cold ligroin. One kg of activated carbon was added to the bromine solution in a large metal can. The slurry was stirred with a large paddle during the addition and for a short time afterwards until all the bromine had reacted with the carbon as indicated by the disappearance of the red color. The slurry was filtered using a Buchner funnel under vacuum. The carbon cake that was collected on the filter was dried in an oven at 110° C. for several hours until it appeared dry and a constant weight was obtained. As in Example 1-1, some moisture was left in the carbon, however. The dried carbon was then tumbled in the rotating barrel with metal pieces to break up and fluff the carbon.
A bench-scale procedure based on the above description was used to test the initial activities and capacities of several promoted activated carbon sorbents using powdered carbon, including the bromine-containing activated carbons prepared from a commercially available sorbent and an aerogel carbon film sorbent, as well as the original precursor carbons for comparison. Bromine-treated carbons were prepared by impregnation of the powdered activated carbon precursors in a stirred solution of bromine in carbon tetrachloride or methylene chloride, or alternatively, in an aqueous solution of HBr, followed by drying in air at ambient temperature and drying in an oven at 100° C. in air or nitrogen. Bromine-treated carbons were also prepared by impregnating bromine from the gas phase by passing the gas through a rotating dry bed of the activated carbon precursor. The results indicated that adding a second component to the solution improved the capacity of the sorbent.
The carbons were initially tested in a heated bed, where a synthetic flue gas stream containing elemental mercury (11 g/m3) was passed through the bed. Concentrations of total and elemental Hg in the effluent gas were determined using a Sir Galahad mercury CEM (“continuous emission monitor”) (mfr. P S Analytical, Deerfield Beach, Fla., USA). The powdered sorbent was supported on a quartz filter during the test, and the other sorbents were tested as a triple layer. A comparison of the original commercial-grade powdered carbon sorbent with the sorbent after it was treated with 0.1 N HBr, and the powder was collected by centrifugation and drying, revealed that the mercury capture activity increased from an initial capture efficiency of about 50% of the Hg in the inlet to 100% capture. A comparison of the sorbent after subsequent regeneration with HBr indicated that it not only captured mercury at the same level as before (100% capture) but its capacity was prolonged by several minutes, and thus enhanced. Similar results were obtained with the carbon film and carbon fiber sorbents by treatment with molecular bromine in solution or in dry beds as described above.
An activated carbon sorbent was prepared by treating the carbon by impregnating molecular bromine from a gas composition containing molecular bromine by flowing the gas through a liquid bromine reservoir in series with a fluidized bed or ebulliated bed of the carbon. The amount of bromine taken up by the carbon ranges (in one example) from <1 to about 30 g per 100 g of activated carbon, depending on the proportions used.
In this example, a baghouse (fabric filter) or ESP was used to collect particulates in the exhaust of a full-scale commercial pulverized coal-burning facility. A scrubber and sorbent bed were also used to remove undesired constituents from the flue gas stream, before being fed to the stack. In this Example, the halogen/halide promoted carbon sorbent was injected into the flue gas after the boiler. In general however, the inventive sorbent can be injected where desired (e.g., before, after, or within the boiler).
In one exemplary test conducted at a facility fired with lignite coal, the flue gas phase mercury (elemental) concentration was between 10 and 11 μg/m3. The ash and injected carbon were collected in the baghouse at 350° F. to 375° F. (about 175-190° C.). Injection of commercial-grade activated carbon powder (untreated) at a rate of 1.0 lb/MACF (“MACF” and “Macf” represent one million actual cubic feet; 1.0 lb/MACF is about 16 kg/MACM (million actual cubic meters)) resulted in mercury effluent concentrations of 3.8-4.2 μg/m3 (representing 62%-58% removal of the mercury from the gas, respectively), and at 2.0 lb/MACF (about 32 kg/MACM), gave 74%-71% removal. Injection of the bromine-treated carbon at 1.0 lb/MACF resulted in 73%-69% removal and at 2.0 lb/MACF gave 86%-84% removal. Thus, a significant increase in the mercury capture was exhibited during use of the bromine promoted carbon sorbent of the present invention.
The efficiency of the activated carbons for mercury capture can be improved considerably by employing a basic material co-injected with the activated carbon, in order to capture any oxidized mercury that may be released from the sorbent, or to capture some of the sulfur or selenium oxides in the flue gas that can have a detrimental effect on the sorbent capacity.
Bench-scale testing was conducted by preparing a filter composed of 37 mg of brominated activated carbon mixed with 113 mg of calcium oxide. The test was conducted as described in Example 1-1 and compared with the same carbon sorbent but with an inert diluent. The breakthrough curve for the mixture of brominated (2%) NORIT Darco FGD sorbent with inert sand is shown in
Tests were conducted on the pilot-scale PTC combustor described above with reference to Example 1-6 while firing a Texas lignite to evaluate mercury control by co-injecting a standard activated carbon (also referred to herein as “AC”) and an alkali material upstream of a fabric filter.
Typical results are illustrated in
Without wishing to be bound by any particular theory, the synergy observed in the improved performance when co-injecting the two materials can be explained as follows. First, tests indicate that binding sites on AC can be consumed by sulfur species and other contaminants. The alkali material interacts and reacts with these species thus minimizing their consumption of AC mercury binding sites. Second, other work has shown that standard AC will continue to oxidize mercury even though the binding sites are fully consumed. This oxidized mercury can then react with alkali material and subsequently be captured by the particulate control device. Thus, combining alkali with treated and/or non-treated AC synergistically takes advantage of these two mechanisms, resulting in improved mercury capture at reduced costs.
Preparation of 5% Br2W-AC.
Using a procedure similar to Example 1-3, a 2.5 wt/vol % solution of bromine in water was prepared. Granular Calgon F400 was added to the bromine solution to give a 5 wt/wt % brominated carbon product. The bromine solution was stirred with a large paddle during and after the addition until the red color in the water disappeared. The suspension was filtered by vacuum on a large Buchner funnel. The filter cake was dried in air, and then in an oven at 110° C. until a stable weight was obtained. The moisture was reduced to 15%.
Preparation of 5% Br2D-AC.
A brominated sorbent was prepared from Br2 addition in solvent as described in Example 1-7, except that dichloromethane was used as the solvent instead of ligroin, and granular Calgon F400 was used.
Preparation of 5% PBr3-AC.
A phosphohalogenated sorbent was prepared from PBr3 using the method described in Example 1-5, except granular Calgon F400 was used.
Testing in Hydrogen Atmosphere—Procedure
To simulate the capture of mercury from a heated fuel gas or syngas from coal gasification, tests were conducted employing a stream including 10% vol/vol hydrogen in nitrogen passing through the sorbent at 500 cc/min. The stream contained 26.9 micrograms/m3 of elemental mercury from a commercial mercury permeation source.
In the tests, the sorbent (0.5 g) was placed in a 0.39 inch (1 cm, inside diameter) glass tube fitted with a medium frit sintered glass filter disc to hold the sorbent in the gas stream. The tube containing the sorbent bed was connected to a gas inlet tube for introducing the gas stream containing the mercury vapor and at the outlet to a tube connection to the detector. The detector was a Semtech 2000 continuous mercury emission monitor. The tube was equilibrated in a nitrogen flow (450 cc/min) for 5 minutes at ambient temperature to protect the system. The detector showed 0 concentration of mercury in the effluent from the sorbent bed. (The blank run with no sorbent read 26.9 micrograms/m3). The tube was then placed in an oven at the selected temperature for the test (from 250° to 400° C.). Effluent mercury concentration data from the detector were collected until the detector showed a constant reading for 5 minutes. Hydrogen (50 cc/min) was then added to the gas stream and detector readings were taken every 5 min. Tests were conducted at several oven temperatures for various periods of time up to 3 hours, depending on the temperature and sorbent. The elemental mercury concentration data were plotted as a percent of inlet mercury concentration versus time as in Example 1-1. All the mercury in the effluent was elemental, so a single detector was sufficient, and no SnCl2 trap was needed to convert to elemental mercury (as in Example 1-1). The time for 50% breakthrough (time to reach 50% capture) was then determined from the breakthrough curves.
Results.
The results are shown in Table 1 (below) for the unbrominated sorbent (Calgon F-400), the brominated sorbents (5% Br2W-AC and 5% BrD-AC), and the phosphobrominated sorbent (5% PBr3-AC). The maximum mercury concentration obtained in the effluent in each run is also reported in Table 1 for the time period indicated in the last column.
Under the reducing hydrogen conditions, the unbrominated sorbent broke through immediately and was exhausted after only 6.5 min. This complete failure occurred because the hydrogen reduces the captured mercury in the unbrominated sorbent at any temperature above 100° C.
Both of the brominated sorbents exhibited excellent reactivity and good capacity at all temperatures, up to at least 400° C. The phosphobrominated sorbent exhibited superior reactivity and capacity at all temperatures, up to at least 400° C.
Part II. Activated Carbon Sorbent Including Nitrogen.
A carbon (20×60 mesh) prepared by steam activation of a lignite char was stirred with an aqueous solution of dextrose and ethanolamine in ratio of 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts of dextrose. The water solvent was removed by rotovaporation and the impregnated carbon was air-dried. The dried material was reactivated at 750° C. for 2 hours under nitrogen stream.
A char (20×60 mesh) prepared by heating a lignite at 400° C. was stirred with an aqueous solution of dextrose and ethanolamine in ratio of 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts of dextrose. The water solvent was removed by rotovaporation and the impregnated carbon was air-dried. The dried material was activated at 750° C. for 2 hours under nitrogen stream.
A carbon (20×60 mesh) prepared by steam activation of a wood char was stirred with an aqueous solution of dextrose and ethanolamine in ratio of 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts of dextrose. The water solvent was removed by rotovaporation and the impregnated carbon was air-dried. The dried material was reactivated at 750° C. for 2 hours under nitrogen stream.
A carbon (20×60 mesh) prepared by steam activation of a wood char was stirred with an aqueous solution of dextrose and alanine in ratio of 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts of alanine. The water solvent was removed by rotovaporation and the impregnated carbon was air-dried. The dried material was reactivated at 750° C. for 2 hours under nitrogen stream.
The molecular sieve carbons obtained as described in Examples 2-1a to 2-1d were impregnated with 5 wt % of sulfuric acid. The impregnated carbon was then dried in an oven at 110° C. The carbon (0.100 g) was packed into a 3 mm diameter pyrex tube and held in place by glass wool plugs at both ends. A constriction in the pyrex tube at exit end prevented the plug from blowing out. The reactor tube was heated in a GC oven at 150° C.±0.50 as a constant temperature device. The mercury vapor was contained in an air flow of 100 cm3/min through the reactor tube at a concentration of 429-447 micrograms/m3, determined with a continuous mercury vapor monitor.
The mercury source was a temperature-calibrated permeation tube. The permeation tube was heated in a double-jacketed glass condenser with a circulating hot silicone oil system. The concentration in the effluent air stream from the reactor tube was monitored with a continuous cold-vapor UV mercury vapor monitor (EPM). Blank runs were conducted before each carbon test to determine the mercury concentration. The instrument was zeroed with an air stream passed through a large iodized carbon filter. This apparatus thus gave the percent of mercury not removed by the carbon bed (the concentration of mercury in the outlet divided by the concentration of mercury in the inlet, times 100). For the nitrogenous molecular sieve carbons (Examples 2-1 to 2-4) only 1% of the mercury vapor was not removed by the carbon bed over a period of several hours.
The sorbent carbon pretreated as in Example 2-le was ground to about 200 mesh and introduced into a tube where it could be drawn by reduced pressure onto a teflon or quartz filter held in a stainless steel holder. The carbon-impregnated filter and holder were then placed in the oven under air flow and tested as described in Example 2-2.
A carbon prepared by steam activation of a lignite was stirred with an aqueous solution of poly(vinylpyrrolidone-co-acrylic acid) for 30 min. The amount of the polymer was selected to provide loadings of 1% to 30% by weight. The solvent was evaporated by rotovaping at 50° C. and further dried in an oven at 110° C. The impregnated carbon was reactivated by heating at 750° C. for 2 hours in a stream of nitrogen. Approximately 40% of the polymer weight was converted to surface coating and 60% was volatilized.
An activated carbon was impregnated with poly(vinylpyrrolidone-co-vinyl acetate) dissolved in dichloromethane. The solvent was evaporated and the impregnated carbon died in an oven at 110° C. The impregnated carbon was then activated by heating at 750° C. for 2 hours in a nitrogen stream.
An activated carbon was impregnated with one of poly(vinylpyrrolidone) and the copolymers described in Examples 2-4a to 2-4b and activated as described in Example 2-4a.
A KOH-activated lignite was impregnated with one of polyvinylpyrrolidone and and the copolymers described in Examples 2-4a to 2-4b and activated as described in Example 2-4a.
Wood-derived charcoal was impregnated with one of poly(vinylpyrrolidone) and the copolymers described in Examples 2-4a to 2-4b and activated as described in Example 2-4a.
Chars are produced by carbonization of a lignite, impregnated by one of poly(vinylpyrrolidone) and the copolymers described in Examples 2-4a to 2-4b, and activated as described in Example 2-4a. As an alternative, steam activation can be used.
Examples 2-4a to 2-4b were carried out using steam activation of the carbon material impregnated with nitrogen-containing polymers to generate effective sorbents.
Lignite (as received) was stirred with an aqueous solution of DABCO in a ratio of 1 part of coal to 0.02 parts of DABCO. The water solvent was removed by filtration, and the impregnated coal was air-dried. The dried material was carbonized at 400° C. and activated at 750° C. for 2 hours under a nitrogen stream.
Lignite (as received) was stirred with an aqueous solution of sulfamic acid in a ratio of 1 part of coal to 0.02 parts of sulfamic acid. The water solvent was removed by filtration, and the impregnated coal was air-dried. The dried material was carbonized and activated at 750° C. for 2 hours under a nitrogen stream.
Lignite was carbonized at 400° C. for 30 minutes, and the resulting char was treated by stirring with sulfamic acid solution as described in Example 2-5b. The treated char was then activated as described in Example 2-5b.
Steam activation of the DABCO or sulfamic acid-impregnated chars was also effective in producing mercury sorbent carbons.
Nitrogen-containing pitches were prepared using a procedure reported by Mochida et al. (Mochida, I.; An, K. H.; Korai. Y. Carbon 1995, 33, 1069). Preparations are summarized in Table 2. As an example, a mixture of isoquinoline (26 g, 0.2 mole), anhydrous aluminum(III) chloride (13.3 g, 0.25 mole), and nitrobenzene (7.68 g, 0.06 mole) was placed in a two-necked flask equipped with a reflux condenser and a nitrogen inlet tube. The mixture was refluxed at 280° C. for 4 hours. The residue was extracted with 0.1 N hydrochloric acid and filtered. The residue was washed with 0.1 N hydrochloric acid. The residue was further extracted with methanol to remove any monomer. The methanol-insoluble pitch was dried in vacuo. The yield of the pitch was 49%. A portion of the nitrogen-containing pitches were carbonized using Procedure A or B in a nitrogen stream, as described in Example 2-7.
Several modifications of the method were utilized for the quinoline polymerization. In addition to the flask method, a Parr reactor was used for the reaction, and temperatures and reaction times were varied. The yields are reported in Table 3. In this procedure, 64.5 g of quinoline and 33.25 g of aluminum(III) chloride were placed in a 300-mL Parr autoclave. The reactor was sealed under nitrogen and heated at 280° C. for 4 hours. The hard black mass was extracted with 0.1 N hydrochloric acid followed by extraction with methanol and drying in vacuo. In order to determine the solubility of the polymer, a 10-g portion of this black mass was extracted with 100 mL of ethanol. Extraction data showed that 27 wt % of the product dissolved in ethanol.
Impregnations and recarbonizations were performed to investigate the effects of precursor concentration, activation procedure, and sorbent particle size on mercury sorption. The precursor base carbon, granular activated carbon (Calgon F400 or Gascoyne AC, 20×60) was impregnated with various nitrogen-containing polymers and pitches using an incipient wetness method, described below. For the fine-particle sorbent tests in flue gas compositions, the Calgon carbon was ground to about a 400 mesh size prior to impregnation. The nitrogen polymers such as vinylpyrrolidone polymers and copolymers are commercially available. The urea, alanine-dextrose, piperazine-dextrose, and polyethylenimine-dextrose compositions were prepared similarly.
In a typical procedure for the incipient wetness method, the desired amount of polymer or pitch dissolved in an appropriate solvent was added to the carbon slowly with thorough mixing. The paste was dried to remove solvent. The dried product was packed in a stainless steel tube and activated in a gentle flow of nitrogen using procedure A or procedure B.
Procedure A included: Heated from 25° C. to 400° C. at 10° C./min; held at 400° C. for 30 min; heated from 400° to 750° C. at 20° C./min; and held at 750° C. for 4 hr.
Procedure B included: Heat from 25° C. to 225° C. at 15° C./min; heated from 225° C. 270° C. at 1° C./min; held at 270° C. for 1 hr; cooled to room temperature; heated up to 750° C. at 15° C./min; and held at 750° C. for 4 hr.
Insoluble fractions of pitches described in Table 2 were converted into nitrogen-containing carbons by heating in a gentle flow of nitrogen using Procedure B as described above. The resulting carbons were porous glassy materials, similar to cokes.
Capture of SO3 and subsequent sulfuric acid formation on the surface of the nitrogen containing carbons in the hot flue gas stream was simulated by adding 5 wt % sulfuric acid by the incipient wetness method. The acid-impregnated carbons were dried at 110° C.
Packed-bed tests in airflow were conducted on the granular carbon products to evaluate the effects of surface modification. The mercury sorption was tested in a flow-through tubular reactor system equipped with continuous in-line mercury analysis of the effluent from the bed to determine mercury removal rates as a function of time. Integration of breakthrough volumes allows determination of mercury sorption per unit mass carbon (mg/g). Air with an elemental mercury concentration of 56 or 81 μg/m3 was passed through the heated (150° C.) reactor. To obtain this concentration, the mercury source was placed in a double-jacketed glass condenser and heated to the desired temperature by pumping hot oil through the condenser.
A glass tube with constriction and glass wool plug was used as the reactor for the mercury sorption tests. A gas chromatography (GC) oven was used as a constant temperature (150° C.) chamber for the reactor. Before the actual test, a blank test was run. The glass tube was attached to the source and the mercury analyzer by Teflon tubes. Mercury vapors diluted with air (2000-4000 cm3/min or 4-8 scfh measured at the detector end) were passed through the tube. The mercury analyzer (Environmental and Process Monitoring [EPM] continuous vapor monitor) was interfaced to a Hydra and personal computer (PC) to record the data. For the packed-bed tests, impregnated activated carbons (20×60-mesh size) were used. In an actual test, about 0.2-0.6 g of sorbent was packed in the glass tube and held by glass wool plugs on both ends. The tests were conducted with a source temperature of 150° C., an oven temperature of 150° C., and an airflow=4 or 8 scfh (4000 cm3/min). Numerous tests were performed at 4000 cm3/min (8 scfh) with carbons prepared by impregnation of various nitrogen compounds, polymers, and pitches into a base Calgon carbon (Tables 4 and 5). These conditions gave partial breakthroughs for the sorbents and allowed comparisons of their kinetic activities.
Carbons prepared by impregnation of urea or sulfamic acid into the Calgon base carbon and recarbonization gave initial capture rates of 95% or 92%, respectively. These results are significantly better than those observed with the unmodified Calgon carbon. Testing the urea carbon at lower temperature (75° C.) gave 100% initial capture. Carbons prepared by impregnation of a nitrogen-containing polymer were highly active in these tests. The sorbent prepared by impregnation of 5 wt % PVP and activated using procedure A (fast heating rate) demonstrated superior activity. The initial removal was 94%, and the decrease to 50% removal required 2217 min. Thus this sorbent retains its high activity far longer than the urea carbon. The sorbent prepared using 10% PVP (also Procedure A) was less active (initially 88% removal decreasing to 50% at 150 min.
Using procedure B (slower heating rate) gave more active sorbent at the 10% PVP concentration level. Another set of carbons was prepared with different concentrations using Procedure B. Again, the impregnation with 5% concentration of PVP resulted in high activity (initially 98% removal, decreasing to 50% at 3315 mm). The 10% PVP was again less active, and the 2% PVP concentration was the least active.
The carbons prepared from the copolymers of PVP were also prepared and evaluated. The copolymer with vinyl acetate (PVPcoVA) impregnated at 5% concentration (Procedure A) gave a sorbent with relatively low activity. The poly(vinylpyrrolidone-co-acrylic acid) (PVPc0AA) at 5% also gave a low activity sorbent. Using Procedure B for activation improved the activity slightly.
Another type of N-polymer-impregnated carbon was prepared using polyethylenimine. This polymer precursor contains nitrogen in the polymer backbone, in contrast to the PVP where the nitrogen is attached to the carbon chain backbone. The activity was similar to that of the 10% PVP polymers.
Several carbons were prepared by impregnating mixtures of dextrose and amines. None of these exhibited high activities in these tests. Previous tests showed that the dextrose+alanine-impregnated carbon (Procedure B) was fairly active. Since Procedure A was used in the present study, decreases in activity might be related to the fast heating rate used. It may be quite beneficial to perform the reaction slowly in preparing sorbents from these precursors.
The sorbents prepared by impregnation of the nitrogenous pitches prepared by polymerization of various heterocyclics were all fairly active (Table 5), but significant differences in activity were observed. The N-carbon prepared from impregnation of quinoxaline pitch was 2-3 times more active than the quinoline-derived N-carbon. The activity of the isoquinoline-derived carbon was also very high. The high activity of the indole-derived carbon was also of great interest. It is an important lead since indoles are more readily available than the quinoxaline precursors.
Testing was also conducted on the carbonized pitches prepared from the insoluble fractions of the nitrogenous pitches. The activities of the carbonized pitches were very poor. Initial breakthrough was substantial, with percent removals of 21% to 54%, possibly related to the glassy nature of the carbonized pitches. Although the surface areas were not determined, they may be very low, since the materials did not resemble activated carbons but, rather, cokes.
Part III. Promoted Ammonium Salt-Protected Sorbent.
Tests were conducted on a full-scale 550 Mw plant equipped with an ESP for particulate control and that burns a low-sulfur coal for SO2 compliance. SO3 ash conditioning was used to assist the ESP in controlling opacity and particulate matter (PM) stack emissions. During the test, SO3 was injected upstream of the ESP in the range of 0-20 ppmv. The addition of SO3 to the flue gas has been previously shown to significantly negatively impact mercury capture efficiency. All tests were conducted at full load.
During the test, a halogen promoter (NaBr, to form HBr) was injected into the furnace along with three different sorbents included activated carbon and additional components to protect mercury binding sites. These sorbents were injected upstream of the air heaters. Sorbent 1 was approximately 75% activated carbon and 25% clay material (bentonite, as described in U.S. Pat. No. 8,652,235 B2). Sorbent 2 was approximately 75% activated carbon and 25% hydrated lime (per U.S. Pat. No. 7,435,286 B). Sorbent 3 included approximately 75% activated carbon and 25% ammonium sulfate. The activated carbon component had a mean size of approximately 14-18 microns. Each of the other three components (clay, alkali, and ammonium salt) had a mean size of approximately 4-9 microns. The halogen promoter was injected with rates in the range of 0.0-0.7 lb/Macf (million actual cubic feet) and the sorbents were injected in the range of 0-7 lb/Macf. Each sorbent was tested separately along with the halogen promoter.
Typical results are illustrated in
Data from similar tests show that injecting similar quantities of other alkali and ammonium along with activated carbon show improved mercury capture. This indicates that synergy occurs that improves performance when adding (or co-injecting) two materials together.
Tests were conducted on a full-scale 150 Mw plant equipped with an ESP for particulate control. During the test, the plant burned a blended coal with a sulfur content of approximately 2%. High sulfur coals produce flue gas contaminants (sulfur species, SO2, SO3, etc.) that significantly impact mercury capture efficiency. SO2 emissions of 1200-1600 ppm were measured at the stack and SO3 concentrations of 15-25 ppm were measured in the flue gas at the point of sorbent injection. All tests were conducted at full load.
During the test, a halide promoter (NaBr, to form HBr) was injected into the furnace along with three different sorbents including activated carbon and additional components to protect mercury binding sites. These sorbents were injected upstream of the air heaters, with limited distance and residence time between the air heaters and ESP inlet. Sorbent 1 was approximately 75% activated carbon and 25% clay material (bentonite, as described in U.S. Pat. No. 8,652,235 B2). Sorbent 2 was approximately 75% activated carbon and 25% hydrated lime (per U.S. Pat. No. 7,435,286 B2. Sorbent 3 was approximately 75% activated carbon and 25% ammonium salts (ammonium sulfate specifically). The activated carbon and added components had a mean size of approximately 6-9 microns. Larger sized sorbents were tested, but were shown to be not as effective. The halogen promoter was injected at rates in the range of 0.0-4.0 lb/Macf (million actual cubic feet) and the sorbents were injected in the range of 0-20 lb/Macf. Each sorbent was tested separately along with the halogen promoter with results discussed below.
Typical results are illustrated in
While the addition of optional components such as alkali and ammonium convincingly assist in protecting binding sites, they cannot totally eliminate the impact of contaminant flue gas components (e.g., sulfur species such as SO2 and SO3) that are generated when combusting a high sulfur coal. Data from similar tests show that injecting similar quantities of other alkali and ammonium along with activated carbon show improved mercury capture. This indicates that synergy occurs that improves performance when adding (or co-injecting) two materials together.
The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present invention.
The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:
Embodiment 1 provides a method for separating mercury from a mercury-containing gas stream, the method comprising:
contacting a mercury-containing gas stream with an activated carbon sorbent comprising promoted ammonium salt-protected activated carbon sorbent particles, to form a mercury-sorbent composition; and
separating at least some of the mercury-sorbent composition from the mercury-containing gas stream, to give a separated gas.
Embodiment 2 provides the method of Embodiment 1, further comprising combusting coal to form the mercury-containing gas stream.
Embodiment 3 provides the method of any one of Embodiments 1-2, wherein the mercury-containing gas stream comprises a concentration of sulfur(VI) that is about 1 ppm-2000 ppm.
Embodiment 4 provides the method of any one of Embodiments 1-3, wherein the activated carbon sorbent combines with about 0.001 wt % to about 100 wt % of mercury in the mercury-containing gas stream to form the mercury-sorbent composition.
Embodiment 5 provides the method of any one of Embodiments 1-4, wherein the activated carbon sorbent combines with at least about 70 wt % of mercury in the mercury-containing gas stream to form the mercury-sorbent composition.
Embodiment 6 provides the method of any one of Embodiments 1-5, wherein the activated carbon sorbent is in a fixed bed, in a moving bed, in a scrubber, in a filter, suspended in the mercury-containing gas stream, or a combination thereof.
Embodiment 7 provides the method of any one of Embodiments 1-6, further comprising injecting a sorbent into the mercury-containing gas stream, wherein
the injected sorbent is the activated carbon sorbent comprising the promoted ammonium salt-protected activated carbon sorbent particles,
the injected sorbent is a precursor of the activated carbon sorbent comprising the promoted ammonium salt-protected activated carbon sorbent particles with halide-promotion, ammonium salt-protection, or a combination thereof, occurring after the injection of the precursor, or
a combination thereof.
Embodiment 8 provides the method of Embodiment 7, wherein the injected sorbent is the activated carbon sorbent comprising the promoted ammonium salt-protected activated carbon sorbent particles.
Embodiment 9 provides the method of any one of Embodiments 7-8, wherein the precursor is a promoted non-ammonium salt-protected activated carbon sorbent, wherein the ammonium salt-protection occurs after injection of the precursor into the mercury-containing gas stream.
Embodiment 10 provides the method of any one of Embodiments 7-9, wherein the precursor is an ammonium salt-protected non-promoted activated carbon sorbent, wherein the halide-promotion occurs after injection of the precursor into the mercury-containing gas stream.
Embodiment 11 provides the method of any one of Embodiments 7-10, wherein the precursor is a non-promoted non-ammonium salt-protected activated carbon sorbent, wherein halide-promotion and ammonium salt-protection occurs after injection of the precursor in the mercury-containing gas stream.
Embodiment 12 provides the method of any one of Embodiments 1-11, wherein the activated carbon sorbent comprises an alkaline component selected from the group consisting of alkali elements, alkaline earth elements, alkali salts, alkaline earth salts, and combinations thereof.
Embodiment 13 provides the method of any one of Embodiments 1-12, wherein the activated carbon sorbent comprises a mercury-stabilizing reagent selected from the group consisting of S, Se, H2S, SO2, H2Se, SeO2, CS2, P2S5, and combinations thereof.
Embodiment 14 provides the method of any one of Embodiments 1-13, wherein the activated carbon sorbent further comprises a substrate comprising at least one of diatomaceous earth, a clay, a zeolite, or a mineral.
Embodiment 15 provides the method of Embodiment 14, wherein the activated carbon sorbent comprises a product of subjecting a mixture comprising a carbonaceous material and the substrate to heating, microwaving, irradiating, or a combination thereof, comprises a material derived from the product via one or more of halide-promotion and ammonium salt-protection, or a combination thereof.
Embodiment 16 provides the method of Embodiment 15, wherein the heating comprises heating to about 100° C. to about 1200° C.
Embodiment 17 provides the method of any one of Embodiments 15-16, wherein the heating of the mixture comprising the carbonaceous material and the substrate to form the product thereof is performed prior to contacting the activated sorbent and the mercury-containing gas stream.
Embodiment 18 provides the method of any one of Embodiments 1-17, wherein the activated carbon sorbent comprises a carbon nanocomposite sorbent.
Embodiment 19 provides the method of any one of Embodiments 1-18, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise promoted ammonium salt-protected powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, or a combination thereof.
Embodiment 20 provides the method of Embodiment 19, wherein the promoted ammonium salt-protected powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, or a combination thereof have a particle size of about 0.1 μm to about 1000 μm.
Embodiment 21 provides the method of any one of Embodiments 19-20, wherein the promoted ammonium salt-protected powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, or a combination thereof have a particle size of about 0.1 μm to about 30 μm.
Embodiment 22 provides the method of any one of Embodiments 1-21, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise a product of subjecting a mixture comprising a carbonaceous material and a nitrogenous material to heating, microwaving, irradiating, or a combination thereof, comprise a material derived from the product via one or more of halide-promotion and ammonium salt-protection, or a combination thereof.
Embodiment 23 provides the method of Embodiment 22, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise a product of acid or base treatment of the product of subjecting a mixture comprising a carbonaceous material and a nitrogenous material to heating, microwaving, irradiating, or a combination thereof.
Embodiment 24 provides the method of any one of Embodiments 22-23, wherein the carbonaceous material comprises powdered activated carbon, granular activated carbon, carbon black, carbon fiber, aerogel carbon, pyrolysis char, brown sugar, barley sugar, caramel, cane sugar, corn syrup, starch, molasses, a glucan, a galactan, a xylan, a sugar waste product, or a combination thereof.
Embodiment 25 provides the method of any one of Embodiments 22-24, wherein the nitrogenous material comprises a nitrogen-containing organic or inorganic material.
Embodiment 26 provides the method of Embodiment 25, wherein the nitrogenous material comprises a nitrogen heterocycle, a nitrogen-containing polymer or copolymer, a nitrile, a carbamate, an amino acid, nitrobenzene, hydroxylamine, urea, hydrazine, sulfamic acid, an ammonium salt, or a combination thereof.
Embodiment 27 provides the method of any one of Embodiments 25-26, wherein the nitrogenous material comprises indole, quinoxaline, carbazole, isoquinoline, nitrobenzene, urea, sulfamic acid, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, vinylpyrrolidone-acrylic acid copolymer, vinylpyrrolidone-maleic acid copolymer, polyethylenimine, alanine, piperazine, quinolone, quinoxaline, diazabicyclooctane, an amino acid, an ammonium salt, or a combination thereof.
Embodiment 28 provides the method of any one of Embodiments 1-27, wherein the promoted ammonium salt-protected activated carbon comprises a halide, a hydrogen halide, or a combination thereof.
Embodiment 29 provides the method of Embodiment 28, wherein the halide, hydrogen halide, or combination thereof is about 0.001 wt % to about 30 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 30 provides the method of any one of Embodiments 28-29, wherein the halide, hydrogen halide, or combination thereof is about 1 wt % to about 15 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 31 provides the method of any one of Embodiments 1-30, wherein the promoted ammonium salt-protected activated carbon comprises ammonia, the ammonium salt, or a combination thereof.
Embodiment 32 provides the method of Embodiment 31, wherein the ammonia, the ammonium salt, or the combination thereof, is about 0.001 wt % to about 30 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 33 provides the method of any one of Embodiments 31-32, wherein the ammonia, the ammonium salt, or the combination thereof, is about 0.01 wt % to about 15 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 34 provides the method of any one of Embodiments 1-33, wherein the promoted ammonium salt-protected activated carbon comprises an anionic counterion of the ammonium salt.
Embodiment 35 provides the method of Embodiment 34, wherein the anionic counterion of the ammonium salt is about 0.001 wt % to about 30 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 36 provides the method of any one of Embodiments 34-35, wherein the anionic counterion of the ammonium salt is about 0.01 wt % to about 15 wt % of the promoted ammonium salt-protected activated carbon.
Embodiment 37 provides the method of any one of Embodiments 1-36, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise nitrogen atoms in at least a surface layer thereof.
Embodiment 38 provides the method of Embodiment 37, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles is a continuous surface layer.
Embodiment 39 provides the method of any one of Embodiments 37-38, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles has a thickness of about 0.001% to about 99% of a radius of the particles.
Embodiment 40 provides the method of any one of Embodiments 37-39, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles has a thickness of about 0.001% to about 50% of a radius of the particles.
Embodiment 41 provides the method of any one of Embodiments 37-40, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles comprises about 0.001 wt % to about 99 wt % nitrogen.
Embodiment 42 provides the method of any one of Embodiments 37-41, wherein the promoted ammonium salt-protected activated carbon sorbent particles have an overall nitrogen atom concentration of about 0.001 wt % to about 50 wt %.
Embodiment 43 provides the method of any one of Embodiments 37-42, wherein a concentration of nitrogen atoms in the surface layer is greater than a concentration of nitrogen atoms in a core of the promoted ammonium salt-protected activated carbon sorbent particles.
Embodiment 44 provides the method of Embodiment 43, wherein the core of the promoted ammonium salt-protected activated carbon sorbent particles comprises about 0 wt % to about 99 wt % nitrogen atoms.
Embodiment 45 provides the method of any one of Embodiments 43-44, wherein the core of the promoted ammonium salt-protected activated carbon sorbent particles comprises about 1 wt % to about 6 wt % nitrogen atoms.
Embodiment 46 provides the method of any one of Embodiments 43-45, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles comprises about 0.001 wt % to about 99 wt % nitrogen atoms.
Embodiment 47 provides the method of any one of Embodiments 43-46, wherein the surface layer of the promoted ammonium salt-protected activated carbon sorbent particles comprises about 5 wt % to about 80 wt % nitrogen atoms.
Embodiment 48 provides the method of any one of Embodiments 37-47, wherein nitrogen atoms are substantially homogeneously distributed throughout the promoted ammonium salt-protected activated carbon sorbent particles.
Embodiment 49 provides the method of any one of Embodiments 37-48, wherein the nitrogen in the surface layer decreases neutralization of carbocations in the promoted ammonium salt-protected activated carbon sorbent particles by at least one of SO3, H2SO4, and HSO41−, as compared to corresponding promoted ammonium salt-protected activated carbon sorbent particles comprising less or substantially no nitrogen in a corresponding particle surface layer.
Embodiment 50 provides the method of any one of Embodiments 37-49, wherein the nitrogen in the surface layer at least partially blocks carbocations in the promoted ammonium salt-protected activated carbon sorbent particles from at least one of SO3, H2SO4, and HSO4−1, as compared to a corresponding promoted ammonium salt-protected activated carbon sorbent particles comprising less or substantially no nitrogen in a corresponding particle surface layer.
Embodiment 51 provides the method of any one of Embodiments 37-50, wherein the mercury-containing gas stream further comprises a concentration of sulfur(VI) that is greater than about 0 ppm by mole and the activated carbon sorbent forms a mercury-sorbent composition at a higher absorption rate relative to a corresponding activated carbon sorbent comprising less or substantially no ammonium salt-protection.
Embodiment 52 provides the method of any one of Embodiments 1-51, wherein the mercury-containing gas stream further comprises a concentration of sulfur(VI) that is greater than about 0 ppm by mole and the activated carbon sorbent forms a mercury-sorbent composition at a higher absorption rate relative to a corresponding activated carbon sorbent comprising at least one of
a) less or substantially no halide- or halogen-promotion, wherein the activated carbon sorbent comprising the activated carbon sorbent particles is halide- or halogen-promoted, and
b) less or substantially no ammonium salt-protection.
Embodiment 53 provides the method of any one of Embodiments 1-52, wherein the promoted ammonium salt-protected activated carbon sorbent particles have a particle size of about 0.1 μm to about 1000 μm.
Embodiment 54 provides the method of any one of Embodiments 1-53, wherein the promoted ammonium salt-protected activated carbon sorbent particles have a particle size of about 0.1 μm to about 10 μm.
Embodiment 55 provides the method of any one of Embodiments 1-54, wherein the promoted ammonium salt-protected activated carbon sorbent particles are promoted prior to addition to the mercury-containing gas stream.
Embodiment 56 provides the method of any one of Embodiments 1-55, further comprising promoting precursor activated carbon sorbent particles with a promoter to form promoted activated carbon sorbent particles.
Embodiment 57 provides the method of Embodiment 56, wherein promoting precursor activated carbon sorbent particles with the promoter comprises chemically reacting carbene species edge sites in the activated carbon sorbent particles with the promoter.
Embodiment 58 provides the method of any one of Embodiments 56-57, wherein promoting precursor activated carbon sorbent particles with the promoter comprises subjecting a mixture comprising the precursor activated carbon sorbent particles and the promoter to heating, microwaving, irradiating, or a combination thereof.
Embodiment 59 provides the method of any one of Embodiments 56-58, wherein during the promoting the promoter is substantially in vapor or gaseous form.
Embodiment 60 provides the method of any one of Embodiments 56-59, wherein the promoting of the precursor activated carbon sorbent particles occurs in-flight in the mercury-containing gas stream.
Embodiment 61 provides the method of any one of Embodiments 56-60, wherein the promoting of the precursor activated carbon sorbent particles occurs prior to addition of the activated carbon sorbent particles to the mercury-containing gas stream.
Embodiment 62 provides the method of any one of Embodiments 56-61, further comprising combusting coal that comprises the promoter, a promoter precursor, or a combination thereof.
Embodiment 63 provides the method of Embodiment 62, wherein the promoter precursor transforms into the promoter which then reacts with a precursor activated carbon sorbent to give a promoted activated carbon sorbent.
Embodiment 64 provides the method of any one of Embodiments 62-63, further comprising adding the promoter, promoter precursor, or a combination thereof, to the coal prior to the combustion thereof.
Embodiment 65 provides the method of Embodiment 64, wherein the promoter, promoter precursor, or a combination thereof, is added to the coal in an organic solvent.
Embodiment 66 provides the method of Embodiment 65, wherein the organic solvent is a hydrocarbon, a chlorinated hydrocarbon, supercritical carbon dioxide, or a combination thereof.
Embodiment 67 provides the method of any one of Embodiments 56-66, wherein the promoting occurs in an aqueous scrubber, wherein the scrubber comprises an aqueous slurry that comprises the promoter.
Embodiment 68 provides the method of any one of Embodiments 56-67, further comprising injecting into the mercury-containing gas stream the promoter, a promoter precursor, or a combination thereof.
Embodiment 69 provides the method of Embodiment 68, wherein the promoter, promoter precursor, or a combination thereof, is added together with the precursor activated carbon sorbent particles into the mercury-containing gas stream.
Embodiment 70 provides the method of any one of Embodiments 68-69, wherein the promoter, promoter precursor, or a combination thereof, is added into the mercury-containing gas stream separately from addition of the precursor activated carbon sorbent particles into the mercury-containing gas stream.
Embodiment 71 provides the method of any one of Embodiments 56-70, wherein the promoter is HCl, HBr, HI, Br2, Cl2, I2, BrCl, IBr, ICl, ClF, PBr3, PCl5, SCl2, CuCl2, CuBr2, Al2Br6, FeIx (x=1, 2, 3, or 4), FeBry (y=1, 2, 3, or 4), FeClz (z=1, 2, 3, or 4), MnBr2, MnCl2, NiBr2, NiCl2, NiI2, ZnBr2, ZnCl2, ZnI2, NHBr, NH4Cl, NH4I, NH4F, or a combination thereof.
Embodiment 72 provides the method of any one of Embodiments 56-71, wherein the promoter is HBr.
Embodiment 73 provides the method of any one of Embodiments 56-72, further comprising forming the promoter from a promoter precursor.
Embodiment 74 provides the method of Embodiment 73, wherein the promoter precursor is an elemental halogen, a Group V halide, a Group VI halide, a hydrohalide, an ammonium halide, a metal halide, a nonmetal halide, an alkali earth metal halide, an alkaline earth metal halide, or a combination thereof.
Embodiment 75 provides the method of any one of Embodiments 73-74, wherein the promoter precursor is NaBr, NaCl, NaI, Br−, Cl−, I−, KI, KCl, LiCl, LiBr, CuCl2, CuBr2, AgCl, AgBr, CHI3, CH3Br, AuBr, FeIx (x=1, 2, 3, or 4), FeBry (y=1, 2, 3, or 4), FeClz (z=1, 2, 3, or 4), MgBr2, MgCl2, MnBr2, MnCl2, NiBr2, NiCl2, NiI2, ZnBr2, ZnCl2, ZnI2, CaI2, CaBr2, CaCl2, or a combination thereof.
Embodiment 76 provides the method of any one of Embodiments 73-75, wherein the promoter precursor has a particle size of about 0.1 μm to about 1000 μm.
Embodiment 77 provides the method of any one of Embodiments 1-76, further comprising protecting promoted activated carbon sorbent particles with an ammonium salt, to form the promoted ammonium salt-protected activated carbon sorbent particles.
Embodiment 78 provides the method of Embodiment 77, wherein protecting promoted activated carbon sorbent particles with the ammonium salt comprises subjecting a mixture comprising the promoted activated carbon sorbent particles and the ammonium salt to heating, microwaving, irradiating, or a combination thereof.
Embodiment 79 provides the method of Embodiment 78, wherein the mixture comprising the promoted activated carbon sorbent particles and the ammonium salt has a ratio of the promoted activated carbon sorbent particles to the ammonium salt of about 1:100 to about 100:1.
Embodiment 80 provides the method of any one of Embodiments 78-79, wherein the mixture comprising the promoted activated carbon sorbent particles and the ammonium salt has a ratio of the promoted activated carbon sorbent particles to the ammonium salt of about 1:1 to about 1:5.
Embodiment 81 provides the method of any one of Embodiments 1-80, wherein the promoted ammonium salt-protected activated carbon sorbent particles are ammonium salt-protected prior to addition to the mercury-containing gas stream.
Embodiment 82 provides the method of any one of Embodiments 77-81, wherein the ammonium salt-protection of the promoted activated carbon sorbent particles or of precursor activated carbon sorbent particles occurs in-flight in the mercury-containing gas stream.
Embodiment 83 provides the method of any one of Embodiments 77-82, wherein the ammonium salt-protection of the promoted activated carbon sorbent particles or of precursor activated carbon sorbent particles occurs prior to addition of the promoted activated carbon sorbent particles to the mercury-containing gas stream.
Embodiment 84 provides the method of any one of Embodiments 77-83, further comprising combusting coal that comprises the ammonium salt.
Embodiment 85 provides the method of any one of Embodiments 77-84, further comprising injecting into the mercury-containing gas stream the ammonium salt.
Embodiment 86 provides the method of Embodiment 85, wherein the ammonium salt is added together with the promoted activated carbon sorbent particles or precursor activated carbon sorbent particles into the mercury-containing gas stream.
Embodiment 87 provides the method of any one of Embodiments 85-86, wherein the ammonium salt is added into the mercury-containing gas stream separately from addition of the promoted activated carbon sorbent particles or precursor activated carbon sorbent particles into the mercury-containing gas stream.
Embodiment 88 provides the method of any one of Embodiments 77-87, wherein the ammonium salt is an ammonium halide, a methylammonium halide, an ammonium salt of an oxyacid of a Group VI element, an ammonium salt of an oxyacid of a Group V element, or a combination thereof.
Embodiment 89 provides the method of any one of Embodiments 77-88, wherein the ammonium salt is ammonium bromide, ammonium iodide, ammonium chloride, an organic halide with a formula of CH3NH3X (wherein X is Cl, Br or I), ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, ammonium persulfate, ammonium pyrosulfate, ammonium thiosulphate, ammonium dithionite, ammonium aluminium sulfate, ammonium iron sulfate, ammonium sulfamate, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium thiophosate, ammonium nitrate, ammonium nitrite, ammonium carbonate, ammonium thiocyanate, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium chlorate, ammonium chromate, ammonium fluoride, ammonium formate, ammonium hydroxide, ammonium perchlorate, or a combination thereof.
Embodiment 90 provides the method of any one of Embodiments 77-89, wherein the ammonium salt is ammonium sulfate.
Embodiment 91 provides the method of any one of Embodiments 77-90, wherein the ammonium salt has a particle size of about 0.1 μm to about 1000 μm.
Embodiment 92 provides the method of any one of Embodiments 77-91, wherein the ammonium salt has a particle size of about 0.1 μm to about 10 μm.
Embodiment 93 provides the method of any one of Embodiments 1-92, wherein contacting the mercury-containing gas stream with the activated carbon sorbent comprising promoted ammonium salt-protected activated carbon sorbent particles to form the mercury-sorbent composition comprises chemically reacting the mercury in the mercury-containing gas stream with the promoted ammonium salt-protected activated carbon sorbent.
Embodiment 94 provides the method of any one of Embodiments 1-93, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise active sites, wherein the active sites comprise halide anions bound to the sorbent particles.
Embodiment 95 provides the method of any one of Embodiments 1-94, wherein the promoted ammonium salt-protected activated carbon sorbent particles comprise active sites, wherein the active sites comprise carbocations bound to halide anions.
Embodiment 96 provides the method of any one of Embodiments 1-95, wherein carbocations in the promoted ammonium salt-protected activated carbon sorbent particles accept electrons from mercury atoms of the mercury-sorbent particulate.
Embodiment 97 provides the method of any one of Embodiments 1-96, wherein in the promoted ammonium salt-protected activated carbon sorbent particles ammonia or an anionic ammonium counterion derived from the ammonium salt intercepts SO2, SO3, NOx, selenates, or a combination thereof, in the mercury-containing gas stream, preventing reaction thereof with active carbon sites in the promoted ammonium salt-protected activated carbon.
Embodiment 98 provides the method of any one of Embodiments 1-97, wherein ammonia or an anionic ammonium counterion derived from the ammonium salt intercepts SO3 in the mercury-containing gas stream, preventing reaction thereof with active carbon sites in the promoted ammonium salt-protected activated carbon.
Embodiment 99 provides the method of any one of Embodiments 1-98, wherein the separating at least some of the mercury-sorbent composition from the mercury-containing gas stream comprises separating in a particulate separator.
Embodiment 100 provides the method of Embodiment 99, wherein the particulate separator comprises an electrostatic precipitator (ESP), a baghouse, a wet scrubber, a filter, cyclone, fabric separator, or any combination thereof.
Embodiment 101 provides the method of any one of Embodiments 1-100, further comprising regenerating the mercury-sorbent composition to give a regenerated activated carbon sorbent.
Embodiment 102 provides the method of any one of Embodiments 1-101, wherein the contacting, the separating, or a combination thereof, occurs in an aqueous scrubber.
Embodiment 103 provides the method of Embodiment 102, wherein the scrubber comprises an aqueous slurry that comprises the activated carbon sorbent.
Embodiment 104 provides a method for separating mercury from a mercury-containing gas stream, the method comprising:
Embodiment 105 provides ammonium salt-protected activated carbon sorbent particles comprising
Embodiment 106 provides the ammonium salt-protected activated carbon sorbent particles of Embodiment 105, wherein the ammonium salt-protected activated carbon sorbent particles are promoted ammonium salt-protected activated carbon sorbent particles comprising active sites that bind with mercury atoms, wherein the active sites comprise carbocations bound to promoter anions.
Embodiment 107 provides the ammonium salt-protected activated carbon sorbent particles of any one of Embodiments 105-106, wherein the promoted ammonium salt-protected activated carbon sorbent particles further comprise an anionic counterion.
Embodiment 108 provides the ammonium salt-protected activated carbon sorbent particles of any one of Embodiments 106-107, wherein the anionic counterion is derived from the ammonium salt.
Embodiment 109 provides a method of making the ammonium salt-protected activated carbon particles of any one of Embodiments 105-108, the method comprising:
Embodiment 110 provides the method of Embodiment 109, wherein the precursor activated carbon sorbent is a promoted activated carbon sorbent.
Embodiment 111 provides the method of any one of Embodiments 109-110, further comprising promoting an activated carbon with a promoter to provide the precursor activated carbon sorbent.
Embodiment 112 provides a method for separating mercury from a mercury-containing gas stream, the method comprising:
Embodiment 113 provides the method of Embodiment 112, wherein the ammonia or a precursor thereof is injected into the mercury-containing gas stream.
Embodiment 114 provides the method or sorbent of any one or any combination of Embodiments 1-113 optionally configured such that all elements or options recited are available to use or select from.
This application is a continuation-in-part of and claims the benefit of priority under 35 U.S.C. § 120 to U.S. patent application Ser. No. 14/712,558, filed on May 14, 2015, which is a continuation of U.S. patent application Ser. No. 13/966,768, filed on Aug. 14, 2013 (now U.S. Pat. No. 8,821,819), which is a continuation of U.S. patent application Ser. No. 13/427,665, filed on Mar. 22, 2012 (now U.S. Pat. No. 8,512,655), which is a continuation of U.S. patent application Ser. No. 12/419,219, filed on Apr. 6, 2009 (now U.S. Pat. No. 8,168,147), which is a continuation of U.S. patent application Ser. No. 12/201,595, filed on Aug. 29, 2008, which is a division of U.S. patent application Ser. No. 11/209,163, filed on Aug. 22, 2005 (now U.S. Pat. No. 7,435,286), which claims the benefit of priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 60/605,640, filed on Aug. 30, 2004, the disclosures of which are incorporated herein in their entirety by reference. This application is also a continuation-in-part of and claims the benefit of priority under 35 U.S.C. § 120 to U.S. Utility application Ser. No. 14/195,360, filed Mar. 3, 2014, which claims the benefit of priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application Ser. No. 61/773,549, filed Mar. 6, 2013, the disclosures of which are incorporated herein in their entirety by reference.
This invention was made with U.S. Government support under grant numbers R 827649-01 and CR 830929-01 awarded by the U.S. Environmental Protection Agency and under Contract Number DE-FC26-98FT40320. The U.S. Government has certain rights in this invention.
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| Number | Date | Country | |
|---|---|---|---|
| 20170100692 A1 | Apr 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61773549 | Mar 2013 | US | |
| 60605640 | Aug 2004 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11209163 | Aug 2005 | US |
| Child | 12201595 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13966768 | Aug 2013 | US |
| Child | 14712558 | US | |
| Parent | 13427665 | Mar 2012 | US |
| Child | 13966768 | US | |
| Parent | 12419219 | Apr 2009 | US |
| Child | 13427665 | US | |
| Parent | 12201595 | Aug 2008 | US |
| Child | 12419219 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14195360 | Mar 2014 | US |
| Child | 15382114 | US | |
| Parent | 14712558 | May 2015 | US |
| Child | 14195360 | US |
