WO2014138572A1

WO2014138572A1 - Use of ferrous sulfide suspension for the removal of mercury from flue gases

Info

Publication number: WO2014138572A1
Application number: PCT/US2014/021714
Authority: WO
Inventors: Thomas P. Mccullough; Gary Joel Meyer; Ralph E. Roper; Anthony J. Kriech
Original assignee: Heritage Research Group
Priority date: 2013-03-07
Filing date: 2014-03-07
Publication date: 2014-09-12
Also published as: DE112014001129B4; KR102164080B1; CN105188888B; JP6486840B2; CN105188888A; GB2526239A; DE112014001129T5; CA2904381A1; GB2526239B; CA2904381C; GB201517093D0; KR20160004264A; JP2016515044A; ZA201507347B

Abstract

A ferrous sulfide suspension that includes at least FeSm and Al(OH)₃ and which can be used to reduce mercury emissions in flue gases. Through a combination of complex chemical reactions, precipitation, co-precipitation, and surface adsorption the ferrous sulfide suspension of the present invention effectively removes mercury from gaseous streams while concurrently preventing mercury re-emission.

Description

USE OF FERROUS SULFIDE SUSPENSION FOR THE REMOVAL OF MERCURY FROM FLUE GASES

BACKGROUND

[0001] The present invention relates generally to remediation of pollutants in flue gases. More specific embodiments of the present invention relate to a wet gas scrubbing liquor which comprises an alkaline ferrous sulfide suspension for the treatment and removal of mercury from flue gases, and methods of using the wet gas scrubbing liquor to remove mercury from flue gases. The present invention further relates to methods for producing the ferrous sulfide suspension and methods.

[0002] The emission of pollutants from coal-fired boilers is a major environmental concern. In particular, the emission of mercury into the atmosphere from these sources has garnered increased attention as a threat to human health and the environment since mercury, even at low concentrations, is a neurotoxin. Mercury is contained in varying concentrations in different coal sources and therefore the total quantity of mercury emitted into the atmosphere from the combustion of coal varies significantly between facilities.

[0003] During combustion of the coal, mercury is released in flue gases in the form of elemental mercury (Hg°). As the combustion gases cool, a portion of the mercury transforms to ionic or oxidized mercury (Hg²⁺) in the gas stream. As a result, there are three possible forms of mercury in the gas stream that may be emitted to the atmosphere - elemental (Hg°), ionic or oxidized (Hg²⁺), or mercury that is bound onto particulates or fly ash also contained in the gas stream (Hg_(p)).

[0004] The conversion of elemental mercury (Hg°) to the other forms of mercury is dependent upon several factors, including but not limited to, the cooling rate of the gas stream, the presence of halogens or sulfurous species (e.g. chlorines, bromines, S0₃ ^2"), the amount and composition of fly ash, the presence of unburned carbon, and the removal efficiency of any installed air pollution control equipment. Considering the complex interaction of these various parameters, the form of mercury ultimately released to the atmosphere varies between 10% and 90%, 5% and 15%, and 10% and 90% of the total mercury for elemental, ionic, and particle bound species, respectively.

[0005] Mercury and other pollutants may be captured and removed from flue gas streams by injection of a dry sorbent into the exhaust stream with subsequent collection in a particulate matter control device such as an electrostatic precipitator or a fabric filter. These systems are collectively referred to as "dry scrubber" systems. Of the known dry sorbents for mercury removal, activated carbon and calcium-based sorbents have been the most actively studied and most widely used on commercially.

[0006] Mercury and other pollutants may be captured and removed from the gas stream by injection of a dry sorbent into the exhaust stream with subsequent collection in a particulate matter control device such as an electrostatic precipitator or a fabric filter. Systems based on dry sorbent technologies are collectively referred to as "dry scrubber" systems. Of the known dry sorbents for mercury removal, activated carbon and calcium- based sorbents have been the most actively studied and most widely used on a commercial scale.

[0007] Currently, the most commonly used sorbent in dry scrubber systems for mercury emission reduction is the injection of powdered activated carbon (PAC) into the flue gas stream of coal-fired and oil-fired plants. Although powdered activated carbon (PAC) is effective in capturing ionic or oxidized mercury species (Hg⁺²), powdered activated carbon is not as effective for the removal of elemental mercury (Hg°) which may constitute a significant percentage of the mercury species in flue gases, especially from facilities that use subbituminous coals and lignite fuel sources. There have been efforts to enhance the trapping efficiency of elemental mercury (Hg°) in these systems by incorporating or impregnating the PAC with a bromine species.

[0008] Examples of other sorbents that have been used for mercury removal in dry scrubber systems include those disclosed in U.S. Patent Application Publication No. 2003/0103882 to Biermann et al and in U.S. Patent No. 6,719,828 to Lovell et al. which discloses the preparation of layered sorbents such as clays with metal sulfides interlayered between the clay layers. Other patents for mercury capture by injection of dry sorbents are based upon preparation of the sorbents by thinly layering a chemical compound onto or into a substrate. These types of sorbents use substrates that include sol-gel derivatives as disclosed in U.S. Patent Nos. 7,790,830 to Edmiston; 8,119,759 to Edmiston; and 8,217,131 to Edmiston, self-assembled monolayers on mesoporous supports as disclosed in U.S. Patent Nos. 8,088,283 to Pate; 8,412,664 to Shankle; and 8,197,687 to Krogue et al, phyllosilicates as disclosed in U.S. Patent No. 7,288,499 to Lovell et al., or variety of other substrates. In addition to these U.S. Patent Nos. 7,575,629 to Yang et al. and 7,704,920 to Yang et al. disclose that any metal salt that can release a metal ion when the salt contacts a sulfide salt forming a water insoluble metal sulfide on the substrate surface can be used to produce an effective dry sorbent for mercury removal.

[0009] The production and use of these sorbent dry scrubbers for the removal of mercury from flue gases are complex and expensive.

[0010] Another type of scrubber system that is used to reduce the emission of mercury and other toxic gaseous pollutants to the environment are commonly referred to as "wet scrubbers". In a wet scrubber system, polluted gases are brought into contact with a scrubbing liquid, either by spraying the gases with the liquid, by forcing the gases through a pool of liquid, or by some other contact method, so as to capture and remove pollutants. The liquid compositions used in these wet scrubbers vary depending upon the pollutant targeted for removal. For example, in a wet flue gas desulfurization device (WFGD) used to remove acid gases such as sulfur dioxide (S0₂), a sorbent slurry containing limestone (CaC0₃), oxides or hydroxides of calcium or magnesium, or other mixtures are primarily used.

[0011] Elemental mercury is fairly insoluble in water (approximately 50 μg/L).

Hence, elemental mercury is not effectively removed in wet scrubber systems. Therefore, processes upstream of wet scrubbers that oxidize Hg° in flue gases to Hg²⁺ will improve the effectiveness of overall mercury removal by the downstream wet scrubber systems.

[0012] Since gas phase oxidation is kinetically limited, the need to oxidize any Hg° to Hg²⁺, keep any Hg²⁺ from being reduced back to Hg° (sometimes referred to as

"reconversion" or "re-emission") and then finally capturing the Hg²⁺ in the wet scrubber process is essential for mercury removal.

[0013] Reactions with other ionic species in the gas stream and scrubber liquid also may have a significant impact on the ability of wet scrubber systems to remove Hg²⁺ and the extent reconversion of Hg²⁺ to Hg°. In "Role of Sulfides in the Sequestration of Mercury by Wet Scrubbers," B. Ghorishi et al. as presented at the EPRI-DOE-EPA- AWMA Combined Power Plant Air Pollutant Control Mega Symposium August 28-31, 2006 in Baltimore, Maryland, the authors proposed that once Hg²⁺ dissolves and ionizes in solution, it may be subject to reactions with other dissolved constituents in the scrubber slurry. In the case of impurities such as divalent iron (Fe²⁺), the authors theorized that the reduction of Hg²⁺ to Hg° may occur by the following reaction:

2Fe²⁺ + Hg²⁺→ Hg° + 2Fe³⁺ (1 )

[0014] Further, in the presence of an aqueous sulfide ions, ionic or oxidized mercury (Hg²⁺) precipitates as HgS and effectively sequesters the Hg²⁺ as an insoluble solid according to the following reaction:

HS^" + Hg²⁺ HgS| + H⁺ (2)

[0015] Since reactions (1) and (2) occur simultaneously in wet scrubber systems, the amount of Hg° subject to re-emission (reconversion) becomes a "race between the mercury reduction reactions" and the precipitation of Hg²⁺ as HgS. At Fe²⁺

concentrations of less than 1300 ppm in the scrubber liquor, all of the Hg is in the form of HgS and thus no Hg° re-emission occurs. At higher Fe²⁺ concentrations (more than 1300ppm) and higher pH (> 4), any mercury has a higher tendency to be re-emitted as Hg°.

[0016] Based on the above research, U.S. Patent Nos. 6,284,199 to Downs et al, 6,503,470 to Nolan et al. and 6,855,859 to Nolan et al, each disclose methods to minimize the potential of this re-emission (reconversion) of the ionic or oxidized mercury (Hg²⁺) at the gas/liquid interface before it can be reduced by transition metals that may be present as impurities in the scrubber liquid.

[0017] Various means for supplying an aqueous source of sulfide ions to react with the oxidized mercury at the gas/liquid interface in the wet scrubber for the absorption and precipitation of ionized (oxidized) mercury include injecting a mixture of air and hydrogen sulfide (U.S. Patent No. 6,284,199 to Downs et al.) or from addition of aqueous sulfide species into the scrubber liquid that are selected from sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide and sodium sulfide. To further inhibit the reconversion of Hg²⁺ to Hg°, U.S. Patent No. 6,855,859 to Nolan et al.

discloses an additional step whereby an oxidizing agent is first added to the scrubber liquid to convert any Hg° present to Hg²⁺ in the flue gas prior to treatment of the Hg²⁺ with an aqueous sulfide ion. [0018] The known prior art related to mercury removal mechanisms by wet scrubbers systems rely upon absorption of ionic or oxidized mercury (Hg²⁺) by an aqueous sulfide ion. In these cases, absorption is a phenomenon whereby atoms, molecules, or ions that are present in the gas stream are absorbed (taken up) by the volume of the bulk (liquid) phase. On the other hand, "adsorption" is a physical phenomenon where atoms, ions, or molecules from a gas, liquid, or dissolved solid adhere (bind) to another solid surface. The exact nature of the bonding by adsorption is dependent upon the species involved, but the adsorption process is generally classified as physisorption (characteristic of weak van der Waals forces), chemisorption (characteristic of covalent bonding), or some other type of electrostatic attraction. In other words, absorption is the process through which a substance, originally present in one phase, is removed from that phase by dissolution into another phase (typically a liquid), as opposed adsorption which is the accumulation of atoms, ions, or molecules from a bulk liquid or gas onto a solid surface.

[0019] Since the environment in a wet scrubber system is dynamic, removal of mercury from the flue gas stream is complex. Any successful mercury removal methodology must account for the various equilibrium conditions present between the mercury in the flue gas stream, and the other various ions, chemical complexes, or chemical compounds also contained within the flue gas entering the wet scrubber.

[0020] Once the flue gas containing mercury and the other various ions, chemical complexes, or chemical compounds enters the wet scrubber, the successful removal of the mercury from the flue gas stream is predicated on concurrently controlling the equilibrium conditions that are a result of interactions between the mercury containing flue gas and the solid, liquid, and gaseous phases present (or created) in the wet scrubber.

[0021] The present invention overcomes the disadvantage of using sorbents in dry scrubbers which are primarily based on adsorption of mercury onto the sorbent and the disadvantage of wet scrubber systems which are based upon the absorption of mercury by aqueous sulfide ions in the scrubber liquid to form an insoluble mercuric sulfide precipitant. BRIEF SUMMARY

[0022] According to various features, characteristics and embodiments of the present invention which will become apparent as the description thereof proceeds, the present invention provides a reagent for removal of mercury from industrial gases containing elemental and oxidized mercury which reagent comprises a ferrous sulfide suspension that is produced by the steps of:

a) reacting any aqueous solution, including but not limited to, a caustic byproduct that contains at least NaA10₂ and NaOH with any aqueous solution, including but not limited to, a pickle liquor that contains FeCl₂, HCl and water to form a reaction mixture that contains Al³⁺, Fe²⁺, CI^", Na⁺, CI^" and H₂0; and

b) adding a sulfide source, including but not limited to, NaHS to the reaction mixture of step a) to form a ferrous sulfide suspension that contains at least FeS and Al(OH)₃.

[0023] The present invention further provides a method of reducing mercury emissions from an industrial gas containing elemental and oxidized mercury in a wet scrubber system containing an aqueous ferrous sulfide suspension which method comprises:

a) creating a gas-liquid interface within the scrubber and contacting the industrial gas with the ferrous sulfide suspension containing aluminum hydroxide so as to cause at least one of:

i) adsorption of the oxidized or ionic mercury from the industrial gas onto the surface of ferrous sulfide or aluminum hydroxide in the ferrous sulfide suspension containing aluminum hydroxide;

ii) adsorption of the oxidized or ionic mercury onto iron (hydr)-oxides that may be initially present or created as reaction products in the suspension ferrous sulfide suspension containing aluminum hydroxide; and

iii) precipitation of the oxidized or ionic mercury at a gas-liquid interface as a mercuric sulfide; and

b) thereby reduce mercury emissions from an industrial gas

[0024] The present invention further provides a wet scrubber liquid composition for use in a wet gas scrubber which wet scrubber liquid that produced by the steps of: a) reacting a solution that contains at least NaA102 and NaOH with a pickle liquor that contains FeC12, HCl and water to form a reaction mixture that contains Fe2+, C1-, NaCl and H20; and

b) adding NaHS to the reaction mixture of step a) to form a ferrous sulfide suspension that contains at least FeS and Al(OH)3.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be described with reference to the attached drawings which are given as non-limiting examples only, in which:

[0026] Figures la and lb represent a "single cell" and a "sheet" of FeS, respectively.

[0027] Figures 2a and 2b represent a "single cell" and a "sheet" of metacinnabar (β- HgS), respectively.

[0028] Figure 3 is a general is a diagram of a process for removing mercury from a flue gas according to one embodiment of the present invention.

[0029] Figure 4 is schematic diagram of a coal-fired boiler having dual wet FGD scrubber systems.

DETAILED DESCRIPTION OF THE DRAWINGS AND THE PRESENTLY PREFERRED EMBODIMENTS

[0030] According to one embodiment the present invention provides a ferrous sulfide suspension containing aluminum hydroxide, a method for producing the ferrous sulfide suspension containing aluminum hydroxide, and methods for using the ferrous sulfide suspension containing aluminum hydroxide for the treatment and removal of mercury from flue gases.

[0031] The alkaline ferrous sulfide suspension can be used as a wet scrubbing liquor for flue gases (or "wet gas scrubbing liquor") generated by coal-fired or oil-fired boilers.

[0032] According to one embodiment the alkaline ferrous sulfide suspension can be produced by combining together a ferrous ion source (e.g. FeC12), a sulfide ion source (e.g. NaHS), and an alkalinity source (e.g. NaOH). According to another embodiment the alkaline ferrous sulfide suspension further includes aluminum hydroxide.

According to further embodiments of the present invention the molar ratio of the ferrous ion source, sulfide ion source, and alkalinity source can be controlled/adjusted during the scrubbing of a flue gas so as to control/adjust the concentration of the insoluble ferrous sulfide (FeS).

[0033] The ferrous sulfide suspensions of the present invention is a minimally soluble, colloidal suspension that can be used to enhance the total mercury removal capabilities of wet FGD scrubber systems, including but not limited to venturi scrubbers, spray scrubbers, cyclone spray chambers, orifice scrubbers, impingement scrubbers, packed bed scrubbers, etc.

[0034] Through a combination of complex chemical reactions, precipitation, co- precipitation, and surface adsorption the ferrous sulfide suspension containing aluminum hydroxide of the present invention can effectively remove mercury from gaseous streams while concurrently preventing mercury re-emission. Mercury re-emission occurs across a wet FGD when oxidized (or ionic) mercury converts back to its elemental form and subsequently returns to the process stream, increasing total mercury in stack emissions.

[0035] During the course of the present invention the inventors surprisingly discovered that a liquid suspension containing minimally soluble ferrous sulfide (FeS) containing aluminum hydroxide can efficiently and economically remove Hg²⁺ by both absorption and adsorption mechanism while simultaneously minimizing any reconversion of Hg²⁺ to Hg⁰.

[0036] Though the combination of various molar ratios of a ferrous ion source (e.g. FeCl₂), an aluminum ion source (e.g. Al(OH)₃, NaA10₂), a sulfide ion source (e.g. NaHS), and an alkalinity source (e.g. NaOH), the resulting alkaline liquid suspension containing FeS and aluminum hydroxide particles provides an economical and efficient wet scrubber liquid suitable for mercury removal from gas streams.

[0037] Since these combinations of various molar ratios of a ferrous ions, aluminum ions, sulfide ions, and an alkalinity source result in an alkaline liquid suspension containing different proportions of aforementioned ions in equilibrium with any FeS and aluminum hydroxide particles thus formed, the dominant or primary mechanism(s) controlling mercury removal from the flue gases may be different based on the desired specific formulation produced. Therefore, the discussion below of the dominant or primary mechanism(s) believed to control the mercury removal from the flue gases below should in no way be considered as limiting.

[0038] In the present invention, ferrous sulfide, sometimes referred to as

"mackinawite", "disordered mackinawite", "amorphous ferrous sulfide" is formed which disassociates by the following reaction:

FeS <→ Fe²⁺ + S^2" (3)

[0039] Depending upon the environment in which the ferrous sulfide is formed, the solubility product (Ksp) will be between 1 x l CT³ and 1 x 1 CT⁵. Since this is many orders of magnitude higher than the solubility product of HgS (Ksp = 3 x lCf ⁵²), in the presence of Hg²⁺ that is present (or formed) in a wet scrubber system, the formation HgS is favored and rapid. By providing the sulfide ion in the form of a minimally soluble ferrous sulfide solid particle, only the stoichiometric amount of sulfide will enter the wet scrubber liquid that is necessary to precipitate any Hg²⁺ and other metals, if any that form metal sulfide precipitates.

[0040] One advantage of the present invention as compared to the prior art, is the possibility of "over" or "under" dosing the required amount of sulfide necessary to precipitate the Hg²⁺ is reduced.

[0041] Concurrent with the equilibrium mechanism controlling the concentration of sulfides released into the scrubber liquid, the same equilibrium mechanism also contributes in controlling the concentration of Fe²⁺ ions in the scrubber liquid.

[0042] In accordance with reaction (3) above, since each mole of sulfide ion released (required) into the scrubber liquid one mole of Fe²⁺ is also released, the Fe²⁺

concentration is contemporaneously controlled and, especially in the presence high oxygen flue gas concentrations, the potential reduction of any Hg²⁺ to (Hg°) is reduced in accordance with reaction (1) above.

[0043] Figure la and lb represent a "single cell" and a "sheet" of FeS, respectively. In these figures it is noted that each iron ion is "four-way" coordinated to each sulfur ion.

[0044] Figures 2a and 2b represent a "single cell" and a "sheet" of metacinnabar (β- HgS), respectively. In these figures it is noted that similar to FeS, each mercury ion is "four-way" coordinated to the sulfur ions. [0045] Although the two structures in Figs, la, lb and 2a, 2b are very similar, the key difference is that FeS forms into sheets while the metacinnabar (β-HgS) tends to "bulk precipitate" and does not form into "sheets".

[0046] Mercury reacts with and dissolves FeS during the formation of metacinnabar (β-HgS).

[0047] Thus, another advantage of the present invention is that in addition to the removal of aqueous Hg²⁺ by its combination with aqueous sulfide ions to form and insoluble HgS precipitate through absorption, the present invention also promotes removal of Hg²⁺ through adsorption to the FeS particle surface.

[0048] In "Sorption of Mercuric Ion by Synthetic Nanocrystalline Mackinawite (FeS)", Hoon Y. Jeong, et. al, Environ. Sci. Technol. 2007 (41), 7699-7705, the authors concluded that in addition to absorption, an adsorption mechanism also contributes to the removal of Hg²⁺ from aqueous solutions.

[0049] The removal mechanisms are dependent on the relative concentrations of Hg²⁺ and FeS. When the molar ratio of [Hg²⁺]/[FeS] is as low as 0.05, adsorption is mainly responsible for Hg²⁺ removal. As the molar ratio increases, the adsorption capacity becomes saturated and results in precipitation of HgS. Concurrently with HgS precipitation, the released Fe²⁺ from FeS is resorbed by an adsorption mechanism in the acidic pH range and either adsorption or precipitation as iron (hydr)-oxides at neutral to basic pHs. Subsequently, the iron (hydr)-oxides precipitates formed at neutral to basic pHs may also serve as an adsorbent for Hg²⁺.

[0050] Therefore, the proposed mechanisms for binding Hg²⁺ to FeS are believed to involve precipitation as metacinnabar (β-HgS) and Hg²⁺ adsorption to the FeS surface (≡FeS) by the following reactions:

FeS_(s) + Hg²⁺→ P-HgS + Fe²⁺ (4) ≡FeS + Hg²⁺ <→≡FeS-Hg²⁺ (5)

[0051] As used herein, adsorption is meant to encompass all processes responsible for Hg²⁺ accumulation at the solid-liquid interface, including but not limited to surface complexation (at low surface coverage) and surface precipitation (at high surface coverage).

[0052] The present invention provides for the ability to adjust the molar ratios of the ferrous ion source, sulfide ion source, and alkalinity source so as to optimize the mercury removal efficiency of the scrubber liquid on a real-time, continuous basis. The ability to adjust the concentration of insoluble FeS in suspension, the ability to produce scrubber solutions with specified concentrations of ferrous ions (or sulfide ions) by adjusting the stoichiometry of the feedstocks, pH, or combinations of both offers unique flexibility to wet flue gas scrubber operators.

[0053] In addition to the proposed aforementioned mechanisms for removal of mercury from flue gas streams by iron sulfides in wet scrubbers, the presence of aluminum oxides or hydroxides (e.g. amorphous Al(OH)_3(s) , gibbsite, bayerite) are also effective in removing mercury from flue gases in wet scrubber systems.

[0054] According to one embodiment of the present invention the ferrous sulfide suspension may be produced from a caustic byproduct of an aluminum anodizing facility. According to this method in an aluminum anodizing facility solid aluminum is washed in a NaOH bath as follows:

2A1_(S) + 2NaOH +2H₂0 <→ 2NaA10₂ + 3H_2(g) (6)

[0055] Eventually the bath becomes saturated with NaA10₂ at which point aluminum hydroxide (Al(OH)₃) precipitates in accordance with the reaction:

2NaA10₂ + 4H₂0 <→ 2Al(OH)_3(s) + 2NaOH (7)

[0056] Prior to this second reaction occurring and fouling the system the anodizing bath is sent for recycling. For purposes of the present invention the caustic byproduct is a saturated mixture of NaA10₂, NaOH and possibly Al(OH)_3(s).

[0057] Pickle liquor (primarily a mixture of FeCl₂, HC1 and water) is mixed with the requisite amount of the caustic byproduct to achieve a final pH of about 8:

[Fe²⁺ + 2C1^"] + [H⁺ + CI^"] + [Na⁺ + Al³⁺ +20₂ ^"] + 2[Na⁺ + OH^"] + [H⁺ + OH^"] <→

Fe²⁺ + CI^" + Al(OH)_3(s) + 3NaCl + 20H^" (8)

[0058] In the resulting mixture Al(OH)_3(s) precipitate as amorphous Al(OH)₃, gibbsite, or bayerite; the "NaCl" forms as a result of the "strong acid/strong base reaction", and the ferrous ion (Fe²⁺) is predominately in solution.

[0059] Sodium hydrosulfide (NaHS) is added to the resulting mixture. Although there are an infinite number of possibilities, the present inventors believe that a variation of the reaction below is most likely. The amount of aqueous of solid products formed is dependent upon the initial stoichiometric amounts of the reactants and the final pH:

Fe²⁺ + CI^" + Al(OH)_3(s) + 3NaCl + 20H^" + [Na⁺ + If +S^2"] <→ FeS_(s) + Al(OH)_3(s) + 4NaCl + H₂0 + OH^"

[0060] Since the solubility of NaCl is high (360g/L), the sodium and chloride ions are most likely in the aqueous phase. Upon drying, the NaCl will precipitate as halite (NaCl). The "aluminum hydroxide" fraction is in the form of a precipitate (e.g. amorphous Al(OH)_3(s) , gibbsite, bayerite). As stated previously, the FeS_(s) formed is sometimes referred to as "mackinawite", "disordered mackinawite", "amorphous ferrous sulfide". Depending upon the stoichiometric amounts of NaHS added there may be excess aqueous sulfide (S^2") or ferrous iron (Fe²⁺).

[0061] The concentration of any individual solid phase is dependent upon numerous environmental factors (e.g. pH, temperature, other ions present, etc.). With respect to the "aluminum hydroxide phase" as it relates to the present invention, since the operating pH of most wet scrubbers is between 5 and 7, any aluminum hydroxide will be as solid particles given the low solubility product (Ksp approximately 1 xlCf ⁷ and 1 x lCf ⁸)

[0062] In "EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I.

Effects of pH", Christopher S. Kim, et. al, Journal of Colloid and Interface Science 271 (2004), 1-15, and "EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: II. Effects of Chloride and Sulfate", Christopher S. Kim, et. al, Journal of Colloid and Interface Science 270 (2004), 9-20, Hg²⁺ adsorbs strongly as a corner-sharing bidentate, and edge-sharing bidentate complexes to the Al(0,OH)₆ octahedra that compose the bayerite structure. This adsorption of Hg²⁺ is both inhibited and promoted in the presence of chloride and sulfate ions which are present in typical wet scrubber systems

[0063] The authors noted that in the presence of bayerite and chloride concentrations (CI^" >10^"3) and at a pH of 6, the portion of aqueousHg²⁺ not sorbed to the bayerite surface facilitated reduction of the aqueous Hg²⁺ to Hg⁺ and the formation of Hg₂Cl_2(S) (calomel) or Hg₂Cl_2(aq) species. With respect to the present invention, this formation of Hg₂Cl_2(s) or Hg₂Cl_2(aq) species may benefit the overall removal efficiency in a wet scrubber by slowing

2_|_ 2^_i~

or prohibiting the complete reduction of Hg to Hg^ ' by Fe in accordance with equation (l) or (4).

[0064] Further, the authors noted that bayerite in the presence of sulfate ions (S0₄ ^2"), enhanced Hg²⁺ sorption surface coverage. They postulated that is effect may be due to the sorption or accumulation of sulfate ions at the bayerite surface by effectively reducing the positive surface charge that electrostatically inhibits Hg²⁺ sorption. [0065] In summary, the FeS portion in the ferrous sulfide suspension promotes the formation of HgS_(s) either by dissolution and/or the re-precipitation as HgS, or via binding of the Hg²⁺ with the sulfhydryl groups on the FeS surface (e.g.,≡FeS-Hg). Once this occurs, oxidation and dissolution reactions of the iron sulfides and mercury sulfides are significantly reduced. With respect to the bayerite, sulfate ions tend to promote direct Hg²⁺ adsorption/accumulation at bayerite surfaces. Although chlorides tend to reduce surface uptake of Hg²⁺ to bayerite, the formation of Hg₂Cl_2(S) in the aqueous phase is overall beneficial by minimizing the complete reduction of Hg²⁺ to Hg° and the potential for mercury re-emission.

[0066] Figure 1 is a general diagram of a process for removing mercury from a flu gas according to one embodiment of the present invention. As depicted in Fig. 1 a source of ferrous ions (e.g. FeCl₂) 4, a source of sulfide ions (e.g. NaHS) 5, and an alkalinity source (e.g. NaOH) 6 are combined together to produce an alkaline liquid suspension of ferrous sulfide particles. The alkaline liquid suspension of ferrous sulfide particles is used as a wet scrubber liquor in a wet gas scrubber 1 through which a flue gas stream 2 is passed to produce a cleaned gas stream 3.

[0067] The process depicted in Fig. 1 allows for control/adjustment of the molar ratio of the ferrous ion source, sulfide ion source, and alkalinity source during processing so as to allow for real time control/adjustment of the concentration of the insoluble ferrous sulfide (FeS) in the wet scrubbing liquor.

[0068] The present invention will be discussed with reference to the following non- limiting examples which are to be considered merely representative of the present invention and, thus, should not be considered as limiting.

Example 1

[0069] In this example a ferrous sulfide suspension was tested at a facility with a 250 MW pulverized coal boiler burning bituminous coal. The boiler utilized an SCR to control NO_x, a baghouse to remove particulate, and a wet flue gas desulfurization (FGD) unit for S0₂ emission control. The test setup is shown in Figure 3. Each scrubber had a working volume of approximately 30,000 gallons.

[0070] At the start of this example 60 gallons of the ferrous sulfide suspension was pumped into the discharge of each pump. The pumps supplied the ferrous sulfide

suspension into each scrubber system at a rate of 6gpm, so that it took approximate 10 minutes to get the 60 gallons into each scrubber system at the outlet of each side's recycle pump.

[0071] Within 5 minutes after the ferrous sulfide suspension was introduced into the scrubber towers, the total Hg trend dropped significantly from the Hg CEMS. The

injection was then stopped for 2 hours after the initial charge of 60 gallons of ferrous sulfide suspension was pumped into the scrubber systems.

[0072] After the initial charge of the ferrous sulfide suspension tests were performed on a maintenance charge. The stack Hg level dropped below the baseline (1.3 lb/TBtu on average) value and settled at ~0.1 μg/dscm during the two hour window after the initial charge. When the Hg reading was observed to increase back to 50% of the baseline, a maintenance charge was started by the injection of the ferrous sulfide suspension at the lowest pumping rate of approximately 0.7 gpm through the pumps. The ferrous sulfide suspension maintenance injection lasted for 5 hours until the suspension was exhausted.

Three runs of stack Hg testing which applied the EPA reference Method 30B were

performed between 10:45 and 13 :20, the testing results have been summarized in Table 1 below.

Table 1

Ferrous Sulfide Suspension Application Stack Hg Testing Results

Date Run Unit Hg in Ferrous FGD M-P M-P M-P M-P M-P Hg Re- Overall

# Load Coal Sulfide pH North North Oxidation Stack Stack Emission Hg

2013 Blend Suspension FGD FGD FGD HgO HgT Removal

[0073] As indicated in Table 1 , the baseline stack Hg (T) with no flue gas treatment averaged ~1.3 lb/TBtu; the Hg re-emission was determined to be 57.1% (the Hg (0) portion increased by 57.1% on average across the scrubber) and the overall Hg (T) removal efficiency was averaged at 79.1%.

[0074] During the ferrous sulfide suspension injection, the three runs of Method 30B were averaged at 0.46 lb/TBtu for the stack Hg(T), the Hg Re-emission column showed three negative numbers (-28.7%, -81.5% and -84.0%) which indicated that the Hg re- emission issue across the scrubber was completely eliminated, and the overall Hg(T) removal efficiency was determined to improve by 13% at 92.3% on average.

Example 2

[0075] In this example various amounts of the ferrous sulfide suspension were injected into the same 250 MW pulverized coal boiler burning bituminous coal used in Example 1.

[0076] Initial baseline mercury testing was as follows:

[0077] On July 11 , 2013, the overall Hg removal efficiency was 76.5%. Although the native Hg oxidation at the FGD inlet was 88.7%, test results showed a substantial increase (56%) in HgO across the wet FGD attributed to mercury re-emission. [0078] On July 25, 2013, the overall Hg removal efficiency was 75.0% and the native Hg oxidization at the wet FGD inlet was 98.3%. Test results again showed a substantial increase (1 ,200%) in mercury re-emission across the wet FGD.

[0079] Finally, on November 1 1 , 2013, the overall Hg removal efficiency was 87.8%, the native Hg oxidization at the wet FGD inlet was 97.0%. HgO increased by 239%.

[0080] The significant increase in Hg° attributed to mercury re-emission across the wet FGD prevented the unit from achieving a mercury emission level adequate to demonstrate compliance with the upcoming MATS regulatory limit of 1.20 lb/TBtu at baseline operating conditions.

[0081] On November 12, 2013 series of injections of the ferrous sulfide suspension were performed for parametric testing. The objective of the testing was two-fold; first, to determine whether the ferrous sulfide suspension injection could stabilize Hg° through the wet FGD, and second, to estimate the required minimum injection rate of the ferrous sulfide suspension to provide steady-state control of stack Hg.

[0082] The target injections rates of the ferrous sulfide suspension used in this example were 40, 20, 10, and 5 gallons per hour (gph) into each of the two FGD scrubber modules. At each injection rate and after steady state conditions were achieved (~1.5 hours after initiating injection). The testing took three measurements of Hg in accordance with EPA Method 30B.

[0083] On November 12, 2013 the ferrous sulfide suspension was injected at a rate of 40 gph/scrubber. Overall Hg removal efficiency was 95.1%. Total mercury decreased from 10.99 lb/TBtu to 0.59 lb/TBtu, and the Hg° fraction decreased from 0.90 lb/TBtu to 0.40 lb/TBtu. Results indicated the injection of the ferrous sulfide suspension successfully resolved the mercury re-emission issue and brought mercury emission levels within the MATS compliance limit of 1.2 lb/TBtu at the stack.

[0084] On November 19, 2013 the ferrous sulfide suspension was injected at a rate to 20 gph/scrubber. The overall Hg removal efficiency was 96.1%, and the total mercury decreased from 9.6 lb/TBtu to 0.46 lb/TBtu. The Hg° fraction decreased from 1.08 lb/TBtu to 0.30 lb/TBtu. Again, the ferrous sulfide suspension injection brought emissions levels within MATS compliance at 20 gph.

[0085] To determine if MATS compliance could be achievable with an even lower dosage the ferrous sulfide suspension was injected at a rate of 10 gph/scrubber during the November 19 testing. At this injection rate, overall Hg removal efficiency was 97.3%, total mercury decreased from 8.55 lb/TBtu to 0.33 lb/TBtu, and the Hg° fraction decreased from 0.93 lb/TBtu to 0.23 lb/TBtu. The injection of the ferrous sulfide suspension continued to demonstrate MATS compliance at the 10-gph rate.

[0086] On November 20 the ferrous sulfide suspension was injected at a rate to 5 gph/scrubber to establish an optimal rate for achieving compliance. The overall Hg removal efficiency was 95.8%, total mercury decreased from 9.88 lb/TBtu to 0.50 lb/TBtu, and the Hg° fraction decreased from 0.84 lb/TBtu to 0.31 lb/TBtu. Even at this low injection rate the ferrous sulfide suspension success-fully brought the boiler stack emissions within the MATS compliance limits of <1.2 lb/TBtu.

[0087] The results of the tests performed in this example are presented in Table 2 below.

Table 2

Summary of Testing of Ferrous Sulfide Suspension at Different Injection Rates

Stack System 2013 Coal Amount HgO HgT % Hg HgO HgT % Hg %

B= lb/TBtu GPH lb/TBtu lb/TBtu Oxidation lb/TBtu lb/TBtu Re- Overall

Baseline emission Hg

P= Removal

Parametric

7/1 1 B 6 0 0.68 3.13 88.7 1.06 1.41 56 76.5

7/25 B 9 0 0.15 5.91 98.3 1.95 2.25 1200 75.0

11/11 B 12 0 0.36 6.72 97.0 1.21 1.46 239 87.8

11/12 P 12 40 0.90 10.99 92.5 0.40 0.59 0 95.1

11/19 P 12 20 1.08 9.60 91.0 0.30 0.46 0 96.2

11/19 P 12 10 0.93 8.55 92.3 0.23 0.33 0 97.3

11/20 P 12 5 0.83 9.88 93.0 0.31 0.50 0 95.8

[0088] From these tests it can be observed that even at the lowest injection rate of 5 gph the ferrous sulfide suspension appeared to stabilize oxidized mercury with no apparent increase of elemental mercury across the wet FGD.

[0089] In addition the ferrous sulfide suspension injection improved mercury removal efficiency of the overall system and reduced the total stack mercury to approximately 60% lower than the MATS limit of 1.2 lb/TBtu.

[0090] These results indicate further reduction of the ferrous sulfide suspension injection rates may also be achievable with long-term, continuous injections. [0091] The results of these tests demonstrate that the ferrous sulfide suspension has the capacity to provide a cost-effective method for reducing mercury stack emissions and achieving compliance with up-coming USEPA MATS limits at coal-fired facilities. [0092] Although the present invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention and various changes and modifications can be made to adapt the various uses and characteristics without departing from the spirit and scope of the present invention as described above and set forth in the attached claims.

Claims

1. A reagent for removal of mercury from industrial gases containing elemental and oxidized mercury which reagent comprises a ferrous sulfide suspension that is produced by the steps of: a) reacting a solution that contains at least NaA10₂ and NaOH with a pickle liquor that contains FeCl₂, HC1 and water to form a reaction mixture that contains Fe²⁺, CI^", NaCl and H₂0; and b) adding NaHS to the reaction mixture of step a) to form a ferrous sulfide suspension that contains at least FeS and Al(OH)₃.

2. A reagent for removal of mercury from industrial gas containing elemental and oxidized mercury according to claim I, the solution that contains at least NaA10₂ and NaOH reacted in step a) comprises a caustic NaOH bath used for washing solid aluminum.

3. A reagent for removal of mercury from industrial gas containing elemental and oxidized mercury according to claim I, wherein the reaction mixture of step a) has a pH of about 8.

4. A reagent for removal of mercury from industrial gas containing elemental and oxidized mercury according to claim 1 , wherein the Al(OH)₃ comprises any combination of gibbsite, bayerite, or amorphous aluminum hydroxides.

5. A reagent for removal of mercury from industrial gas containing elemental and oxidized mercury according to claim I, wherein the FeS comprises of any combination of "mackinawite", "disordered mackinawite", or "amorphous ferrous sulfide".

6. A method of reducing mercury emissions from an industrial gas containing elemental and oxidized mercury in a wet scrubber system containing an aqueous ferrous sulfide suspension which method comprises: a) creating a gas-liquid interface within the scrubber and contacting the industrial gas with the ferrous sulfide suspension so as to cause at least one of: i) adsorption of the oxidized or ionic mercury from the industrial gas onto the surface of ferrous sulfide in the ferrous sulfide suspension; ii) adsorption of the oxidized or ionic mercury onto iron (hydr)-oxides; and iii) precipitation of the oxidized or ionic mercury at a gas-liquid interface as a mercuric sulfide; and b) thereby reduce mercury emissions from an industrial gas.

7. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the industrial gas comprises a flue gas.

8. The method of reducing mercury emissions from an industrial gas according to claim 7, wherein the industrial gas comprises a flue gas from a coal-fired furnace or boiler.

9. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the ferrous sulfide suspension is caustic.

10. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the ferrous sulfide suspension comprises at least FeS and Al(OH)₃.

11. The method of reducing mercury emissions from an industrial gas according to claim 10, wherein the Al(OH)₃ comprises gibbsite, bayerite, or amorphous aluminum hydroxides.

12. The method of reducing mercury emissions from an industrial gas according to claim 10, wherein the FeS comprises mackinawite, "disordered

mackinawite", or "amorphous ferrous sulfide."

13. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the ferrous sulfide suspension is made by combining a ferrous ion source, a sulfide ion source and an alkalinity source the amount of which one or more is controlled so as to control a ratio of ionic mercury to ferrous sulfide in the ferrous sulfide suspension.

14. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the ferrous sulfide suspension inhibits reconversion of ionic or oxidized mercury to elemental mercury.

15. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the scrubber system comprises a wet flue gas

desulfurization device.

16. The method of reducing mercury emissions from an industrial gas according to claim 6, wherein the wet flue gas desulfurization device comprises a venturi scrubber, a spray scrubber, a cyclone spray chamber, an orifice scrubber, an impingement scrubber or a packed bed scrubber.

17. A wet scrubber liquid composition for use in a wet gas scrubber which wet scrubber liquid that produced by the steps of: a) reacting a solution that contains at least NaA10₂ and NaOH with a pickle liquor that contains FeCl₂, HC1 and water to form a reaction mixture that contains Fe²⁺, CI^", NaCl and H₂0; and b) adding NaHS to the reaction mixture of step a) to form a ferrous sulfide suspension that contains at least FeS and Al(OH)₃.

18. A wet scrubber liquid composition for use in a wet gas scrubber which wet scrubber liquid according to claim 17, wherein the reaction mixture of step a) has a pH of about 8.

19. A wet scrubber liquid composition for use in a wet gas scrubber which wet scrubber liquid according to claim 17, wherein the Al(OH)₃ comprises any combination of gibbsite, bayerite, or amorphous aluminum hydroxides.

20. A wet scrubber liquid composition for use in a wet gas scrubber which wet scrubber liquid according to claim 17, wherein the FeS comprises of any combination of "mackinawite", "disordered mackinawite", or "amorphous ferrous sulfide".