1. Field of the Invention
The present invention relates to a mercury reduction system and a mercury reduction method of flue gas containing mercury that reduce mercury in flue gas discharged from a boiler and the like.
2. Description of the Related Art
Coal combustion flue gas and flue gas generated by burning heavy fuel oil may contain dust, sulfur oxide (SOx), and nitrogen oxide (NOx), as well as metallic mercury)(Hg0). In recent years, various proposals have been made on methods and apparatuses for treating the metallic mercury, by combining a denitration apparatus that reduces NOx and a wet desulfurization apparatus that uses an alkali absorbent as an SOx absorbent.
As a method for treating metallic mercury in flue gas, a system in which NOx in a flue is removed by spraying ammonia (NH3) in the upstream process of a high-temperature denitration apparatus, and mercury is oxidized (chlorinated) on a denitration catalyst by spraying a chlorinating agent such as hydrochloric acid (HCl), turned into an aqueous mercury chloride solution, and removed by a wet desulfurization apparatus installed downstream has been proposed (for example, see Patent Document 1).
An NH3 injection spot 111 is provided upstream of the reduction denitration apparatus 103, and nitrogen oxide is reduced by NH3 supplied from an NH3 tank 112.
A hydrochloric acid measuring unit 113 installed upstream of the desulfurization apparatus 107 in the flue measures the concentration of hydrochloric acid (HCl) used as a mercury chlorinating agent, and a mercury concentration measuring unit 114 installed downstream of the desulfurization apparatus 107 measures the concentration of mercury (Hg). An arithmetic unit 117 calculates an initial concentration of aqueous hydrogen chloride (HCl) solution 116 supplied from a hydrochloric acid solution tank 115, based on the measured concentration values of hydrochloric acid and mercury (Hg). A controlling unit 118 controls the supply of evaporated hydrochloric acid (evaporated HCl) supplied into the flue from the hydrochloric acid solution tank 115 through an HCl injection spot 119.
As a method of spraying HCl from the HCl injection spot 119, a method of reducing mercury combined with a hydrogen chloride (HCl) vaporizer has been proposed (for example, refer to Patent Document 2).
As a method of supplying HCl, a method of reducing mercury combined with an apparatus for sublimating ammonium chloride (NH4Cl) solid has been similarly proposed (for example, refer to Patent Document 3).
Patent Document 1: Japanese Patent Publication Laid-open No. H10-230137
Patent Document 2: Japanese Patent Publication Laid-open No. 2007-167743
Patent Document 3: Japanese Patent Publication Laid-open No. 2008-221087
However, in the air pollution control system 100 including a mercury reduction system shown in
As the mercury chlorinating agent feed apparatus of the mercury reduction system shown in
As the air pollution control apparatus shown in
The present invention is made in view of the foregoing, and has an object to provide a mercury reduction system and a mercury reduction method of flue gas containing mercury with enhanced mercury reduction performance and low operational cost.
According to an aspect of the present invention, a mercury reduction system that reduces nitrogen oxide and mercury in flue gas discharged from a boiler includes: an oxidation-reduction agent supplying unit that sprays an oxidation-reduction agent for producing hydrogen chloride and ammonia when evaporated into a flue of the boiler in a liquid state; a reduction denitration apparatus that includes a denitration catalyst for reducing nitrogen oxide in the flue gas with ammonia and for oxidizing mercury in a presence of hydrogen chloride; and a wet desulfurization apparatus that reduces mercury oxidized in the reduction denitration apparatus with an alkali absorbent. The oxidation-reduction agent being sprayed into the flue in the liquid state is evaporated, and decomposed into hydrogen chloride and ammonia.
Advantageously, in the mercury reduction system, the oxidation-reduction agent is ammonium chloride.
Advantageously, in the mercury reduction system, concentration of the oxidation-reduction agent is equal to or less than 43 wt %.
Advantageously, in the mercury reduction system, the oxidation-reduction agent supplying unit includes an oxidation-reduction agent feed pipe through which the oxidation-reduction agent is supplied into the flue in a liquid state, a blow pipe with an injection hole that is inserted into the flue so as to surround the oxidation-reduction agent feed pipe, and through which air supplied therein is injected into the flue, and an injection nozzle that is fitted to an end of the oxidation-reduction agent feed pipe and through which the oxidation-reduction agent is injected, and the oxidation-reduction agent is sprayed into the flue accompanied with the air.
Advantageously, in the mercury reduction system, the spraying unit is a two-fluid nozzle through which the oxidation-reduction agent and the air for spraying the oxidation-reduction agent are injected.
Advantageously, in the mercury reduction system, the oxidation-reduction agent supplying unit includes an oxidation-reduction agent feed pipe through which the oxidation-reduction agent is supplied into the flue in a liquid state, an air feed pipe that is inserted into the flue so as to surround the oxidation-reduction agent feed pipe, and through which air for spraying the oxidation-reduction agent is supplied into the flue, and a two-fluid nozzle that is fitted to an end of the oxidation-reduction agent feed pipe and the air feed pipe, and through which the oxidation-reduction agent and the air are injected, and the oxidation-reduction agent is sprayed into the flue accompanied with the air.
Advantageously, in the mercury reduction system, a diameter of a liquid droplet of the oxidation-reduction agent sprayed from the oxidation-reduction agent supplying unit is equal to or more than 1 nanometer and equal to or less than 100 micrometers on average.
Advantageously, in the mercury reduction system, temperature of the flue gas is equal to or more than 320° C. and equal to or less than 420° C.
Advantageously, the mercury reduction system further includes a nitrogen oxide concentration meter that is provided upstream and downstream of the reduction denitration apparatus, and measures concentration of nitrogen oxide in the flue gas.
Advantageously, the mercury reduction system further includes an ammonia supplying unit that is provided between the oxidation-reduction agent supplying unit and the reduction denitration apparatus, and supplies ammonia into the flue.
Advantageously, the mercury reduction system further includes a hydrogen chloride supplying unit that is provided between the oxidation-reduction agent supplying unit and the reduction denitration apparatus, and supplies hydrogen chloride into the flue.
According to another aspect of the present invention, a mercury reduction method of flue gas containing mercury for reducing nitrogen oxide and mercury in flue gas discharged from a boiler, the mercury reduction method of flue gas containing mercury includes: a step of oxidation-reduction agent supplying for spraying an oxidation-reduction agent for producing hydrogen chloride and ammonia when evaporated into a flue of the boiler; a step of reduction denitration treating for reducing nitrogen oxide in the flue gas with ammonia on a denitration catalyst and oxidizing mercury in a presence of hydrogen chloride; and a step of wet desulfurizing for reducing mercury oxidized at the step of reduction denitration treating with an alkali absorbent. The oxidation-reduction agent being sprayed into the flue in a liquid state is evaporated, and decomposed into hydrogen chloride and ammonia.
Advantageously, in the mercury reduction method of flue gas containing mercury, the oxidation-reduction agent is ammonium chloride.
Advantageously, in the mercury reduction method of flue gas containing mercury, the oxidation-reduction agent is sprayed with a two-fluid nozzle at the step of oxidation-reduction agent supplying.
Advantageously, the mercury reduction method of flue gas containing mercury further includes: a step of nitrogen oxide concentration measuring that is provided prior to and subsequent to the step of reduction denitration treating, and measures concentration of nitrogen oxide in the flue gas; and a step of mercury concentration measuring that is provided subsequent to the step of reduction denitration treating, and measures concentration of mercury in the flue gas. Supply of the oxidation-reduction agent supplied at the step of oxidation-reduction agent supplying is adjusted, based on at least one of the concentration of nitrogen oxide in the flue gas obtained at the step of nitrogen oxide concentration measuring and the concentration of mercury in the flue gas obtained at the step of mercury concentration measuring, or both.
Advantageously, the mercury reduction method of flue gas containing mercury further includes: at least one of a step of ammonia supplying that supplies ammonia into the flue and a step of hydrogen chloride supplying that supplies hydrogen chloride into the flue, or both, between the step of oxidation-reduction agent supplying and the step of reduction denitration treating. Supply of at least one of ammonia and hydrogen chloride or both supplied at least one of at the step of ammonia supplying and at the step of hydrogen chloride supplying or both is adjusted, based on at least one of the concentration of nitrogen oxide in the flue gas obtained at the step of nitrogen oxide concentration measuring and the concentration of mercury in the flue gas obtained at the step of mercury concentration measuring or both.
Advantageously, in the mercury reduction method of flue gas containing mercury, supply of the oxidation-reduction agent is determined by calculating contents of nitrogen oxide and mercury in the flue gas from property of coal used in the boiler.
Advantageously, in the mercury reduction method of flue gas containing mercury, supplies of the oxidation-reduction agent, the ammonia, and the hydrogen chloride are determined by calculating contents of nitrogen oxide and mercury in the flue gas from property of coal used in the boiler.
Exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The present invention is not limited by the embodiments. Constituent elements according to the embodiments below include elements that can be easily conceived by a person skilled in the art, or elements being substantially the same as those elements.
A mercury reduction system according to a first embodiment of the present invention will be described with reference to the accompanying drawings.
As shown in
In the mercury reduction system 10 according to the present embodiment, NH4Cl is used as an oxidation-reduction agent. However, the present invention is not limited thereto. Any agent that generates hydrogen chloride (HCl) and ammonia (NH3) when evaporated, may be used as the oxidation-reduction agent.
In the present invention, the oxidation-reduction agent functions as an oxidizing agent for oxidizing and chlorinating mercury (Hg) in the presence of hydrogen chloride (HCl), and a reducing agent for reducing ammonia(NH3).
(Adjusting NH4Cl Solution)
The NH4Cl solution 14 is adjusted to a predetermined concentration. Ammonium chloride (NH4Cl) powder 21 is conveyed and supplied to a silo 22 in which the NH4Cl powder 21 is temporarily retained. A blower 23 supplies air 24 to the NH4Cl powder 21 in the silo 22 and prevents the NH4Cl powder 21 from drying and fixing in the silo 22. A predetermined amount of the NH4Cl powder 21 in the silo 22 is supplied to an NH4Cl powder feed path 26 from the silo 22 by a feeder 25, and fed into an NH4Cl dissolving tank 27. A water supplying tank 28 feeds water 29 into the NH4Cl dissolving tank 27. The NH4Cl dissolving tank 27 includes a stirring unit 30-1, and the NH4Cl powder 21 supplied into the NH4Cl dissolving tank 27 is dissolved in the water 29, thereby generating the NH4Cl solution 14 of a predetermined concentration. The stirring unit 30-1 keeps the concentration of the NH4Cl solution 14 constant. The water 29 supplied from the water supplying tank 28 is adjusted by a valve V1.
The concentration of the NH4Cl solution 14 is preferably more than 0 wt % and equal to or less than 43 wt %, more preferably equal to or more than 10 wt % and equal to or less than 23 wt %, more preferably equal to or more than 18 wt % and equal to or less than 23 wt %, and most preferably about 20 wt %. This is because, the NH4Cl powder 21 needs to be dissolved in the water 29 at least at room temperature (for example, at around 20° C.), and the concentration of the NH4Cl solution 14 should be equal to or less than saturation concentration of NH4Cl in water.
(Controlling the Concentration of NH4Cl Solution)
The NH4Cl solution 14 in the NH4Cl dissolving tank 27 is measured by an ammonium chloride (NH4Cl) concentration meter 31 and the measured concentration value of the NH4Cl solution 14 is transmitted to an arithmetic apparatus 32. The arithmetic apparatus 32 determines the supplies of the NH4Cl powder 21 and the water 29, based on the concentration of the NH4Cl solution 14. The arithmetic apparatus 32 transmits control signals to the feeder 25 and the valve V1, and adjusts the supplies of the NH4Cl powder 21 and the water 29. The concentration of the NH4Cl solution 14 in the NH4Cl dissolving tank 27 is adjusted so as to fall within a range more than 0 wt % and equal to or less than 43 wt %.
In the mercury reduction system 10A according to the present embodiment, the NH4Cl supplying unit 15A includes an NH4Cl solution feed pipe 33 that supplies the NH4Cl solution 14 into the flue 13 in a liquid state, a blow pipe 36 (see
The NH4Cl solution 14 in the NH4Cl dissolving tank 27 is fed into a dissolved NH4Cl feed tank 41, and the dissolved NH4Cl feed tank 41 temporarily retains the NH4Cl solution in the NH4Cl dissolving tank 27. The NH4Cl dissolving tank 27 includes a stirring unit 30-2 that keeps the NH4Cl concentration of the NH4Cl solution in the NH4Cl dissolving tank 27 constant. The NH4Cl solution 14 in the dissolved NH4Cl feed tank 41 is then fed to the two-fluid nozzle 37, through the NH4Cl solution feed pipe 33 by a feed pump 42. The flow rate of the NH4Cl solution 14 in the NH4Cl solution feed pipe 33 is measured by a flowmeter 43-1, and the supply of the NH4Cl solution 14 is adjusted by a valve V2. The dissolved NH4Cl feed tank 41 is not essential and may not be used.
An air supplying unit 46 feeds the air 38 to the two-fluid nozzle 37 through the air feed pipe 39A, and the air 38 is used as compressing air for spraying the NH4Cl solution 14 from the two-fluid nozzle 37. Accordingly, the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 can be sprayed in fine liquid droplets: As shown in
The flow rate of the air 38 injected from the two-fluid nozzle 37 preferably has an air-water ratio of equal to or more than 100 and equal to or less than 10000 (volume ratio), for example. This is to spray the NH4Cl solution 14 injected from the two-fluid nozzle 37 into the flue 13, in fine liquid droplets.
The air supplying unit 46 feeds the air 34 into the blow pipe 36 through the air feed pipe 40, and the air 34 is used as compressing air for dispersing the liquid droplets of the NH4Cl solution 14 sprayed from the two-fluid nozzle 37. As shown in
The air 34 injected from the injection hole 35 is used to prevent the NH4Cl solution 14 injected from the two-fluid nozzle 37 from being fixed to the blow pipe 36, and to prevent the temperature in the blow pipe 36 from increasing. The air 34 is also used to prevent the NH4Cl solution 14 from boiling and ammonium chloride particles from depositing.
The air 34 flows between the blow pipe 36 and the NH4Cl solution feed pipe 33. Accordingly, the air 34 acts as air for cooling the NH4Cl solution 14, and prevents the heat of the flue gas 12 in the flue 13 from being transmitted to the NH4Cl solution feed pipe 33 from the outside of the blow pipe 36. The temperature in the blow pipe 36 is prevented from increasing and the NH4Cl solution 14 is prevented from being heated. Consequently, the NH4Cl solution 14 is prevented from boiling in the blow pipe 36, and maintained in a liquid state up to when the NH4Cl solution 14 is injected. It is also possible to prevent the two-fluid nozzle 37 from corroding.
Because the temperature in the blow pipe 36 can be prevented from increasing, a metal material can be used for the NH4Cl solution feed pipe 33 and the air feed pipe 39A. The material for the NH4Cl solution feed pipe 33 and the air feed pipe 39A may be, for example, as follows: The NH4Cl solution feed pipe 33 may be a corrosion resistant metal such as a nickel based heat resistant and corrosion resistant alloy like Hastelloy C, and a resin-lined steel pipe (low temperature portion). The air feed pipe 39A may be carbon steel, stainless-steel, and the like. The material for the NH4Cl solution feed pipe 33 and the air feed pipe 39A is not particularly limited to the metal material.
Because the NH4Cl solution 14 can be supplied into the flue 13 from the dissolved NH4Cl feed tank 41 in a room temperature, an inexpensive resin or a resin-lined pipe can be used as a material for the NH4Cl solution feed pipe 33 and the blow pipe 36.
In the mercury reduction system 10A according to the present embodiment, for example, a few to, at most, a few tens of two-fluid nozzles 37 are provided in the flue 13. Conventionally, a few hundreds to a few thousands of NH3 grids are provided in the flue 13, for example. By contrast, only a few to, at most, a few tens of two-fluid nozzles 37 are provided in the flue 13, and the two-fluid nozzles 37 are fixed by flange portions 51 and 53. Accordingly, the nozzles can be replaced easily. In
As shown in
The two-fluid nozzles 37 are used for spraying the NH4Cl solution 14. However, the present invention is not limited thereto, and an ordinary injection nozzle for spraying liquid may also be used.
The blow pipe 36 includes the NH4Cl solution feed pipe 33 and the air feed pipe 39A therein, and the NH4Cl solution 14 is sprayed into the flue 13 from the two-fluid nozzles 37. However, the present invention is not limited thereto. If the NH4Cl solution 14 in the NH4Cl solution feed pipe 33 is prevented from being heated, the NH4Cl solution 14 may be sprayed into the flue 13, by connecting the NH4Cl solution feed pipe 33 and the air feed pipe 39A with the two-fluid nozzles 37, without using the blow pipe 36.
In other words, as shown in
The air 38 is supplied from an air supplying unit 45 and the air 34 is supplied from the air supplying unit 46. In other words, air is separately supplied from different supplying sources. However, the present invention is not limited thereto, and the air may be supplied from the same supplying source. In other words, the air 34 may be supplied from the air supplying unit 45, and the air 38 may be supplied from the air supplying unit 46.
The temperature of the flue gas 12 in the flue 13, for example, is equal to or more than 320° C. and equal to or less than 420° C., and is very hot. The NH4Cl solution feed pipe 33 is provided in the blow pipe 36, and the air 34 is used to cool the NH4Cl solution 14. Accordingly, the NH4Cl solution 14 is maintained in a liquid state up to when the NH4Cl solution 14 is injected from the two-fluid nozzles 37. Because the NH4Cl solution 14 is sprayed from the two-fluid nozzles 37 in liquid droplets, the liquid droplets of the sprayed NH4Cl solution 14 are evaporated, due to the high ambient temperature of the flue gas 12.
In other words, the sprayed liquid droplets of the NH4Cl solution 14 temporarily generate fine NH4Cl solid particles, because the liquid droplets are evaporated by the high ambient temperature of the flue gas 12, and as represented by the following formula (1), decomposed into HCl and NH3, and sublimated. Accordingly, it is possible to generate HCl and NH3 from the liquid droplets of the NH4Cl solution 14 sprayed from the two-fluid nozzles 37, and supply the HCl and NH3 into the flue 13.
NH4Cl→NH3+HCl (1)
The temperature of the flue gas 12 in the flue 13, although depending on the combustion condition of the boiler 11, for example, is preferably equal to or more than 320° C. and equal to or less than 420° C., more preferably equal to or more than 320° C. and equal to or less than 380° C., and more preferably equal to or more than 350° C. and equal to or less than 380° C. This is because the reduction reaction of NOx and the oxidation reaction of Hg can be simultaneously carried out on a denitration catalyst.
NH3 concentration and HCl concentration in the flue gas 12 in the flue 13 are set, relative to NOx concentration in the flue gas 12, so that the ratio of the molar number of NH3 to the molar number of NOx in the flue gas 12 (NH3(NOx molar ratio) is a value equal to or less than one, based on the required denitration performance.
Although depending on the NOx concentration in the flue gas 12, the NH4Cl solution 14 may be sprayed, so that the NH3 concentration and the HCl concentration fall within a range from a few tens to a few hundreds parts per million, or preferably from a few tens to 200 parts per million. This is because NH3 and NOx react at a molar ratio of 1:1, and if NH3 is over-supplied, an excess of NH3 is remained after the reaction. Acid sulfate is produced from NH3 and the components in the flue gas 12. By spraying the NH4Cl solution 14 as the above, it is possible to prevent the inside of the flue 13, the air heater 17, the dust collector 18, and the like from being corroded and damaged, and from being blocked due to ash deposition. It is also possible to prevent the flue gas 12 from leaking from the damaged flue 13.
The Hg concentration in the flue gas 12 is preferably set in a range equal to or more than 0.1 μg/m3N and equal to or less than a few ten μg/m3N, and relative to the HCl concentration in the flue gas 12, it is preferable to set in a range equal to or less than 1/1000 in molar ratio.
The hole diameter of each two-fluid nozzle 37 is preferably equal to or more than 0.01 millimeter and equal to or less than 10 millimeters, and more preferably equal to or more than 0.1 millimeter and equal to or less than 5 millimeters.
The size of the liquid droplets of the NH4Cl solution 14 spayed from the two-fluid nozzle 37 is preferably fine liquid droplets of equal to or more than 1 nanometer and equal to or less than 100 micrometers in average. By generating the fine liquid droplets of equal to or more than 1 nanometer and equal to or less than 100 micrometers in average, the solid particles of NH4Cl generated from the liquid droplets of the sprayed NH4Cl solution 14 can be decomposed into NH3 and HCl in the flue gas 12 in a short retention time, and sublimated. Because the NH4Cl solution 14 does not need to be heated in advance, it is possible to prevent the flue 13 and the two-fluid nozzle 37 from being degraded and corroded.
Accordingly, in the mercury reduction system 10A according to the present embodiment, the NH4Cl solution 14 is sprayed from the two-fluid nozzle 37 in a liquid state. Consequently, the NH4Cl solution 14 is decomposed into HCl and NH3, due to the high ambient temperature of the flue gas 12, and supplied into the flue 13. As a result, the hydrogen chloride vaporizer 122, a spray grid, the hydrochloric acid solution tank 116, and the like in the mercury chlorinating agent feed apparatus of the conventional mercury reduction system, as shown in
The NH4Cl powder 21 used for adjusting the NH4Cl solution 14 is neutral salt. Accordingly, the NH4Cl powder 21 is easy to handle, and inexpensive and easy to obtain as can be used as fertilizer. Because NH3 can be generated from the NH4Cl solution 14, the usage of NH3 can be reduced. Because HCl is a dangerous substance, handling costs, such as a cost for transportation, a cost for legislative permission, and a cost for safety control are expensive. However, the NH4Cl powder 21 can significantly reduce the handling cost.
The NH4Cl solution 14 is dissolved in water and fully evaporated into NH3 and HCl. Because NH4Cl solid particles do not remain, it is possible to prevent the NH4Cl solid particles from accumulating in the flue 13 and on the denitration catalyst provided downstream. It is also possible to prevent the denitration catalyst from deteriorating.
The NH4Cl solution 14 is evaporated into NH3 and HCl, by using the flue gas 12 as a heat source. Accordingly, the installation of sublimation equipment such as a new heat source like steam, for evaporating the NH4Cl solution 14, can be omitted. It is also possible to reduce the retention time required for evaporating the NH4Cl solution 14 in the flue gas 12.
The flow rate of the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 is only a small amount of a few t/h, compared with the amount of flue gas, for example, of 1,500,000 m3N/h. Accordingly, the temperature of the flue gas 12 can be prevented from lowering, for example, to equal to or less than a few degrees. Consequently, it is possible to prevent SO3 in the flue gas 12 from condensing, and also prevent ash in the flue gas 12 from accumulating and fixing in the flue 13 and the like.
Compared with the conventional flue gas control apparatus shown in
Because the NH4Cl powder 21 is used for the NH4Cl solution 14, NH4Cl need not be finely crushed as the conventional method, but may be stored in the pellet state and used accordingly.
It is less expensive to supply a single piece of NH4Cl than to purchase NH3 and HCl separately, as in a conventional manner. Accordingly, operational costs of the device can be reduced, thereby easily collecting the facility costs required for installation.
The supplies of the NH4Cl powder 21 and the water 29 can be adjusted, based on the concentration of the NH4Cl solution 14. Accordingly, the concentration of the NH4Cl solution 14 can be adjusted, based on the concentrations of NOx and Hg in the flue gas 12.
HCl and NH3 generated from the liquid droplets of the NH4Cl solution 14, as shown in
In other words, the reduction denitration apparatus 16 is filled with denitration catalyst. On the denitration catalyst, NH3 is used to reduce NOx as represented by the following formula (2), and HCl is used to oxidize Hg as represented by the following formula (3).
4NO+4NH3+O2→4N2+6H2O (2)
Hg+½O2+2HCl→HgCl2+H2O (3)
As shown in
A mixer that mixes NH3 and HCl may be provided downstream of the two-fluid nozzle 37 and upstream of the reduction denitration apparatus 16. The mixer, for example, may be a static mixer. If NH3 and HCl generated by evaporating the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 are not dispersed enough, the mixer provided upstream of the reduction denitration apparatus 16 can uniformly disperse NH3 and HCl in the flue gas 12.
A flowmeter 61 that measures the flow rate of the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 may be provided downstream of the two-fluid nozzle 37. Accordingly, the flow rate of the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 can be measured. The flow velocity of the flue gas 12 in the flue 13 can also be measured.
NOx concentration meters 62-1 and 62-2 are provided inlet side and the outlet side of the reduction denitration apparatus 16. The reduction rate of NOx in the reduction denitration apparatus 16 can be identified, from the NOx concentration values in the flue gas 12 measured by the NOx concentration meters 62-1 and 62-2. Accordingly, by controlling the NH4Cl concentration and the supply flow rate of the NH4Cl solution 14, from the values of NOx concentration in the flue gas 12 measured by the NOx concentration meters 62-1 and 62-2, the NH4Cl concentration in the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 can be set, so as to satisfy a predetermined denitration performance.
The mercury reduction system 10A according to the present embodiment also includes a mercury (Hg) concentration meter 63 that measures Hg contained in the treatment gas discharged from the reduction denitration apparatus 16, and a hydrogen chloride (HCl) concentration meter 64 that measures HCl contained in the flue gas 12 supplied to the wet desulfurization apparatus 20. The Hg concentration meter 63 may be provided downstream of the wet desulfurization apparatus 20, and measure mercury (Hg) contained in the treatment gas discharged from the wet desulfurization apparatus 20.
The oxidation rate of Hg in the reduction denitration apparatus 16 can be identified, from values of the HCl concentration and the Hg concentration in the flue gas 12, measured by the Hg concentration meter 63 and the HCl concentration meter 64. By controlling the NH4Cl concentration and the supply flow rate of the NH4Cl solution 14, from the Hg concentration value in the flue gas 12 measured by the Hg concentration meter 63 and the HCl concentration meter 64, the NH4Cl concentration and the supply flow rate of the NH4Cl solution 14 sprayed from the two-fluid nozzle 37 can be set so as to satisfy the predetermined denitration performance and to maintain the oxidation performance of Hg.
The additional amount of the NH4Cl solution 14 is controlled, so that the mercury oxidation rate (Hg2+/HgT) is equal to or more than 90%, or the oxidized mercury concentration (Hg2+) is equal to or less than 1 μg/Nm3, at the outlet of the reduction denitration apparatus 16. HgT is the total mercury concentration, and expressed by a sum of the metallic mercury concentration (Hg0) and the oxidized mercury concentration (Hg2+), as the following formula (4).
HgT=Hg0+Hg2+ (4)
The supply of the NH4Cl solution 14 may be determined, by calculating the contents of NOx and Hg in the flue gas 12, from the property of coal used in the boiler 11. In other words, the contents of NOx and Hg in the flue gas 12 can be obtained by burning the property of coal in the boiler 11. If the coal is burnt in the boiler 11 to the maximum extent, the maximum amounts of NOx and Hy in the flue gas 12 can be obtained from the combustion amount of the boiler 11. Consequently, the supply of the NH4Cl solution 14 can be determined, by obtaining the contents of NOx and Hg in the flue gas 12 from the property of the coal used in the boiler 11.
As described below, if equipment for supplying NH3 and HCl is provided in the flue 13, the contents of NOx, Hg, and HCl in the flue gas 12 can be obtained from the property of coal used in the boiler 11, thereby determining the supplies of the NH4Cl solution 14, NH3, and HCl, respectively.
<Configuration of Mercury Reduction System in Which Equipment for Supplying NH3 and HCl are Provided>
As shown in
When the NH3 supplying unit 71 that sprays NH3 into the flue 13 is included, the supply of NH3 supplied from the NH3 supplying unit 71 is also controlled, based on the values of the nitrogen oxide (NOx) concentration meters 62-1 and 62-2.
If the NH3 supplying unit 71, for example, is already installed in the flue 13 and the like, or if the amount of HCl is required less than NH3, the NH4Cl solution 14 is supplied up to the required amount of HCl, and NH3 is added if the amount of NH3 is equal to or more than the required mount of HCl.
The NH3 concentration and the HCl concentration in the flue 13 are controlled, so that the combination of NH3 dissociated from the NH4Cl solution 14 and NH3 to be added is, similar to the above, a value in which the molar ratio of NH3/NOx is a value equal to or less than one, based on the required denitration performance.
The oxidation ratio of Hg in the reduction denitration apparatus 16 is identified, by measuring the Hg concentration and the HCl concentration in the flue gas 12, by the Hg concentration meter 63 and the HCl concentration meter 64 provided downstream of the reduction denitration apparatus 16. The supply of HCl supplied from the HCl supplying unit 72 is also controlled, with the values obtained by the Hg concentration meter 63 and the HCl concentration meter 64.
The additional amount of HCl is set, so that the combination of HCl dissociated from the NH4Cl solution 14 and HCl added by the HCl supplying unit 72 has, similar to the above, the mercury oxidation rate (Hg2+/HgT) of equal to or more than 90%, or the oxidized mercury concentration (Hg2+) of equal to or less than 1 μg/Nm3, at the outlet of the reduction denitration apparatus 16.
<When Concentrations of NOx and Hg are Different>
If the balance of the concentrations of NOx and Hg in the flue gas 12 discharged from combustion equipment such as the boiler 11 is different from ordinary one, the required amount of HCl or NH3 may be supplied into the flue 13, so as to correspond thereto.
In other words, if the HCl concentration required for oxidizing Hg, and the NH3 concentration required for reducing NOx are different, at least one of the required HCl and NH3 may be supplied.
For example, if the amount of HCl required for oxidizing Hg is larger than that of NH3 required for reducing NOx, it means that the amount of HCl is in short supply. In this case, as shown in
If the amount of HCl required for oxidizing Hg is less than that of NH3 required for reducing NOx, it means that the amount of NH3 is in short supply. In such an event, as shown in
The order of the position from which the HCl supplying unit 72 supplies HCl, the position from which the NH3 supplying unit 71 supplies NH3, and the position from which the two-fluid nozzle 37 sprays the NH4Cl solution 14 may be arbitrary. However, it is preferable that the position from which the NH4Cl solution 14 is sprayed, is provided closer to the upstream than the positions from which NH3 and HCl are supplied. This is because the NH4Cl solution 14 takes more time to evaporate and vaporize, than NH3 and HCl.
Accordingly, for example, to supply HCl and the NH4Cl solution 14 into the flue 13, it is preferable to spray HCl from the HCl supplying unit 71, after the two-fluid nozzle 37 sprays the NH4Cl solution 14 from the upstream side.
To supply NH3 and the NH4Cl solution 14 into the flue 13, it is preferable to spray NH3 or urea from the NH3 supplying unit 71, after the two-fluid nozzle 37 sprays the NH4Cl solution 14 from the upstream side.
To supply HCl and NH3 into the flue 13, it is preferable to spray NH3 or urea from the NH3 supplying unit 71, after the HCl supplying unit 72 supplies HCl from the upstream side.
Accordingly, in the mercury reduction system 10A according to the present embodiment, as shown in
In the mercury reduction system 10A according to the present embodiment, NH4Cl is used as an oxidation reduction agent. However, an ammonium halide such as ammonium bromide (NH4Br) and ammonium iodide (NH4I) other than NH4Cl may be used as the oxidation-reduction agent, and use the aqueous solution.
In the mercury reduction system 10A according to the present embodiment, the NH4Cl solution 14 may be used, by mixing at least one of a solution containing a reducing agent and a solution containing a mercury chlorinating agent or both.
As shown in
NH3 is used as a reducing agent. However, urea ((H2N)2C═O) and the like with reducing action may be used as the reducing agent, and use the aqueous solution. To adjust the NH4Cl solution 14, urea ((H2N)2C═O) may be dissolved into the water 39 as well as the NH4Cl powder 31, and the aqueous solution in which the NH4Cl powder 31 and the urea are mixed may be used. In a boiler facility, the NOx concentration varies. In such an event, the supply of NH3 may be increased, by adding urea as well as NH4Cl.
HCl is used as a mercury chlorinating agent. However, a hydrogen halide such as hydrogen bromide (Hbr) and hydrogen iodide (HI) other than HCl may be used as the mercury chlorinating agent, and use the aqueous solution.
In this manner, in the mercury reduction system 10A according to the present embodiment, the non-gaseous NH4Cl solution 14 is sprayed to the upstream of the reduction denitration apparatus 16 in the flue 13 in a liquid state, at ordinary pressure and room temperature, and the sprayed NH4Cl solution 14 is evaporated and decomposed into HCl and NH3. Accordingly, on the denitration catalyst, Hg and NOx in the flue gas 12 can be oxidized and reduced, respectively. Consequently, the reduction performance of Hg in the flue gas 12 can be maintained. The installation of equipment such as an HCl vaporizer, a spray grid, and a storage tank, can be omitted. Because the NH4Cl powder 21 is easy to handle, it is possible to significantly reduce the cost for legislative permission and the installation cost required for safety control. The chemical cost of the NH4Cl powder 21 is also inexpensive, and the flue gas 12 is used as a heat source to sublimate NH4Cl generated from the liquid droplets of the NH4Cl solution 14 being sprayed. As a result, new sublimation equipment is not required, thereby reducing operational cost.
A mercury reduction system according to a second embodiment of the present invention will be described with reference to the accompanying drawings.
As shown in
The arithmetic apparatus 32 calculates the supply speed of the NH4Cl solution 14, based on the concentration value of the NH4Cl solution 14 measured by the NH4Cl concentration meter 31. The supply speed of the NH4Cl solution 14 calculated by the arithmetic apparatus 32 is transmitted to the valve V2. Accordingly, the flow rate of the NH4Cl solution 14 that flows through the NH4Cl solution feed pipe 33 can be adjusted, by adjusting the opening and closing of the valve V2. For example, on referring to the flow rate of the NH4Cl solution 14 when the concentration of the NH4Cl solution 14 is about 20 wt %, if the concentration of the NH4Cl solution 14 is higher than 20 wt %, the flow rate of the NH4Cl solution 14 is lowered, and if the concentration of the NH4Cl solution 14 is lower than 20 wt %, the flow rate of the NH4Cl solution 14 is increased.
Accordingly, the NH4Cl solution 14 can be supplied into the flue 13 from the two-fluid nozzle 37 at an appropriate flow rate, based on the concentration of the NH4Cl solution 14 in the NH4Cl dissolving tank 27. In this manner, it is possible to reliably evaporate NH4Cl, thereby more reliably preventing the powder and the like resulting from NH4Cl from remaining.
A mercury reduction system according to a third embodiment of the present invention will be described with reference to the accompanying drawings.
As shown in
The concentration of the NH4Cl solution 14 can be arbitrarily adjusted, because the arithmetic apparatus 32 adjusts the supply of the NH4Cl powder 21 fed into the NH4Cl dissolving tank 27 by the feeder 25, and the supply of the water 29 fed into the NH4Cl dissolving tank 27 by a valve V1, based on the NOx concentration and the Hg concentration in the flue gas 12, corresponding to the concentration value of the NH4Cl solution 14 measured by the NH4Cl concentration meter 31. The flow rate of the NH4Cl solution 14 that flows through the NH4Cl solution feed pipe 33 can be adjusted with a valve V2, by the feed rate of the NH4Cl solution 14, corresponding to the adjusted concentration of the NH4Cl solution 14.
The concentration of the NH4Cl solution 14 can be arbitrary adjusted, based on the NOx concentration and the Hg concentration in the flue gas 12. Accordingly, it is possible to supply the NH4Cl solution 14 in an appropriate flow rate into the flue 13 from the two-fluid nozzle 37, based on the adjusted concentration of the NH4Cl solution 14. Consequently, the required amount of NH4Cl can be supplied into the flue gas 12, corresponding to the concentrations of NOx and Hg in the flue gas discharged from combustion equipment such as a boiler. In this manner, it is possible to reliably evaporate NH4Cl, thereby more reliably preventing the powder and the like resulting from NH4Cl from remaining.
In this manner, the mercury reduction system according to the present invention sprays NH4Cl into the flue in a liquid state, evaporates NH4Cl generated from the fine liquid droplets of the sprayed NH4Cl by the flue gas that passes through the flue, and decomposes into HCl and NH3. Accordingly, it is possible to prevent operational costs from increasing, while maintaining the reduction performance of Hg.
With the present invention, an oxidation-reduction agent is sprayed to the upstream of a reduction denitration apparatus in a flue in a liquid state, and the sprayed non-gaseous oxidation-reduction agent is evaporated and decomposed into hydrogen chloride and ammonia. Accordingly, mercury and NOx in flue gas can be oxidized and reduced, respectively. As a result, it is possible to keep operational cost low, while maintaining the mercury reduction performance in a wet desulfurization apparatus.
This patent document claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 61/223,177, filed on Jul. 6, 2009, which is herein incorporated by reference.
Number | Date | Country | |
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61223177 | Jul 2009 | US |