WO2006096993A1

WO2006096993A1 - Removal of hg, nox and sox using oxidants and staged gas/liquid contact

Info

Publication number: WO2006096993A1
Application number: PCT/CA2006/000407
Authority: WO
Inventors: Dennis W. Johnson
Original assignee: Airborne Industrial Minerals Inc.
Priority date: 2005-03-17
Filing date: 2006-03-15
Publication date: 2006-09-21
Also published as: US20050214187A1; EP1901832A1; CA2646013A1; US20100068110A1; US8242324B2; US7628967B2; EP1901832A4

Abstract

A method of scrubbing mercury compounds and nitrogen oxides from a gas stream employing a scrubbing operation. The method involves the contact of the stream which contains mercury, SOx and NOx compounds with a sorbent to remove at least a portion of the latter compounds. This results in a partially cleaned stream. The method further involves contacting the latter stream with an oxidant to oxidize and remove substantially all residual nitrogen oxides, mercury and mercury compounds remaining in the stream.

Description

REMOVAL OF Hg, NO_x, AND SO_x USING OXIDANTS AND STAGED GAS/LIQUID CONTACT

[0001] This application claims priority to U.S. Patent Application Serial No. 11/081,612, filed March 17, 2005.

FIELD OF THE INVENTION

[0002] The present invention relates to removal of SO_x and NO_x and mercury with oxidants, and more particularly, the present invention relates to removal of SO_x, NO_x, and Hg with staged gas/liquid contact.

BACKGROUND OF THE INVENTION

[0003] In the pollution control field, several approaches are used to remove sulfur oxides and other contaminants from a flue gas produced by the burning of a fossil fuel in order to comply with Federal and State emissions requirements. One approach involves locating and utilizing fossil fuels lower in sulfur content and/or other contaminants. A second approach involves removing or reducing the sulfur content and/or other contaminants in the fuel, prior to combustion, via mechanical and/or chemical processes. A major disadvantage to the second approach is the limited cost effectiveness of the mechanical and/or chemical processing required to achieve the mandated reduction levels of sulfur oxides and/or other contaminants .

[0004] By and large, the most widely used approaches to removing sulfur oxides and/or other contaminants from flue gas involve post-combustion clean up of the flue gas. Several methods have been developed to remove the SO₂ species from flue gases .

[0005] A first method for removing SO₂ from flue gas involves either mixing dry alkali material with the fuel prior to combustion, or injection of pulverized alkali material directly into the hot combustion gases to remove sulfur oxides and other contaminants

U:\AllStaffλcaldwell\Scan-l .doc via absorption or absorption followed by oxidation. Major disadvantages of this first method include: fouling of heat transfer surfaces (which then requires more frequent soot blowing of these heat transfer surfaces), low to moderate removal efficiencies, poor reagent utilization, and increased particulate loading in the combustion gases which may require additional conditioning (i.e. humidification or sulfur trioxide injection) of the gas if an electrostatic precipitator is used for downstream particulate collection.

[0006] A second method for removing SO₂ from flue gas, collectively referred to as wet chemical absorption processes and also known as wet scrubbing, involves "washing" the hot flue gases with an aqueous alkaline solution or slurry in a gas-liquid contact device to remove sulfur oxides and other contaminants. Major disadvantages associated with these wet scrubbing processes include: the loss of liquid both to the atmosphere (i.e., due to saturation of the flue gas and mist carry-over) and to the sludge produced in the process; and the economics associated with the construction materials for the absorber module itself and all related auxiliary downstream equipment (i.e., primary/secondary dewatering and waste water treatment subsystems) . A typical wet scrubbing system is shown in Figure 1.

[0007] A third method, collectively referred to as spray drying chemical absorption processes and also known as dry scrubbing, involves spraying an aqueous alkaline solution or slurry which has been finely atomized via mechanical, dual-fluid or rotary type atomizers, into the hot flue gases to remove sulfur oxides and other contaminants. Major disadvantages associated with these dry scrubbing processes include: moderate to high gas-side pressure drop across the spray dryer gas inlet distribution device, and limitations on the spray down temperature (i.e., the approach to flue gas saturation temperature) required to maintain controlled operations . [0008] There are several methods for controlling NO_x emissions. Selective Catalytic Reduction (SCR) is the most common method. In these processes, ammonia is injected and mixed with the flue gas at low to medium temperatures . The mixture then flows across a catalyst (often vanadium based over a stainless steel substrate) and the NO_x is reduced to N₂. The problems with SCR systems is the high initial cost, high cost of ammonia which is thermally or chemically decomposed, and the introduction of ammonia into the gas stream causing problems with the formation of ammonium bisulfate and ammonia slip the atmosphere. Selective Non-catalytic Reduction (SNCR) methods are also employed. In these processes ammonia or urea is injected into hot flue gases resulting with a direct reaction forming N₂. The problems with SNCR systems is the challenges with mixing and maintaining proper residence time and operating conditions for the reactions to take place optimally, sensitivity to changes in operating load, the high cost of ammonia which is thermally or chemically decomposed

(even more, than SCRs) , and the introduction of ammonia into the gas stream causing problems with the formation of ammonium bisulfate and ammonia slip (as high as 50 ppm or higher) to the atmosphere .

[0009] NO_x removal through injection of sodium bicarbonate (NaHCO₃) has been demonstrated by NaTec and others.

[0010] In the prior art for wet chemical NO_x reduction, the use of oxidants such as hydrogen peroxide is employed. Hydrogen peroxide is an oxidizing agent for organic and inorganic chemical processing as well as semi-conductor, applications bleach for textiles and pulp, and a treatment for municipal and industrial waste. Hydrogen Peroxide (H₂O₂) is an effective means of scrubbing Nitrogen Oxides . It has been used for many years . The use of H₂O₂ and HNO₃ to scrub both NO and NO₂ is an attractive option because the combination handles widely varying rates of NO to NO₂, adds no contaminants to the scrubbing solution or blow-down/waste stream and allows a commercial product to be recovered from the process, i.e. nitric acid or ammonium nitrate.

- 3 -

U:\AIIStafAcaldwell\Scan-l .doc [0011] Gas scrubbing is another common form of NO_x treatment, with sodium hydroxide being the conventional scrubbing medium. However, the absorbed NO_x is converted to nitrite and nitrate which may- present wastewater disposal problems. Scrubbing solutions containing hydrogen peroxide are also effective at removing NO_x, and can afford benefits not available with NaOH. For example, H₂O₂ adds no contaminants to the scrubbing solution and so allows commercial products to be recovered from the process, e.g., nitric acid. In its simplest application, H₂O₂ and nitric acid are used to scrub both nitric oxide (NO) and nitrogen dioxide (NO₂) - the chief components of NO_x from many utility and industrial sources .

[0012] There are several other processes which also use hydrogen peroxide to remove NO_x. The Kanto Denka process employs a scrubbing solution containing 0.2% hydrogen peroxide and 10% nitric acid while the Nikon process uses a 10% sodium hydroxide solution containing 3.5% hydrogen peroxide. A fourth process, the Ozawa process, scrubs NO_x by spraying a hydrogen peroxide solution into the exhaust gas stream. The liquid is then separated from the gas stream, and the nitric acid formed is neutralized with potassium hydroxide. The excess potassium nitrate is crystallized out, and the solution reused after recharging with hydrogen. In addition to the methods cited above in which NO_x is oxidized to nitric acid or nitrate salts, a series of Japanese patents describe processes and equipment for reducing NO_x to nitrogen using hydrogen peroxide and ammonia.

[0013] Also worth mentioning is the fact that H₂O₂ is used for the measurement of Nitrogen Oxide in the Standard Reference Method 7 of the Code of Federal Regulations (CFR) promulgated test methods published in the Federal Register as final rules by the US Environmental Protection Agency (EPA). In this procedure, an H₂O₂ solution is used in a flask to effectively capture the NO_x. This, however is a slow reaction that requires several hours to complete .

[0014] There are two primary reasons that H₂O₂ has not gained widespread use as a reagent for removal of NO_x in utility and large industrial applications. The first is that it is not a selective oxidant. Most of these sources also contain other species, primarily, SO₂ which are also effectively removed with hydrogen peroxide. Thus, a large quantity of H₂O₂ would be required compared to the amount of NO_x removal sought. Even after a limestone scrubber, the amount of SO₂ present in flue gas may be equal to or greater than the amount of NO_x.

[0015] The second reason that H₂O₂ has not gained widespread use is the cost, especially when much more is required due to reactions with SO₂, for example, which can be better done prior to the H₂O₂ stage .

The overall reactions are:

1 ) 3H₂O₂ + 2NO → 2HNO₃ + 2H₂O

2 ) H₂O₂ + 2NO₂ -+ 2HNO₃

3 ) H₂O₂ + SO₂ -, H₂SO₄

[0016] Oxidation utilizing gases have been demonstrated in the art. It has been shown that over 90% of gas phase NO can be converted to NO₂ rapidly by ClO₂ at an applied rate of approximately 1.2 kg C10₂/kg NO. This of course requires proper mixing conditions. ClO₂ is a much stronger oxidizer than hydrogen peroxide, sodium chlorate or sodium chlorite and would be a preferred oxidizer. Ozone is also a possibility, but has orders of magnitude greater capital costs relative to ClO₂ generators.

[0017] Sulfur dioxide reacts with chlorine dioxide in the gas phase to form sulfuric and hydrochloric acid.

4) 2ClO₂ + 5SO₂ + 6H₂O > 5H₂SO₄ + 2HCl

[0018] Assuming SO₂ is the dominant species in the ClO₂ reaction in the presence of SO₂ and NO, then it is advisable, according to this invention, to add ClO₂ after having scrubbed out SO_x to keep the economics of adding ClO₂ good. [0019] A different process employs a proprietary oxidizing compound plus dilute sulfuric acid in a first stage and an irreversible process involving proprietary solutions and chemistries in a second stage. The system operates at greater than 99% efficiency on both NO and NO₂ and will accommodate ambient temperature gas streams .

[0020] The prior art also does not teach simultaneous removal of mercury and NO_x, especially elemental mercury (Hg°) removal. The prior art does teach limited capture of mercury using activated carbon and capture of oxidized mercury (Hg⁺² such as in the form of HgCl₂) (United States Patent No. 6,503,470 to Nolan, et al . ) in wet scrubbers that use an alkali reagent. This process also uses additives such as sodium hydrogen sulfide (NaHS) or other sulfides to chemically bind with the mercury to form compounds such as HgS.

SUMMARY OF THE INVENTION

[0021] One object of one embodiment of the present invention is to provide an improved method for scrubbing flue gas streams.

[0022] A further object of one embodiment of the present invention is to provide a method of scrubbing Hg compounds from a flue gas stream, comprising a scrubbing operation, including: contacting a flue gas stream containing Hg, SO_x and NO_x compounds with a sorbent for removing at least a portion of said SO_x, Hg and NO_x compounds present in said stream to provide a partially cleaned flue gas stream; and contacting said partially cleaned flue gas stream with an oxidant to oxidize and capture substantially all residual Hg remaining in said stream.

[0023] Yet another object of one embodiment of the present invention is to provide a method of scrubbing NO_x compounds from a flue gas stream containing said NO_x compounds, a scrubbing operation, including: contacting a flue gas stream containing SO_x and NO_x compounds with a sorbent for removing at least a portion of said SO_x and NO_x compounds present in said stream to provide a partially cleaned flue gas stream; and contacting said partially cleaned flue gas stream with an oxidant to oxidize and capture substantially all residual NO_x remaining in said stream.

[0024] A host of advantages are realized by practicing the methodology of the invention. One advantage is that a high removal of SO₂ and NO_x(NO, NO₂, and dimers) is achieved with essentially all of the acid gas and air toxics {including NO_x) in the flue gas being removed. Particularly convenient is the fact that NO_x is removed without the use of ammonia and no SCR (Selective Catalytic Reduction) system is required for NO_x removal. The methodology also results in the high removal of Hg without the use of expensive activated carbon systems; in the preferred embodiment, all emissions removal is accomplished in a single, staged tower.

[0025] It has been found that the oxidant will also effectively remove any SO₂ in the flue gas with the overall cost of this ultra high removal system being lower than a system with multiple vessels .

[0026] In terms of other features, less physical space is required than conventional multi-step processes which would employ separate vessels and much more equipment in the gas stream; the amount of oxidant required is reduced, since almost all the sulfur compounds and some of the NO_x and Hg are removed prior to the oxidant stage.

[0027] The process permits many choices for reagents for SO₂ control in the first add-on stage with sodium alkalis being the preferred reagents due to gas phase reactions in the stage, production of sodium sulfate, the ability to regenerate the sodium alkali, and conveniently, carbon injection equipment is not required as Hg and other air toxics are removed by the staged process steps.

[0028] Further advantages include: each stage can be custom designed to meet the pollutant removal characteristics of the constituents removed in each individual stage; the chemistry of each stage is independently controlled and monitored to optimize the performance; each stage is isolated to prevent contamination of reagents/solutions; and the solutions in each stage are handled separately.

[0029] Having thus described the invention, reference will now be made to the accompanying drawings illustrating preferred embodiments .

BRIEF DESCRIPTION OF THE DRAWINGS [0030] Figure 1 is a prior art scrubber arrangement;

[0031] Figure 2 is a scrubber arrangement according to the present invention;

[0032] Figure 3 is a prior scrubber arrangement incorporating a wet electrostatic precipitator (WESP) for the purpose of removing condensables, like H₂SO₄ which forms from SO₃ gas and water;

[0033] Figure 4 is a graphical representation of data in accordance with the present invention; and

[0034] Figure 5 is a further graphical representation of data in accordance with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] Wet scrubbing systems such as that shown on Figure 1 and globally denoted by numeral 10 use lime, limestone, soda ash, sodium, magnesium, and calcium or other compounds for scrubbing. They also can employ any of a number of additives to enhance removal _r control chemistry, and reduce chemical scale. These systems are adequate at removing SO₂ up to maybe 90 — 98%, but do not effectively remove NO_x or Hg.

[0036] In the combined system of the present invention, the flue gas is scrubbed by wet scrubbing using prior art technologies like that shown on Figure 1 for partial removal of SO₂ (partial removal means less than 100% or typically 90 - 95% such as is known in the prior art for calcium based scrubbers) . [0037] The gas could be, optionally, conditioned by injection of absorbents, reagents, or sorbents to reduce a portion of the inlet SO₃. Some sulfur dioxide, hydrochloric acid, NO_x or other acid gases may also be removed by the injection. This can be by wet or dry injection with almost any alkali at any of several possible and known locations or temperature zones from the source of the flue gas to the scrubber inlet. However, dry sodium bicarbonate injection is preferred since it will react with the SO₃, NO_x and SO₂ and other acid gasses including HCl, HF, H₂S, etc. in the gas stream. When injection of sorbents is employed, the need for a wet electrostatic precipitator such as that shown on Figure 3 is eliminated. H₂SO₄ is not formed since SO3 is effectively removed upstream of the wet scrubbing system.

[0038] Following the optional injection step, SO₂ and acidic NO_x compounds such as NO₂, N₂O3 and N₂O₅ and their associated dimmers, i.e. N₂O₄ are removed in the wet scrubber. In the prior art with sodium bicarbonate injection, the conversion of NO to NO₂ was considered undesirable since the NO₂ was a brown gas that was not captured by the downstream equipment. In this case, the wet scrubber effectively captures some of the NO₂, N₂O₅, etc. Some of the NO is captured directly by the sodium bicarbonate.

[0039] In the prior art, including United States Patent No. 6,143,263 and United States Patent No. 6,303,083, Method and System for SO₂ and SO₃ Control by Dry Sorbent/Reagent Injection and Wet Scrubbing, there is no teaching for NO_x removal in any form as the NO_x is known to be primarily in the form of NO which is not effectively captured with conventional based sorbents such as lime, limestone, or sodium.

[0040] The present invention is a one to three step add-on technology. This applies to all scrubbing systems for gases that contain SO₂, NO_x, and Hg such as from the combustion of coal or other industrial fuels or from chemical processes. This also applies to both new applications or modifications of existing units .

[0041] For the one stage add-on step, all or almost all SO₂ is removed by the prior art system such as a high efficiency scrubber that employs a reagent based on sodium, magnesium, buffered calcium, etc. High removal of SO₂ is not necessary, but is preferred. If the SO₂ removal is low, then it will be removed by the oxidant. This will require a significant quantity of a higher cost reactant.

[0042] For a 2-stage add-on step, the first a stage is added to effectively remove all or almost all of the remaining SO₂. This uses a tray like a bubble cap tray (not shown) or a separate vessel (not shown) to keep the 2^nd-stage SO₂ reagent stream separate from the lower stage acid gas absorber stage. This is done ^'preferably, using a soluble scrubbing solution such as a sodium or magnesium based reagent (hydroxide, carbonate, sulfite, bicarbonate, bisulfite, etc. and may include buffering agents, additives, organic acids, etc.) with the appropriate mass transfer surfaces including any combination of sprays, packing, trays, etc.

[0043] Therefore, for both cases, all or almost all of the SO₂ is removed prior to the oxidant stage .

[0044] In the oxidant stage, NO_x (primarily in the form of NO, NO₂, or other dimers) and mercury (elemental and oxidized) are removed. Like the first stage of the 2-stage add-on step, this uses a tray like a bubble cap tray or a separate vessel (neither of which are shown) to keep the reagent, in this case an oxidant stream, separate from the lower stages. Mass transfer surfaces such as additional trays, sprays or packing are added as required. The result is that the gas leaving this stage is essentially free of all SO_x and has at up to 90% or more of the mercury and NO_x removed. This eliminates Hg, SO_x, and NO_x contamination in the final stage. [0045] An optional add-on stage is used as a final wash. This would be used to make sure any byproduct from the oxidant such as chlorine gas, NO₂, etc. is washed from the flue gas. The final wash, if required, would be with water or an appropriate solution.

[0046] A preferred embodiment (see Figure 4) therefore consists of 2 to 5 or more stages. In a five stage system, the first stage is a dry injection step. The second stage is the wet acid gas scrubber using conventional steps known in the art and denoted by numeral 12. The third stage is a polishing step to remove the remaining SO₂. The preferred embodiment of the third stage (first add-on stage) is a reaction zone that uses a sodium carbonate (Na₂CC>₃) , caustic soda (NaOH) or sodium bicarbonate (NaHCO₃) reactant. This would produce sodium sulfate by the following overall reactions:

5) 2NaHCO₃ + SO₂ +V=O₂ → Na₂SO₄ + 2CO₂T + H₂O

6) Na₂CO₃ + SO₂ + VJO₂ → Na₂SO₄ + CO₂T + H₂O

7) 2NaOH + SO₂ + Y2O2 → Na₂SO₄ + H₂O

[0047] The sodium carbonate, caustic soda, or sodium bicarbonate (or other reactants) can be purchased. Sodium bicarbonate can be regenerated on site using the processes developed by Airborne Pollution Control. Caustic soda can be produced on site using electrochemical methods from sodium sulfate. In this case, sodium sulfate is split and reacted with ammonia to produce NaOH and (NH₄) ₂SO₄. The NaOH is used in the scrubber and the (NH₄J₂SO₄ can be sold as a fertilizer.

[0048] The forth stage is the oxidant stage is used to remove NO_x and/or mercury. One embodiment of the oxidant stage would be an integral reaction zone that recirculates an aqueous solution of oxidant and reaction products to effectively remove all the NO_x and much of "the mercury, simultaneously. No sulfur oxides would be removed in this step as they are effectively removed prior to the oxidant stage.

[0049] The fifth stage is the final wash. [0050] Other embodiments would use 2, 3, 4, 5 or more stages depending upon the pollutants that will be removed and the operating conditions. For example, Stage 1 of the preferred embodiment, would not be required if SO3 was not present, Stages 1 and 2 are not required if there is no SO_x present, and Stage 5 is not required if species that require a final wash are not present. The oxidant would be selected depending upon the desired level of removal of NO_x and/or Hg.

[0051] The following is a partial list of oxidants that are useful for capture of NO_x and/or Hg or Hg compounds:

1 ) Hydrogen Peroxide

2) Hydrogen Peroxide/Nitric Acid Solution (H₂O₂/HNO₃)

3) Hydrogen Peroxide/Nitric Acid/Hydrochloric Acid Solution (H₂O₂/HNO₃/HCl)

4) Sodium Chlorate Solution (NaClO₃)

5) Sodium Chlorite Solution (NaClO₂)

6) Sodium Hypochlorite Solution (NaClO)

7) Sodium Perchlorite Solution (NaClO₄)

8) Chloric Acid Solution (HClO₃)

9) Oxone Solution (2KHSO₅-KHSO₄-K₂SO₄ Triple Salt)

10) Potassium Chlorate Solution (KClO₃)

11) Potassium Chlorite Solution (KC102)

12) Potassium Hypochlorite Solution (KClO)

13) Potassium Perchlorite Solution (KClO₄)

14) Potassium Permanganate (KMnO₄)

15) Potassium Permanganate/Sodium Hydroxide Solution

[0052] Other oxidants or combinations of oxidants are possible. Further, sodium carbonate and sodium bicarbonate or other alkalis can be substituted for the sodium hydroxide solutions used for pH adjustment and to provide the ions for complete reactions. Oxidants can be selected to remove just NO_x, remove just Hg or simultaneously remove both NO_x and Hg. Additionally, gaseous oxidants such as ozone, O₃, or Chloride dioxide, CIO₂, can be injected into the gas that has had all or most of the SO₂ removed. With proper mixing and sufficient residence, the oxidation of NO or Hg in the gas phase by gaseous oxidants occurs . Gaseous oxidants are capable of oxidizing NO not only to NO₂ but also to N₂O₅ which rapidly reacts with water or alkaline solutions to form nitric acid or nitrates.

[0053] Bench-scale screening of potential solutions for capturing NO_x and Hg° was performed using a simple gaseous mixture (Hg° + NO + NO₂ + CO₂ + H₂O + N₂ + O₂) and an impinger sampling train similar to that described in the American Society of Testing and Materials Method D6784-02 (Ontario Hydro method) . Testing has identified solutions that effectively removed both NO_x and Hg° . The results are shown in the table below:

[0054] The results show that there are several possible solutions from which to choose. Even the situations that show medium removal ranges such as (Nitric Acid (40%) + Hydrogen Peroxide) or Acidified Potassium Permanganate will remove at higher rates with an appropriate modification to the mass transfer means. The oxidant selected, will then be based on economics, availability, desired level of capture, and/or desired end product.

[0055] Further results are shown on Figures 3 & 4, with Figure 3 illustrating mercury removal as a functioning time using NaClO at pH 5.73 and Figure 4 illustrating mercury and NO_x removal as a function of time using 0.1 M NaClO solution at pH 8. The proposed reactions with Sodium Hypochlorite (NaOCl) and NO_x and Hg are:

8) 2NO + 3NaClO + 2NaOH → 2NaNO₃ + 3NaCl + H₂O

9) 2NO + 3NaClO + Na₂CO₃ → 2NaNO₃ + 3NaCl + C0₂t

10) 2N0 + 3NaClO + 2NaHCO₃ → 2NaNO₃ + 3NaCl + 2CO₂! + H₂O

11) 2NO₂ + NaClO + 2NaOH - 2NaNO₃ + NaCl + H₂O

12) 2NO₂ + NaClO + Na₂CO₃ → 2NaNO₃ + NaCl + C0₂t

13) 2NO₂ + NaClO + 2NaHCO₃ → 2NaNO₃ + NaCl + 2C0₂f + H₂O

14) 2Hg + 4NaClO + 2H₂O → 2HgCl₂ + 4NaOH + O₂

[0056] In these reactions, an additional source of sodium such as bicarbonate, carbonate or hydroxide is provided to balance the reaction and in order to limit the potentially deleterious reaction of liberating Cl₂ gas. Thus the washing step would not be required. Sodium Chlorite (NaClO₂), Sodium Chlorate (NaClO₃) and Sodium Perchlorite (NaClθ4) can also be used for removal of NO_x and Hg.

[0057] The products of the NO_x reactions can be regenerated by the Airborne Process™ by the reactions:

15) NaNO₃ + H₂O + NH₃ + CO₂ → NaHCO₃I + NH₄NO₃

16) NaCl + H₂O + NH₃ + CO₂ → NaHCO₃ ; + NH₄Cl

[0058] Although embodiments of the invention have been described above, it is not limited thereto and it will be apparent to those skilled in the art that numerous modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the claimed and described invention.

Claims

I CLAIM:

1. A method of scrubbing Hg compounds from a gas stream, comprising: a scrubbing operation, including:

contacting a gas stream containing Hg or Hg compounds and SO_x compounds with a sorbent for removing at least a portion of said SO_x, compounds present in said stream to provide a partially cleaned gas stream; and

contacting said partially cleaned gas stream with an oxidant or oxidant solution to oxidize and/or remove residual Hg or Hg compounds remaining in said stream.

2. The method as set forth in Claim 1, wherein said gas stream includes NO_x compounds and a potion of the NO_x compounds and/or a portion of the Hg or Hg compounds present in the gas are removed in said scrubbing operation.

3. The method as set forth in Claim 1, wherein said partially cleaned gas stream is further contacted with a second sorbent selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium hydroxide, calcium carbonate, calcium oxide, and calcium hydroxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, buffering agents, additives, organic acids, or combinations thereof to remove substantially all remaining SO_x compounds prior to said contacting with an oxidant or oxidant solution.

4. The method as set forth in Claim 1, wherein substantially all of the residual Hg or Hg Compounds are removed from said partially cleaned gas stream.

5. The method as set forth in Claim 2, wherein said partially cleaned gas stream containing NO_x compounds is further contacted with a second sorbent selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium hydroxide, calcium carbonate, calcium oxide, and calcium hydroxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, buffering agents, additives, organic acids, or combinations thereof to remove substantially all remaining SO_x compounds prior to said contacting with an oxidant.

6. The method as set forth in Claim 2, wherein contacting of said partially cleaned gas stream with an oxidant to remove residual Hg or Hg compounds remaining in said stream further removes at least a portion of NO_x in said gas or converts all or part of the NO to NO₂.

7. The method as set forth in Claim 6, including contacting said gas containing NO₂ with water or an aqueous alkali to remove said NO₂.

8. The method as set forth in Claim 1, including contacting said gas with a final wash.

9. The method as set forth in Claim 1, wherein said oxidant is selected from a group consisting of solutions of hydrogen peroxide, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium perchlorite, chloric acid/sodium chlorate, chloric acid, potassium chlorate, potassium chlorite, potassium hypochlorite, potassium perchlorite, potassium permanganate, or a combination thereof or from a group of gaseous oxidants consisting of ozone, chlorine dioxide, or combination thereof.

10. The method as set forth in Claim 2, wherein said oxidant is selected from a group consisting of solutions of hydrogen peroxide, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium perchlorite, chloric acid/sodium chlorate, chloric acid, potassium chlorate, potassium chlorite, potassium hypochlorite, potassium perchlorite, potassium permanganate, or a combination thereof or from a group of gaseous oxidants consisting of ozone, chlorine dioxide, or combination thereof.

11. The method as set forth in Claim 9, wherein said oxidant is in solution with an acid selected from the group consisting of nitric acid, hydrochloric acid and sulfuric acid.

12. The method as set forth in Claim 9, wherein said oxidant is in solution with an alkali.

13. The method as set forth in Claim 12, wherein said alkali is selected from a group including: caustic soda, sodium carbonate, or sodium bicarbonate.

14. The method as set forth in Claim 9, wherein said oxidant includes chloride ions .

15. The method as set forth in Claim 1, wherein said SO_x compounds include SO₂ and SO₃.

16. The method as set forth in Claim 2, wherein said NO_x compounds include NO₂, N₂O₃, N₂O₅, N_x0_y and dimers thereof.

17. The method as set forth in Claim 1, further including the step of recirculating unreacted sorbent for use in said scrubbing operation.

18. The method as set forth in Claim 2, further including the step of recirculating unreacted sorbent for use in said scrubbing operation.

19. The method as set forth in Claim 1, wherein said gas is conditioned by injection of sorbent to reduce a portion of the inlet SO₃.

20. The method as set forth in Claim 2, wherein said gas is conditioned by injection of sorbent to reduce a portion of the inlet SO₃.

21. The method as set forth in Claim 19, wherein at least some of said sulfur dioxide is removed and/or hydrochloric acid, NO_x or other acid gases are removed by the said injection.

22. A method of scrubbing NO_x compounds from a gas stream containing said NO_x compounds comprising a scrubbing operation, including :

contacting a gas stream containing SO_x and NO_x compounds with a sorbent for removing at least a portion of said SO_x compounds present in said stream to provide a partially cleaned gas stream; and

contacting said partially cleaned gas stream with an oxidant or oxidant solution to oxidize and/or remove residual NO_x remaining in said stream.

23. The method as set forth in Claim 22, wherein at least some of the NO_x compounds present in the gas are removed in said scrubbing operation .

24. The method as set forth in Claim 22, wherein said partially cleaned gas is further contacted with a second sorbent selected from the group consisting of sodium bicarbonate, sodium carbonate, sodium hydroxide, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, buffering agents, additives, organic acids, or combinations thereof to remove substantially all remaining SO_x compounds prior to said contacting with an oxidant .

25. The method as set forth in Claim 22, wherein substantially all of the residual NO_x Compounds are removed from said partially cleaned gas stream.

26. The method as set forth in Claim 22, wherein oxidation of said partially cleaned gas stream with an oxidant to remove residual NO_x remaining in said stream further removes at least a portion of Hg or Hg compounds in said gas.

27. The method as set forth in Claim 22, including contacting said gas containing NO2 with water or an aqueous alkali to remove said NO2.

28. The method as set forth in Claim 22, including contacting said gas with a final wash.

29. The method as set forth in Claim 22, wherein said oxidant is selected from a group consisting of solutions of hydrogen peroxide, sodium chlorate, sodium chlorite, sodium hypochlorite, sodium perchlorite, chloric acid/sodium chlorate, chloric acid, potassium chlorate, potassium chlorite, potassium hypochlorite, potassium perchlorite, potassium permanganate, or a combination thereof or from a group of gaseous oxidants consisting of ozone, chlorine dioxide, or combination thereof.

30. The method as set forth in Claim 29, wherein said oxidant is in solution with an acid selected from the group consisting of nitric acid, hydrochloric acid and sulfuric acid.

31. The method as set forth in Claim 29, wherein said oxidant is in solution with an alkali .

32. The method as set forth in Claim 31, wherein said alkali is selected from a group including: caustic soda, sodium carbonate, or sodium bicarbonate .

33. The method as set forth in Claim 29, wherein said oxidant includes chloride ions .

34. The method as set forth in Claim 22, wherein said gas is conditioned by injection of sorbent to reduce a portion of the inlet SO₃.

35. The method as set forth in Claim 22, wherein said gas is conditioned by injection of sorbent to reduce a portion of the inlet SO₃.

36. The method as set forth in Claim 35, wherein a portion of said sulfur dioxide is removed and/or hydrochloric acid, NO_x or other acid gases are removed by the said injection.

37. The method as forth in claim 2, including contacting said gas with a final wash.

38. The method as set forth in claim 2, wherein said SO_x compounds include SO₂ and SO₃.