TWI484995B - Dry processes, apparatus, compositions and systems for reducing sulfur oxides and hci - Google Patents

Description

Dry method, device, composition and system for reducing sulfur oxides and hydrogen chloride Cross reference and priority claim

The present application claims priority to PCT Application No. PCT/US13/34,807 filed on Apr. 1, 2013, the entire disclosure of which is hereby incorporated by reference.

The present invention relates to a dry process, apparatus, composition and system for reducing sulfur oxides (and in particular sulfur dioxide), and HCl emissions, in a process utilizing an efficient combination of an adsorbent and an adsorbent dopant, The purpose of the efficient combination is to achieve the carrying of SO _x and/or HCl-containing gas with a short but effective residence time at a high reaction rate and adsorbent utilization rate at a temperature effective to provide a significant reduction in sulfur dioxide and/or HCl. Coverage of the entire cross section of the channel. The present invention provides an once-through, dry process, and which advantageously introduces the adsorbent and adsorbs the dopant in the form of a slurry to enable uniform processing.

Due to the perceived harmful effects of acid rain, the problem of sulfur oxides has become a challenge for manufacturers and regulators of combustion plants. Department of sulfur oxides formed during the combustion of sulfur-containing carbonaceous fuel, and is generally referred to as SO _x, and comprising sulfur dioxide (SO ₂₎ and sulfur trioxide (SO _3). The vast majority of SO _x systems exist as SO ₂ . However, SO ₃ (such as H ₂ SO ₄ ) increases the emitted particulates and can cause cold end corrosion. Therefore, an effective system must be able to cope with both SO ₂ and SO ₃ . Ideally, this method should also solve the problem of hydrochloric acid (HCl).

This technology has provided numerous technologies. In general, they can be referred to as flue gas desulfurization technology, FGD. See, for example, Srivastava, Ravi K .; Controlling SO ₂ Emissions: A Review of Technologies; EPA/600/R-00/093, November 2000 . These technologies include both wet and dry technologies, and can employ existing equipment such as duct work or provide separate reactors.

According to Srivastava, FGD can be divided into two broad categories: (1) once-through and (2) reproducibility. In the former, the adsorbent is discarded after use; in the latter, the adsorbent is regenerated after adsorbing SO ₂ .

In a one-shot process, the adsorbed SO ₂ is bound by an adsorbent and the adsorbent is considered to be depleted. The spent adsorbent can be disposed of or recovered as a useful by-product such as gypsum, depending on quality and market factors.

It is considered renewable based techniques may be treated to the adsorbent to release SO _2, and to give useful products. After regeneration, the adsorbent may be recycled for washing the additional SO _2.

Disposable and regenerative technologies can each be further divided into wet or dry. The wet process produces wet slurry waste or by-products, and the washed flue gas is filled with water. The dry process produces dry waste and the washed flue gas is not filled with water.

To further understand the various technologies, Srivastava has been mentioned to the readers above, in which the authors divided the main FGD technologies into three broad categories: wet FGD (consisting of disposable wet FGD), and (2) dry FGD (by disposable dry FGD). Composition) and (3) Renewable FGD (composed of wet and dry regenerable FGD).

The wet FGD process may employ a wet scrubber, which typically employs a large column that contacts the combustion flue gas with a slurry of calcium carbonate or the like that is counter-phase sprayed with respect to the flue gas stream. Suitable chemical slurries may include calcium carbonate (limestone), lime (CaO, Ca(OH) ₂ in the slurry), trona (sodium dicarbonate), sodium bicarbonate, dolomite, and the like, or such materials. Blend. In limestone-based scrubber, SO _x trap formed by CaSO _3, which is part of the natural-based oxide, or oxidized to form gypsum by significantly (CaSO _4), which can be used for commercial purposes. The SO _x reacts with the adsorbent after a relatively long time in the liquid phase of the stirred tank. Fuels with a high chloride content will change the chemical balance in the liquid and may adversely affect scrubber efficiency. Quality and market factors will determine the value and fate of waste adsorbents. These wet scrubbers are expensive to install and operate and cannot be easily adapted to all plants.

The dry process can introduce these same types of chemicals (whether dry or as a fast-drying slurry) into the flue gas stream of the furnace, a separate reactor or pipe or other passage carrying the flue gas, where SO _{x is} in a certain It is trapped to some extent and can be disposed of in the form of dry particles.

In one type of dry process, the slurry is sprayed into a separate reactor - retrofitted from an industrial spray dryer - for intimate contact with the flue gas for an appropriate reaction time, such as ten seconds or more. These methods are quite effective, but not as effective as wet scrubbers. However, they are also capital intensive, but do not provide the high quality gypsum that can be achieved with wet scrubbers.

In the in-furnace sorbent injection, the dry sorbent is injected directly into the furnace at an optimum temperature range above the flame. As a result of the action of high temperatures (e.g., at a grade of 2000 °F), the adsorbent particles (e.g., typically calcium hydroxide or calcium carbonate) decompose and become porous solids with a high surface system. The residence time is extremely short, on the order of a few seconds, and the sorbent particles tend to foul before the chemical is fully utilized.

As the furnace (in-furnace) sorbent injection as the delivery tube (In-duct) involves injecting an adsorbent containing SO _x sorbent is injected directly into the gas. In these methods, the adsorbent is introduced into the flue gas delivery tube, but the contact does not have the advantage of a reaction vessel as used in a spray dryer compared to spray drying, and is greatly plagued by contact time. For example, usually only a few seconds. Intraductal injections typically employ alkali metal or alkaline earth metal oxides or hydroxides such as trona, sodium carbonate, calcium hydroxide, magnesium hydroxide, dolomite or the like, such as Srivastava, supra and Michalak et al. Patent No. 5,658,547. No. 5,492,685 to Moran describes a hydrated lime having a high surface area and a small particle size, which is prepared by hydrating an aqueous solution of lime and an organic solvent, and preferably washing the resulting hydrate with an aqueous solution of an organic solvent before drying. . The high surface area hydrates (e.g., up to 85 m ² /g) are used to remove SO ₂ from the gas stream.

Case of U.S. Patent No. 5,658,547 Michalak et al., Describes the combustion gases from a large boiler removal of SO _x and particulates. In the primary treatment zone, the system at about 900 ° to about 1300 ℃ temperature (about 165 ° to about 2375 deg.] F) will effectively reduce the SO _x containing alkaline SO _x - reducing composition, and preferably a nitrogen-containing composition The slurry is introduced into the combustion gas. The gases are cooled by initial contact with the steam producing unit and then by contact with a gas-to-gas heat exchanger. The cooled gas is then subjected to a secondary treatment in which it is first humidified and further cooled by introduction of a water spray or aerosol to lower the temperature to 100 ° C (212 ° F) or lower. The SO _x - reducing composition maintains the humidified gas by contacting the reaction time is at least two seconds duration. The particulate solids are then separated from the gases by a fabric filter. The cleaning gas is reheated by a gas-to-gas heat exchanger and then discharged to the atmosphere.

Such method requires a large number of these SO _x - reducing agent fed to the furnace or the rear end of the delivery tube, and added to a large amount of solid dust collecting device, and may reduce the performance in some cases, and under certain operating conditions to cause And processing problems. Dry scrubbing methods still need to be able to increase sorbent utilization and removal efficiency.

Other dry processes may include fluidized beds that provide longer reaction times. These methods are typically designed to recycle the adsorbent multiple times with the combustion gases to increase economic efficiency by increasing the utilization of the adsorbent. Adsorbents used in such processes are intended to be recycled, and thus are more expensive to prepare and process.

An example of such a subsequent type of process can be found in U.S. Patent No. 4,755,499 to the name of U.S. Patent No. 4,755,499, which is incorporated herein by reference. The adsorbent is comprised of (a) an alumina substrate having a specified pore volume and (b) a defined amount of an alkali or alkaline earth component relative to the substrate. Small amounts of other metal oxides can also be used. These adsorbents are made recyclable and wear resistant. its The material can be regenerated by heating in an inert atmosphere at a temperature of up to about 350 ° C and then reused.

In a related disclosure, U.S. Patent No. 6,281,164 in, et al., The teachings of Demmel, having life SO ₂ to SO ₃ and SO ₃ oxidation catalyst component of SO _x absorbing component of the additive may be employed as separate and distinct by The physical particles or pellets are each extended by these components. The particles are subjected to spray drying or drying followed by calcination to produce a size range having substantially all of the particles will be retained by a standard US 200 mesh screen, and substantially all of such particles will pass through a standard US 60 mesh screen. Prepared by microspherical particles. SO _x reduction process of the trapped SO _x must be on the particles, such particles are then regenerated for reuse. Such particles are too expensive for disposable methods and are in fact too large to achieve good utilization in their methods.

Another example of a regenerable adsorbent can be found in U.S. Patent No. 5,114,898 to Pinnavaia et al., which describes the use of heated stratified double hydroxide (LDH) adsorbents from gas streams (especially self-igniting coal to generate electricity). Factory flue gas) method for removing toxic sulfur oxides. The sorbent compositions comprise a metal component that isomorphously replaces all or a portion of the M ¹¹ and/or M ¹¹¹ ions in the LDH structure layer (this patent defines M ¹¹ as a divalent metal) And M ^{111 is} defined as a trivalent metal) or incorporated into the adsorbents by impregnation into a metal salt to promote oxidation of sulfur dioxide.

In another related teachings in U.S. Patent No. 5,520,898 describes Pinnavaia et al of alkali / clay composite is used as an adsorbent to remove SO _x of the flow of flue gas. The composite comprises a bentonite clay and a sorbent component, such as an alkaline earth metal hydroxide and carbonate, and a metal oxide or metal oxide precursor, preferably selected from transition metal ions. It is said that the bentonite clay serves as a support for the reactive substrate and a dispersant for improving reactivity. It is said that the swelling of the bentonite clay is a cause of higher reactivity of the adsorbent. It is contemplated to inject these adsorbents along with coal, especially in boilers (700°-1000°C).

Currently there is a high percentage can be, and needs improvement based on economic manner SO ₂ and / or the capture of HCl from the viewpoint of material technology, equipment and disposal of view.

The present invention provides an extremely reasonable cost by reducing SO _x emissions and HCl generated a very positive impact on the methods, devices, compositions and systems for air quality. The invention can be used as a retrofit solution for existing plants and can be used in the design of new plants.

In one aspect, the present invention provides a SO _x and / or HCl Method combustion chamber for reducing the emissions, comprising: determining a location of a combustion chamber for feeding dolomite hydrate of adsorbent and adsorbed dopant; determining the The physical form of the adsorbent and the adsorbed dopant and the injection parameter; the dolomite hydrate adsorbent and the adsorbed dopant are injected into the combustion gas containing SO _x and/or HCl, and the introduction operation system is effective The adsorbent is used to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent containing no adsorbent dopant; and the spent adsorbent is collected.

In some embodiments, the adsorbing dopants will comprise at least one member selected from the group consisting of compositions comprising adsorbing dopants, the adsorbing dopants comprising selected from the group consisting of copper ammonium acetate, diammonium diacetate, A copper composition of a group consisting of copper copper triacetate, copper triammonium acetate, copper tetraammonium sulfate, copper gluconate (and hydrates thereof), and a mixture of any of these materials. From another point of view, the dopant may be selected from one of the group consisting of a composition defined by the formula Cu(NH ₃ ) _x (lower carboxylate) _y , wherein the lower carboxylic acid The salt is selected from the group consisting of formate, acetate and propionate, x is an integer from 0 to 4, y is an integer from 0 to 2, and x+y is equal to or greater than 1.

In an embodiment of the invention, the dopant will comprise an adsorbing dopant comprising an aqueous lower calcium carboxylate complex of lower calcium carboxylate and lower ammonium carboxylate.

In embodiments, the dopants will comprise a lower aqueous calcium copper carboxylate complex of a lower calcium carboxylate and a lower ammonium carboxylate containing a lower weight carboxylic acid of about 13 parts by weight. Copper acid (measured according to the dihydrate) is about 2 parts of the lower ammonium carboxylate, and about 10 parts of the 29% aqueous ammonia solution, and the pH of the solution is in the range of about 7.1 to 7.4.

In an embodiment, the dolomite sorbent hydrate and the adsorbent dopant are injected by an injection member comprising a plurality of nozzles in the introduction region, and the nozzles are placed to achieve at least 90% in the introduction region Coverage.

In another aspect, the present invention provides a gas flow of SO _x and / or HCl means of reduction, comprising: injection means positioned in the flue gas of the combustion of the fuel passage position by the arising of the other injection member can be with respect to the flue gas SO _x and / or concentration of the HCl feed rate determined in advance and dolomite hydrate adsorbent adsorbing a dopant, and these means can also be injected in a predetermined physical a form and a predetermined injection parameter (including droplet size, momentum and concentration) of the adsorbent and the adsorbed dopant to introduce a dolomite hydrate adsorbent and an adsorbing dopant; thereby having an adsorbing dopant The dolomite hydrate adsorbent can capture sulfur oxides with high efficiency.

In another aspect, the present invention provides for reducing the SO _x and / or HCl of the gas flow system, comprising: means for determining within the combustion chamber and the delivery tube and an adsorbent adsorbing member dolomite hydrate thereof for feeding a position of the dopant, and a computer modeling member that determines a physical form of the dolomite hydrate adsorbent and the adsorbed dopant injection member at the channel position of the flue gas, and the injection member can be relative to the passage SO _x and / or measuring the concentration of the HCl feed rate determined in advance and dolomite hydrate adsorbent adsorbing a dopant, and such means can also be injected in a predetermined physical form of the adsorbent and the adsorbent and The predetermined injection parameters (including droplet size, momentum and concentration) of the dopant are introduced into the dolomite hydrate adsorbent and the adsorbed dopant; thereby, the dolomite hydrate adsorbent having the adsorbed dopant may have The characteristics of sulfur oxides and/or HCl are captured with high efficiency as specified below.

In yet another aspect, the present invention provides a composition for reducing SO _x and/or HCl of a gas stream comprising: a dolomite hydrate adsorbent and an adsorbent dopant comprising copper and/or iron, After introduction into a hot gas stream containing SO _x and/or HCl, it will dehydrate and cause breakage into particles ranging in size from about 0.01 to about 0.2 microns, wherein the weight ratio of dolomite hydrate to adsorbed dopant (dry The base is in the range of from about 100:1 to about 1:1, and the adsorbent dopant is selected from the group consisting of water soluble or water dispersible copper and/or iron compositions in the flue gas treated by Active copper or iron is released upon in situ heating.

Compared with the competitive method, the present invention provides several advantages, wherein the superiority is that the treatment of flue gas to reduce SO _x can also reduce HCl; since the utilization rate of the adsorbent is more effective, the amount of adsorbent material can be reduced; High sulfur removal rates are possible; they can be retrofitted with simple equipment.

Other preferred aspects and advantages thereof are shown in the following description.

10‧‧‧ combustion chamber

12‧‧‧ pipeline

14‧‧‧ pipeline

16‧‧‧burning area

18‧‧‧ arrow

20‧‧‧ Heat exchanger section

28‧‧‧ pipeline

30‧‧‧Mixed platform

32‧‧‧ pipeline

34‧‧‧ pipeline

36‧‧‧ pipeline

36'‧‧‧ pipeline

38‧‧‧ pipeline

38'‧‧‧ pipeline

40‧‧‧ Controller

50‧‧‧Particle recovery component

52‧‧‧ pipeline

54‧‧‧ pipeline

The invention will be more fully understood, and its advantages will become more apparent from the <RTIgt;

2 is a flow chart of another embodiment of the present invention.

Reference will first be made to Figure 1, which is a flow diagram of one embodiment of the present invention. The type of combustion chamber 10 can be used to produce a combustion chamber for steam generation, process steam, heating or incineration for power generation. It will be appreciated that other types of combustion chambers may be employed to take advantage of the present invention. All parts and percentages in this description are based on the weight of the material at the particular point of the process being treated or in the dry state, unless otherwise stated.

Coal is fed to combustion chamber 10 via line 12 and combusted with air from line 14 in combustion zone 16. The combustion of coal having a high sulfur content with the resulting reduced sulfur dioxide is one of the advantages of the present invention. Advantageously, HCl can also be reduced. It will be appreciated that the principles of the present invention are applicable to other carbonaceous fuels and fuel mixtures (any other selected fuel, typically carbonaceous thermal fuel or waste).

The combustion air supplied via line 14 is preferably preheated by a gas-to-gas heat exchanger (not shown) that is self-contained by the gas-to-gas heat exchanger (not shown) Show) transferring heat at the outlet end of the combustion apparatus, such as downstream of heat exchanger section 20, which recovers useful heat energy from the combustion chamber. Hot combustion gases flow through the combustion chamber (as indicated by arrow 18) and flow through heat exchanger portion 20, which transfers the heat of the combustion gases to water or steam used to generate steam or superheated steam. Other heat exchangers, including economizers (downstream, and not shown), may also be provided depending on the design of the particular boiler.

Based on a large number of test procedures, it has been determined, and the sorbent composition of the adsorbed dopant in small portions and far superior to the determined long been associated with this technique described above with an effective reduction of the SO _x sorbent material in the Many sorbent materials. When used together with an adsorbing dopant comprising a copper and/or iron composition, the present invention defines a fine particle size and high surface area dolomite hydrate (also known as hydrated dolomite and dolomite slaked lime) as a high efficiency adsorbent. .

The adsorbent dopant is a water-soluble or water-dispersible composition that can be added to copper and/or iron in a dolomite hydrate adsorbent for introducing a flue gas to be treated (for example, as Used in situ to form copper or iron oxides of copper or iron oxide. When the flue gas being treated is heated in situ by the treated flue gas, the adsorbed dopants release the active form (i.e., the substance) of the oxide of copper and/or iron. The adsorbed dopant is typically used at a ratio of from about 1 to about 10 pounds per ton of fuel (dry basis) and a narrower range is from about 2 to about 6 pounds per ton.

The adsorbent dopant and dolomite hydrate adsorbent will typically be used in a weight ratio (dry basis) of dolomite hydrate to adsorbed dopant in the range of from about 100:1 to about 1:1. A more preferred ratio will range from about 50:1 to about 5:2. Among the adsorbed dopants are the iron salts such as ferric nitrate and copper salts, such as copper nitrate, which are listed below, and the compositions of U.S. Patent Nos. 3,900,504 and 4,020,180, which are incorporated herein by reference. The entire disclosure of such cases is hereby incorporated by reference in its entirety.

In embodiments, the adsorbent dopant may be believed to form a water-soluble or water-dispersible copper and/or iron group of copper and/or iron oxide upon heating in situ by the treated flue gas. Compound. The compositions of particular reference are described in U.S. Patent No. 4,020,180, the disclosure of which is incorporated herein by reference. Preferably, in accordance with U.S. Patent No. 4,020,180, the composite will comprise about 13 parts by weight of lower calcium carboxylate (as measured by dihydrate) to about 2 parts of lower ammonium carboxylate, and about 10 parts of a 29% aqueous ammonia solution having a pH in the range of about 7.1 to 7.4.

In an embodiment, the dopant according to the present invention is highly soluble or dispersible in water and reacts with the hot combustion gases to provide a chemical composition that is chemically different from the contact with the combustion gases. Preferably, the dopant composition comprises a copper composition having copper that can be released in an active form at the temperatures involved to form a reactive copper entity. Although copper is theoretically oxidized to copper oxide, CuO, applicants do not want to be limited by a particular theoretical reaction.

Among the dopants of interest in the present invention are compositions comprising copper and ammonia moieties. Among the compositions are the copper ammonium compositions, including the copper ammonium compositions having one or more copper atoms and one or more ammonium moieties. Water solubility or dispersibility is important because it has been shown that the introduction of water, etc., is an efficient way to achieve the necessary distribution after dissociation. Chemical dispersants and agitation may be employed as necessary.

In an embodiment of the invention, the adsorbing dopants will comprise a solvent selected from the group consisting of copper ammonium acetate, diammonium acetate, copper ammonium triacetate, copper triammonium acetate, copper ammonium tetraammonium, copper gluconate (and hydrates thereof) And a copper composition of a mixture of any of these materials. From another point of view, the dopant may be selected from one of the group consisting of a composition defined by the formula Cu(NH ₃ ) _x (lower carboxylate) _y , wherein the lower carboxylic acid The salt is selected from the group consisting of formate, acetate and propionate, x is an integer from 0 to 4, y is an integer from 0 to 2, and x+y is equal to or greater than 1.

It can be closely related to the present composition and hydrates, as well as other copper sources of similar potency on / or reaction with SO ₂ and HCl. Copper may be part of a composition free of ammonium, it is believed that the utility of such compositions due to the presence of ammonia will be facilitated, because such treatment (e.g., due to the NO _x reduction) of the result, or if necessary make-up ammonia or Urea or other substances that can effectively produce ammonia at the temperatures involved, as well as compounds with comparable effects, such as ammonia and its salts, urea decomposition products, ammonium salts of organic and inorganic acids, ammonium carbamate, biuret, trimerization Monodecyl cyanamide, diammonium cyanamide, ammonium cyanate, ammonium carbonate, ammonium hydrogencarbonate; ammonium carbamate; triuret, cyanuric acid; isocyanic acid; urine formaldehyde; melamine; A mixture and equivalent of a urea and any amount of such materials.

Among the dopants containing copper and not containing ammonium, there are copper acetonitrile (and its hydrates), copper citrate (and its hydrates such as hemipentahydrate), copper formate (and its hydration). , copper acetate monohydrate, copper nitrate (and its hydrates), copper 2,4-pentanedione (and its hydrates), copper sulfate (and its hydrates), copper gluconate (and its hydrates) ), a copper soap of fatty acids, and a mixture of any such materials.

The dolomite hydrate processed by the adsorbent and the gas containing SO _x heat of the flue gas stream composed of dehydrated and crushed to lead in place within a size range of from about 0.01 to about 0.2 microns, and containing Particles of copper and/or iron oxide dispersed sufficiently therein.

Typically, dolomite hydrate the adsorbent with the adsorbed dopant as a slurry with the hot flue gas containing SO _x into contact, and the composition dehydrated, crushed into particles and cause (e.g., from about 0.01 to about 0.2 Within the size range of micrometers) (based on model establishment, proper placement of the syringe and adjustment of droplet size, momentum and concentration prior to introduction), the particles are dispersed in the furnace portion of the flue gas, the delivery tube or other The cross section of the device. The dolomite hydrate can also be used in a dry form, wherein this allows uniform distribution over the flow path of the treated flue gas.

Preferred conditions would require the introduction of the adsorbent and the dopant using modeling techniques such as computational fluid dynamics that can be used to initially determine the optimum location (region) for direct processing of the chemical within the boiler and/or delivery tube. Preferably, the introduction of the preferred adsorbent and dopant will cause the adsorbent and the dopant to substantially reach a three-dimensional portion of the channel that completely covers the gas to be treated. Preferably, a plurality of nozzles will be spaced apart in the regions to achieve a coverage of at least 90% at the temperatures necessary for the reaction. This portion may have a depth in the flow direction as necessary to ensure complete coverage from the adsorbent used and the dopant injector. In other words, the region will preferably have a depth in the flow direction sufficient for each conical or similar spray pattern of the nozzle for introducing the adsorbent and the dopant to overlap with at least one other spray pattern, thereby Adsorbents and dopants are provided throughout the cross section of the region. For processing of the three-dimensional portion may be referred to define lead-in area, and the water adsorbent and the dopants in the effective control of HCl introduced into the lower region and / or conditions of SO _x emissions. After this region (i.e., downstream), so that the combustion gas and the adsorbent now has a dopant in the treatment of those sufficient to HCl gas and / or the reduction of the reaction time after _the SO _x concentration discharged.

According to the present invention, it has been found that a dolomite hydrate adsorbent capable of effectively trapping SO _x and/or HCl is used as dolomite hydrate, and is preferably mixed with water to form a concentration suitable for storage and processing with or without chemical stability. The slurry of the agent, for example, is at least about 25%, and preferably at least about 40%, by weight of the solids. The preferred concentration is in the range of from about 30 to about 50% by weight, such as from about 35 to about 45% by weight, based on the dry weight of the dolomite hydrate. The adsorbed dopant can be blended with the dolomite hydrate adsorbent at any implementable point prior to introduction of the hot combustion gases. In some cases, it is introduced into the slurry tank or injection equipment not long before the introduction of the treated flue gas.

Referring to FIG 1, which depicts the platform 30 for the preparation of mixed dolomite hydrate slurry of the adsorbent, which preferably has the form of a high surface area-based form of, for example, greater than about 100 m ² / g (BET). For example, the dolomite hydrate adsorbent and can be supplied via line 32, water can be supplied via line 34, and the adsorbed dopant can be supplied via line 36. A typical characteristic of the sorbent slurry is from about 25 to about 45 weight percent dolomite hydrate solids in water. Suitable stabilizers can be used to avoid the need to continuously agitate the tank, but it is preferred to provide agitation. The material is further characterized by a mass average particle size of from about 1 to about 5 microns (μ), for example, nominally from about 2 to 4 microns. An alternative procedure is shown in Figure 2 in which the adsorbed dopant can be added to the dolomite hydrate adsorbent slurry in line 38 via 36' and mixed in a suitable manner in the line. In all cases, the relative amounts of such materials to water can be controlled by a suitable controller 40; or the ingredients and feed can be manually adjusted. The dashed lines in the figure schematically designate control lines for proper communication between various control lines and valves and controller 40.

Preferably, the dolomite hydrate adsorbent in the slurry with the adsorbed dopant is introduced into the treated flue gas. The flue gas will typically be at a temperature below about 2200 °F where it is to be treated, and will typically be in the range of from about 2100° to about 1500°F, preferably from about 1900°F to about 1600°F. In the case of reduced HCl, such temperatures are effective at temperatures below 1600 °F, such as typically below 900 °F, such as from about 350 °F to about 700 °F. The slurry will typically be introduced in small droplets having an average diameter of from about 10 to about 350 microns (e.g., from about 50 to about 200 microns) such that the adsorbent will react with the gas when the dolomite hydrate particles are intimately mixed with the adsorbing dopant. contact. Upon contact with the flue gas, the slurry will dry out and it is believed to break up to form ultrafine particles having a particle size of from about 0.01 to about 0.2 microns (e.g., from about 0.02 to about 0.1 microns).

Dolomite hydrate adsorbents feed rate can be set to any calculated to effectively reduce the rate of SO _x concentration in the flue gases, and its amount will depend on the sulfur content of the fuel. For coal having from about 0.2 to about 3% sulfur, the feed rate of about 50 pounds of adsorbent per ton of fuel will be the appropriate starting point, and the exact feed rate is to be determined experimentally. A typical feed rate will be in the range of from about 10 to about 100 pounds of dolomite hydrate (dry weight) per ton of fuel, and a preferred rate will be from about 20 to about 90 pounds per ton of fuel (e.g., from about 30 to about 70). Pounds) Within the range of dolomite hydrates. Dolomite hydrate will generally be from about 0.15: 1 to about 1.4: 1 dolomite hydrate of flue gas SO ₂ weight ratio used. The preferred ratio will range from about 0.45:1 to about 1.2:1.

One of the advantages of the present invention is that the adsorbent and dopant achieve substantially complete coverage in the combustion gases in the introduction zone at the temperatures necessary for the reaction. If necessary, the portion may have a depth in the flow direction to ensure complete coverage from the sorbent injector used, and will depend on the spray pattern of the syringe and the velocity of the gas. In a variant of the invention, white The marble hydrate adsorbent and adsorbent dopant are introduced via separate syringes adjacent or in series such that the spray pattern of each set of syringes (and possibly many syringes across the portion) overlaps at least to some extent . Preferably, the present invention will determine the dolomite hydrate adsorbent and the adsorbed dopant in the combustion chamber by establishing a model (eg, by mechanical modeling, or by computational fluid dynamics of a computer and data input member). The position, and the physical form and injection parameters of the dolomite hydrate adsorbent and the adsorbed dopant injection member at the position on the flue gas passage of the combustion chamber (as in line 18 of Figures 1 and 2) are fully functional. . Note that Figure 2 shows the line 28 after additionally or alternatively introducing slurry into the heat exchanger portion 20 via line 38', where the temperature will become lower, such as below 900 °F, for example from about 700 ° to about Within the range of 200 °F.

The injection of the present invention using a suitable means, such as an internal mixing or external mixing type nozzle (not shown), which may be based (but not necessarily) air atomizing, and can be measured with respect to the passage of the SO _x concentration in a predetermined Rate feed dolomite hydrate adsorbent and adsorbed dopant. Preferred are internal mixing nozzles capable of producing very small droplets. The injection member should also be capable of introducing a dolomite hydrate adsorbent and an adsorbing dopant in a predetermined physical form and predetermined injection parameters (including droplet size, momentum, and concentration) of the adsorbent and the adsorbed dopant.

Preferably, an air assisted atomizing nozzle is provided for introducing the dolomite hydrate adsorbent and adsorbing dopant into the combustion gas prior to flowing through the heat exchanger portion 20. The positions of the nozzles are preferably determined by computational fluid dynamics, as taught by, for example, U.S. Patent No. 5,740,745, the disclosure of which is incorporated herein by reference. The concentration and flow rate will first be determined by modeling to ensure that the proper amount of chemical is supplied to the correct location in the combustion chamber in the correct physical form to achieve the desired result of reducing SO ₂ and/or HCl.

After introduction of the adsorbent and adsorption of the dopant, the gas is passed through a particulate recovery member 50, which may include one or more of a fabric filter and/or an electrostatic precipitator. One of the advantages of the present invention which is based, as the combination of dopants and Adsorption adsorbent after contact time of less than 3 seconds thus efficiently removed based SO _x, as in prior art so as to reduce the activity of the same adsorbent treatment, the fabric filter The increased reaction time is irrelevant. The solids can be recovered via line 52 and the flue gas can be discharged via line 54.

The following examples are presented to further illustrate and illustrate the invention and are not to be considered as limiting in any respect. All parts and percentages are by weight unless otherwise indicated.

Example 1

This example describes a group of the prior art as identified with the combination according to the present invention have utility was the SO _x - reduce the introduction of the adsorbent.

A series of tests were conducted using a laboratory pilot plant scale combustor. The combustion chamber is a vertical, up-fired/28-foot high cylinder with an internal diameter of 3.5 feet, capable of carrying a gas velocity of 10 to 20 feet per second and a residence time of 1.3 to 2.5 seconds, depending on the rate of combustion. (firing rate). The design furnace has an outlet gas temperature of 2200 °F.

The main body of the furnace was constructed from seven four-foot-high sections, each of which was a water-cooled jacket with a four-inch fireside lining cast refractory. The refractory lining limits heat dissipation to ensure proper simulation of the heating environment found in the original size furnace.

The burner is mounted coaxially on the bottom of the furnace, and is preheated by the ignition of the upper end of the natural gas and the coal for testing is pulverized. It is equipped with a flow control system for secondary air flow and a set of registers that are different from flow control for imparting secondary air vortices. The secondary air and primary air-coal mixture enters the furnace via a refractory crater at a 25° half angle. Two clearing ports are provided in this section to periodically remove the bottom ash of the furnace.

The combustion gases exit the vertical furnace via a horizontal convection passage that is designed to remove most of the heat of the flue gas. The heat sink was designed to simulate the time-temperature curve found in the utility boiler. Will be a series of three air cooled tubes (three air- A cooled tube bank is installed in the convection channel and uses air cooling to control the temperature profile of the flue gas or the metal surface temperature of the tube for fouling/ash deposition studies. The convection tube group is followed by a cross-flow tube air preheater for preheating the primary and secondary air. Finally, the flue gas was cooled to a nominal 300 °F using four tube-in-shell recuperators.

The convection section is 1.5 feet by 1.5 feet by 22 feet and provides a gas velocity of 30 to 60 feet per second and a residence time of 0.4 to 0.8 seconds, again at the burning rate. The convection section is designed for a temperature range of 2200 to 1200 °F.

Connect a fully extracted, continuous emission test (CEM) system to a computer control system. The combustion chamber was operated at about 3.4 MMBTU/hr, with a typical combustion chamber having an excess O ₂ concentration of 3%. The combustor measures excess O ₂ at the outlet for control and measures the flue gas shortly before exiting the chimney to monitor other exhaust gases, including O ₂ , CO, CO ₂ , NO, and SO ₂ . In addition, Fourier transform infrared spectroscopy (FTIR) analyzers are used to detect other gases, including CH ₄ , CO, CO ₂ , H ₁ O, H ₂ S, H ₂ SO ₄ , HCl, HF, HBr, N ₂ O. , NH ₃ , NO, NO ₂ , SO ₂ and SO ₃ .

The combustion chamber has a plurality of ports capable of injecting wet or dry material. The location is included in the upper, middle and near the exit of the fireball. Injections can flow up (concurrent) and downward (countercurrent). This example uses a down-dry injection, as opposed to a combustion gas flowing upward.

The compositions prepared for the evaluation of the present invention include ten adsorbent base materials (all commercially available), plus a range of formulations wherein the base materials are reacted, mixed or impregnated with various dopants. A list of the formulations used is shown in Tables 1 and 2 below. Table 1 corresponds to the adsorbent and Table 2 corresponds to the adsorbed dopant. The nomenclature used in the report includes the name of the base material, hyphens, and dopants. For example, dolomite hydrated lime (dolomite hydrate adsorbent) has the name "DL". When treated with the diammonium acetate diammonium phosphate dopant of the name "3", the formulation carries the sample ID of "DL-3". Also included are the receipt state particle size (D ₅₀ weight average) and surface area (BET) properties of each material.

The doped material is impregnated with a water-based solution containing the adsorbent or physically mixed with the base adsorbent. The details of the composition of most of the mixtures are shown in Tables 3-1 and 3-2 below:

Rotary blenders are typically used to prepare the compositions, but in terms of minimizing agglomeration, the liquid solution is applied in a slow, controlled manner using a spray system.

The addition of the adsorbent to the combustion chamber (with or without dopants) is accomplished via dry injection. The combined adsorbent and adsorbent dopant are introduced into the combustion gas as they are, since no additional drying is required for these mixture materials.

These samples were added to a rotary auger that had previously calibrated the rate of addition of each material. The outlet of the screw feeder is transferred to the inlet of the extractor system, The extractor system is injected directly into the desired entry point of the combustion chamber or downstream flue. In the present study, the dry injection was carried out in the mouth of the fireball in the combustion chamber (port 3 in Table 4), wherein the temperature was about 2000 ° ± 100 ° F with the syringe facing up.

In addition, alternative materials are injected into the flue near the heat exchanger, with a typical temperature of 385 °F. This is indicated as "Recap 4" in Table 4. The injection rate was chosen to be 3, 6, 9, 18 pounds per hour (lbs/hr) and is the maximum flow rate for each material. Looking at the material density, the maximum rate varies from 9 to 10 up to 20 lbs/hr. A sample of constant velocity particles of flue gas is obtained during the selected time period. The program uses "Method 17" (40 CFR 60. Appendix A to Part 60) as the basis for collection, but the method has been modified to theoretically collect only the particulate sample. Typically, it takes 30-60 minutes to collect enough samples for further analysis.

Table 4 - Analysis Results (Next Page)

Example 2

This example reports that the test was carried out in a dry injection of the slurry of the material showing the best results in Example 1.

About 257 lbs/hr of coal was added to the combustion chamber during the wet injection. At this rate, a suction pyrometry determines the temperature of port 2 to be 1850-2019 °F.

In the wet injection, the slurry samples of the previously prepared adsorbent "DL" and the additive (1, 2, 3 or 4) were respectively added to the same horizontal plane of the combustion chamber. Although the previous test was evaluated at port 3, the current test was performed at port 2 to better match the previously obtained temperature. This change is necessary because the air preheater does not work.

A sample of constant velocity particles of flue gas is obtained during the selected time period. The program uses "Method 17" as the basis for collection, but the method has been modified to theoretically collect only the particles. sample. Typically, it takes 20-60 minutes to collect enough samples for further analysis.

Example 3

This example reports that the test was performed with dry material that showed the best results in dry injection in Example 1.

Dry mixers are typically prepared using a rotary mixer wherein the liquid solution is applied in a slow, controlled manner using a spray system to minimize agglomeration. plus. These materials are added as they are because no additional drying is required for these mixtures.

For dry injections, the samples are added to a rotary auger that has previously calibrated the rate of addition of each material. The outlet of the auger is transferred to the inlet of the extractor system, which is directly injected into the desired entry point of the combustion chamber or downstream flue. In the present study, the dry injection was performed in port 2 of the combustion chamber with the face up.

Study ₂ In addition to reducing SO, also by dry injection of a set of samples will be injected into the flue gas stream to explore the potential use of additives for reducing the HCl. The temperature selected for this test was about 500 °F. This is indicated in the table as "Recap 2/3". The injection rate was chosen to be 3 to 9 lbs/h.

A sample of constant velocity particles of flue gas is obtained during the selected time period. The program uses "Method 17" as the basis for collection, but the method has been modified to theoretically collect only the particulate sample. Typically, it takes 20-60 minutes to collect enough samples for further analysis. Since it takes a long period of time to collect the modified "Method 17" sample, several samples are taken directly from the baghouse by sweeping the top layer of the drum.

Table 8 - Dry Feed Data

We have reviewed the data obtained and believe that the following conclusions and observations are generated by the data:

a. All grades of calcium aluminate, cement aggregates, magnesium hydroxide (and its enhanced blends), many grades of calcium carbonate (except for one test), trona (sodium dicarbonate) and dioxide Manganese did not play much role in reducing (<20%). Unlike all other materials tested in the furnace, trona was tested at 350 °F and 500 °F due to temperature stability limitations.

b. Calcium hydroxide and its reinforcing mixture are much better, with a percentage reduction of 20 to 40%.

c. One combination exceeds all other combinations, wet (slurry) and dry-dolomite hydrate and copper ammonium acetate; CAA (copper ammonium acetate) is 1-6% of the mass of the dolomite hydrate feed.

d. For the reduction of SO ₂ , _two of the three best performers are a blend of dolomite hydrate and copper ammonium acetate, wherein the best performance of the dry material and its blend is dolomite hydrate. -CAA blend, SO ₂ reduced by 91%. This performance far exceeded the performance of any other adsorbent or sorbent blend tried in the entire set of tests, and the results were unexpected.

e. The three top performers are dolomite hydrate-CAA blends of various dosage chemicals. Best performer based same blend, SO ₂ by 75%. In addition, no other slurried blends performed equally well, which was an unexpected result.

f. Dolomite hydrate plus ferric nitrate, copper nitrate and magnetite blends are all suitably reduced (~50%), but not as good as dolomite CAA blends.

g. Previous tests have shown that the above-to-300 lb/ton fuel feed of high quality lime not only results in a lower SO ₂ reduction (~65%) than the top performance blend discussed here, but also has a relatively inefficient SO ₃ / CaO ratio, which is more similar to baseline chemistry measurements. This result is even more compelling, given that the dolomite hydrate CAA blend test is one-third to one-half the dose of other calcium-based sorbents.

h. In the formulation of high performance (i.e. slaked lime and dolomite CAA) observed / CaO ratio of SO ₃ in the increased. The comparative data shows that the calcium conversion in lime is relatively inefficient, with the SO ₃ /CaO ratio being only 0.64, and the values are similar to the basic conditions. XRD data confirmed the presence of large amounts of unreacted CaO in the fly ash sample.

i. The results of chemical analysis using X-ray diffraction showed good linearity compared to X-ray fluorescence, indicating that the two test methods are well monitored for the final results of the measurement test. In general, the lower the level of unreacted calcium oxide in the dust sample, the higher the efficiency of the process. The high performance combination of dolomite slaked lime and copper ammonium acetate (CAA) is essentially free of unreacted calcium oxide, and the highest level of calcium sulphate is present in dust.

The above description is intended to teach the general practitioner how to implement the invention. We do not intend to detail all of the modifications and variations that have become apparent to the skilled worker after reading the description. However, all such obvious modifications and variations are intended to be included within the scope of the invention as defined by the appended claims. Unless the context clearly dictates otherwise, the scope of the claims is intended to cover the steps and the steps in any order.

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Claims (33)

One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: determining a location of a combustion chamber for feeding dolomite hydrate of adsorbent and adsorbed dopant; determining the adsorbent and the adsorbed dopant Physical form and injection parameters; the dolomite hydrate adsorbent and the adsorbed dopant are injected into the combustion gas containing SO _x and/or HCl together with water, and the introduction operation system is effectively utilizing the adsorbent , collecting the spent adsorbent under conditions that capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent that does not contain the adsorbent dopant; The method of claim 1, wherein the adsorbent is introduced as a slurry having small droplets having an average diameter of from about 25 to about 300 microns at a temperature in the range of from about 2200 ° to 1500 °F. The method of claim 2, wherein the adsorbent is introduced at a temperature in the range of from 1900 ° to about 1600 °F. The method of claim 1 wherein the adsorbent is introduced to reduce HCl at a temperature below about 1600 °F. The method of claim 1, wherein the adsorbent is introduced to reduce HCl at a temperature below 900 °F. The method of claim 1, wherein the adsorbent is introduced as a small droplet having an average diameter of from about 25 to about 350 microns. The method of claim 1 wherein the adsorbent is introduced at a feed rate in the range of from about 25 to about 100 pounds of dolomite hydrate per ton of fuel. The method of claim 1, wherein the dolomite hydrate is used in a weight ratio of from about 0.15:1 to about 1.4:1 dolomite hydrate to the weight of SO ₂ in the flue gas. The method of claim 1, wherein the adsorbing dopant is to be combined with the dolomite hydrate adsorbent in a range of from about 100:1 to about 1:1 with dolomite hydrate versus adsorbing dopant. Use by weight ratio (dry basis). The method of claim 1, wherein the adsorbing dopant is a water-soluble or water-dispersible composition of copper and/or iron. The method of claim 1, wherein the adsorbing dopant comprises a solvent selected from the group consisting of copper ammonium acetate, diammonium diacetate, copper ammonium triacetate, copper triammonium acetate, copper tetraammonium sulfate, copper gluconate (and hydrate thereof). And a copper composition of a group consisting of any of these materials. The method of claim 1, wherein the adsorbing dopant comprises a member selected from the group consisting of a composition defined by the formula Cu(NH ₃ ) _x (lower carboxylate) _y , wherein the lower carboxy group The acid salt is selected from the group consisting of formate, acetate and propionate, x is an integer from 0 to 4, y is an integer from 0 to 2, and x+y is equal to or greater than 1. The method of claim 1, wherein the adsorbing dopant comprises a lower aqueous copper carboxylate complex of lower calcium carboxylate and lower ammonium carboxylate. The method of claim 1, wherein the adsorbing dopant comprises a lower aqueous calcium carboxylate complex of a lower calcium carboxylate and a lower ammonium carboxylate, which comprises a weight ratio of about 13 parts. The lower calcium carboxylate is measured by hydrate to about 2 parts of lower ammonium carboxylate, and about 10 parts of 29% aqueous ammonia, and the pH of the solution is in the range of about 7.1 to 7.4. The method of claim 1, wherein the adsorbing dopant comprises a member selected from the group consisting of acetonitrile copper and its hydrate, copper citrate and its hydrate, copper formate and its hydrate, copper acetate single Hydrates, copper nitrate and its hydrates, copper 2,4-pentanedione and its hydrates, copper sulfate and its hydrates, copper gluconate and its hydrates, copper soaps of fatty acids, and mixtures of any of these . The method of claim 1, wherein the adsorbing dopant comprises diammonium diacetate. The method of claim 1, wherein the adsorbing dopant comprises an experimental copper ammonium complex having C ₂ H ₇ CuNO ₂ . The method of claim 1, wherein the adsorbent is injected as a slurry containing from about 25 to about 45% by weight of dolomite hydrate solids in water. The method of claim 1, wherein the adsorbent has a mass average particle size of from about 1 to about 5 micrometers (μ). The method of claim 1 wherein the dolomite hydrate adsorbent is preferably mixed with water to form a slurry having a concentration of at least about 25% by weight solids. The method of claim 1, wherein the dolomite hydrate adsorbent and the adsorbent dopant are injected by an injection member comprising a plurality of nozzles in the introduction region, and the nozzles are positioned to reach within the introduction region At least 90% coverage. A method for gas stream of SO _x and / or means of HCl reduction, comprising: an injection member positioned at the position on the path of the flue gases from the combustion of fuel produced, these can be injected with respect to such member a dolomite hydrate adsorbent and an adsorbing dopant are fed at a predetermined rate in the concentration of SO _x and/or HCl in the flue gas, and the injection members are also capable of having a predetermined physical form and the adsorbent and the adsorbent Predetermined injection parameters of the dopant (including droplet size, momentum and concentration) introduce the dolomite hydrate adsorbent and the adsorbent dopant together with water; thereby, dolomite hydrate with adsorbed dopant The adsorbent captures sulfur oxides with high efficiency. The device of claim 22, wherein the injection members comprise a plurality of nozzles in the lead-in area, and the nozzles are positioned to achieve at least 90% coverage within the lead-in area. A method for reducing the SO _x gas stream and / or the HCl system, comprising: means for determining for feeding dolomite hydrate sorbent in the combustion chamber and the delivery tube and a suction position of the dopant, and decisions a computer modeling component of a dolomite hydrate adsorbent disposed at a channel location of the flue gas and a physical form of the adsorbed dopant injection member and an injection parameter, the injection member being capable of being opposite to the SO _x and// in the channel Or doping the dolomite hydrate adsorbent and adsorbing the dopant at a predetermined rate of the measured concentration of HCl, and the injection members are further capable of being in a predetermined physical form and a predetermined amount of the adsorbent and the adsorbed dopant The injection parameters (including droplet size, momentum and concentration) introduce the dolomite hydrate adsorbent and the adsorbing dopant together with water; whereby the dolomite hydrate adsorbent having the adsorbing dopant can have the request item Any of 6 to 21 captures the characteristics of sulfur oxides and/or HCl with high efficiency. A method for reducing gas stream of SO _x and / or HCl of the composition, comprising: copper and dolomite hydrate sorbent and / or adsorption of iron dopant, which is incorporated containing SO _x and / or HCl The hot gas stream will then dehydrate and cause breakage into particles ranging in size from about 0.01 to about 0.2 microns, wherein the weight ratio of dolomite hydrate to adsorbed dopant (dry basis) is between about 500:1. Within about 25:1, the adsorbent dopant is selected from the group consisting of water soluble or water dispersible copper and/or iron compositions that release the active material upon in situ heating by the treated flue gas. A method for reducing gas stream of SO _x and / or HCl of the composition, comprising: a request entry as dolomite hydrate thereof and a copper-containing adsorbent of any one of the features of 6-21 and / or Adsorption dopant for iron. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; wherein the introduction is performed A slurry having small droplets having an average diameter of from about 25 to about 300 microns is used at a temperature in the range of about 2200 ° to 1500 °F. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; wherein the introduction is performed At temperatures ranging from 1900° to about 1600°F. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; HCl is reduced at temperatures below about 1600 °F. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; Reduce HCl at temperatures below 900 °F. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent under conditions that capture sulfur oxides and/or HCl at a rate achievable with the same adsorbent that does not contain the adsorbent dopant; and collecting spent adsorbent; wherein the adsorbent acts as Small droplets having an average diameter of from about 25 to about 350 microns are introduced. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; wherein the adsorbent is A feed rate in the range of from about 25 to about 100 pounds of dolomite hydrate per ton of fuel is introduced. One kind of a combustion chamber of SO _x and / or HCl of a method of reducing emissions, comprising: an adsorbent and the adsorbent dolomite hydrate dopant into the combustion gas containing SO _x and / or HCl of, the operating system is introduced Efficiently utilizing the adsorbent to capture sulfur oxides and/or HCl at a rate greater than that achievable with the same adsorbent without adsorbing dopants; and collecting spent adsorbent; wherein the dolomite hydrate It is used in a weight ratio of about 0.15:1 to about 1.4:1 dolomite hydrate to the weight of SO ₂ in the flue gas.