ECONOMIC RECOVERY AND UTILIZATION OF BOILER FLUE GAS POLLUTANTS

Abstract: Method and apparatus for removing unwanted pollutants from flue gas are disclosed. A scrubbing device having a sequence of at least three vertical beds of particulate material (106, 108, 110) is disposed in a flue gas exhaust duct (20). A first bed comprises boiler ash or sand. Lime in the fly ash reacts with sulfuric acid and water in the flue gas to form gypsum, removing the fly ash in the flue gas. In the second bed, sulfuric acid is condensed and removed on a further bed of boiler ash. In the third bed, a catalyst, typically, an activated aluminous particulate with an alkali coating thereon, provided by the addition of ammonia to the flue gas contacts the gas being treated. The catalyst can then be regenerated. This scrubbing device is readily retrofittable into pre-existing power plants burning sulfur containing coal.

Description: ECONOMIC RECOVERY AND UTILIZATION OF BOILER FLUE GAS POLLUTANTS Field of the Invention This invention relates to the removal and economi utilization of noxious elements normally released to the atmosphere when fossil fuel, e.g., sulphur-bearing coal, is burned to make steam in boilers as in the electric utility industry. Background of the Invention Many processes are in use for chemically combinin the oxides of sulphur found in flue gases with purchased alkali or alkaline earth materials, which processes enormou increase the capital and operating costs of generating electric power and prevent American manufacturers from competing in world markets. The added costs escalate when high sulphur coals found in the eastern United States are burned, as occurs to a significant extent in geographic regions where high power consuming industries are located, e.g., near the Ohio River and Mississippi River. Coal mine in the western United States is lower in sulphur content, b shipping it to the eastern United States is not economicall feasible. Air pollution damage to the forests of New Engl and Canada has occasioned an international conference with Canada on sulphur-caused "acid rain" removal. Health probl caused by air pollution have been known throughout the hist of industrial development. Hence improvement in economic removal of sulphur from flue gases is needed. Summary of the Invention This invention discloses means and processes whe coal containing 4% or more of sulphur may be burned in boi plants very economically while as much as 99% of the sulph in the flue gas is removed. Nitrogen dioxide is also eliminated, and valuable byproducts are produced; these ma include concrete additives, liquid fertilizers or alternat liquid sulfuric acid or elemental sulphur as may best suit local market demands. The invention is flexibly applied to coals of continuously varying analyses, is useful in connection wit systems involving variable boiler steam rates, and is eas applied to gas-fired boilers. The invention is financiall reasonable with respect to both capital and operating cost because it involves a substantially dry process for recove of pollutants, and provides a relatively small and compact apparatus that can be retrofit to huge existing power plan The invention considers the principal contaminan of boiler flue gas to be fly ash, sulfuric acid fumes, and much smaller amounts of sulphur dioxide gas found when the former contaminants are removed. Nitrogen dioxide also present is also consumed. This invention removes substantially all of thes impurities by forcing every cubic inch of flue gas to pass successively through thin vertical beds of particles which successively entrain the fly ash, condense the sulfuric ac fumes and adsorb the remaining sulphur dioxide gas on a catalyst, from which sulphurous acid may be recovered by a vacuum leach process. For example, in order to retrofit the flue gas purifier of the invention to a preexisting power plant, a duct section as short as 10 or 15 feet in length is insert in the conventional cylindrical duct which carries boiler gas to a smoke stack. The new section according to this invention comprises two or more, typically three, vertical beds of particulate matter, arranged such that all of the flue gas must pass in succession through each of the three beds. Water tubes control the temperatures of the thre beds, and support and space screens supporting the particulates. In the first vertical bed, the flue gas is cleaned of fly ash by chemical combination with the materia of the bed. In the second vertical bed of particles, sulf acid fumes in the flue gas are made to condense. This is by controlling the bed temperature to a fume condensation temperature. In the third vertical bed, the particulates comprise an catalyst, chosen for its ability to adsorb S02- For example, an activated aluminous catalyst which may be coated with an alkali solution and dried may be used. Preferably, the alkali is ammonia introduced as a gas in th flue gas upstream of this bed, where it instantaneously combines with any sulphur dioxide yet remaining in the flue gas. The reaction is catalyzed by the aluminous particulat of the bed, from which sulphates and sulphites can then eas be vacuum leached. Other catalysts may be employed as well According to an important aspect of this inventio the flue gas travels through the beds at high velocities. This removes the boundary layer of gas from the particulate of the beds, such that very high reaction rates are achieve By comparison, in conventional flue gas cleaning, the particles used for sorption are normally widely spaced in t gas, so that reactors of enormous size are needed. The spaced beds are preferably of novel construct comprising inclined titanium or stainless steel "louvers" o the upstream side, on which the particulates rest, and a fi stainless steel screen on the downstream side, to contain t particles in a slightly fluidized but compacted state. Particles are fed continuously to the top of each bed and a withdrawn, loaded with flue gas contaminants, at the bottom of each bed. In the first upstream bed the preferred particula are coarse sand or crushed and sized bottom-ash slag from t boiler, which entrain fly ash. Lime in the fly ash reacts with the sulfuric acid fumes, which begin to condense with molecule of water at 554 degrees F. and with two molecules water at.332 degrees F. This forms gypsum which can be use to make concrete. In the second bed, downstream from the first, the preferred particulates are the same as in the first bed, bu since only a limited amount of the lime is carried over fro the first bed, and because the temperature in this second b is lower, it is possible to condense sulfuric acid. At the base of this second bed, particulates are continuously withdrawn and leached with a minimum amount of water to obt concentrated sulfuric acid. An acid-resistant vacuum drum filter permits a minimum amount of leach water to be used. In the third bed, the particulates are preferably activated aluminous catalyst wetted with an alkali and drie before use. It is well known that sulphur dioxide will rea with the alkali to form bisulphites and bisulphates. According to this invention, the aluminous particulates are continuously withdrawn at the base of the bed and are leach with water on a vacuum drum filter. Sulphur dioxide gas is then withdrawn, which may be discharged into the flue gas stream ahead of the first or second bed to form respectivel gypsum or sulfuric acid. The preferred alkali in this process step is ammo gas, fed into the flue gas up-stream of the third bed. Ammonia reacts instantaneously with the sulphur dioxide to form ammonium bisulphites or bisulphates on the activated aluminous catalyst, which is then leached in a vacuum filte to recover the sulphur dioxide. Since the sulphur dioxide much more volatile than the ammonia, the latter remains in particulates to be used again. Only enough ammonia for mak up, i.e., to replace losses, is required. In the prior art, use of water solutions of ammon used to spray-wash flue gases always resulted in a visible plume of pollutants above the smoke stack. This has not be observed to date in the practice of this invention, which treats the flue gas with more or less dry particulates, sin the moisture is sorbed thereon. The recovered sulphurous acid can be made into liquid sulphur dioxide by conventional distillation, coolin and compression steps, and can then be converted to element sulphur by the Claus process, but such byproducts do not appear to be cost-effective and so are not presently part o the preferred practice of this invention. In contrast with known processes for flue gas treatment that first use water sprays on the flue gas to greatly cool it and then reheat it to ensure sufficient sta draft, flue gas as treated in the practice of this inventio needs no reheating before exit to the smoke stack. At the same time boiler feedwater can be used to cool the baffles and screen, and thus the beds, to insure sulfuric acid formation and condensation. This will recove heat in the flue gases not currently being recovered, becau the cost of corrosion-proofing such apparatus typically exceeds that of the heat energy saved. Brief Description of the Drawings The invention will be understood if reference is made to the accompanying drawings, in which: Figure 1 is a flow sheet of the preferred process according to the invention. Figure 2 is a horizontal cross-section through a rectangular flue gas duct, connected in a conventional cylindrical duct, and housing three filter beds. Figure 3 is a enlarged portion of Fig. 2 showing cross-section through a portion of a vertical, flue gas fil bed. Figure 4 is a horizontal cross-section through a vertical flue gas filter assembly. Figure 5 is a perspective view at the base of th filter bed of Fig. 3, showing the method of particulate withdrawal. Figure 6 is a vertical cross-section through a vertical pipe and the end of one of the particulate beds; particles are vacuum lifted from the bottom to the top of bed through the pipe. Figure 7 is a perspective view of one of the bed showing a rotary drum employed to filter acids from particulates. Figure 8 is a plan view of two of the filter bed Figure 2 showing details of their piping connections. Description of The Preferred Embodimen Figure 1 shows a flow sheet of a preferred proces according to the invention. The process begins at 100, wherein flue gases are indicated passing through a conventional horizontal duct of circular cross-section. It is convenient to fabricate the flue gas treatment apparatus of the invention to be of square cross-section; where a retrofit installation is envisioned, a funnel-shaped gas fl distributor is provided as indicated at 102 to match a horizontal flue gas duct typically of circular cross-sectio with the square treatment duct according to the invention. As indicated at 104, the flue gases entering this rectangular duct chiefly comprise N2 + C0 2 + H2O + 0 2 + SO2 N0 X . Accordingly to the invention, these flue gases first encounter a first vertical bed 106 of particulates. Preferably these particulates are bottom ash removed from t boiler after combustion of coal which has been crushed and sized accordingly, e.g., to approximately 10-80 mesh. Sand can also be used. Lime in the fly ash in the flue gases reacts with S0 2 and water in the flue gas to form gypsum. gypsum can be recovered from the particulate bed 106 in a manner discussed below and used for example as a constituen of concrete or in fertilizer. Gypsum is thus a valuable byproduct of the process of the invention. The structure of the vertical beds is detailed be in connection with Figures 2 through 4; briefly, each bed comprises means for supporting a quantity of the particulat in a vertically extending layer disposed transverse to the flue gas stream, such that the entire volume of flue gas mu pass through each bed and be reacted thereon. Each bed is supported at least in part by cooling water pipes which als control its temperature. According to an important aspect of the inventio conditions are maintained in at least one of these beds wh encourage sulfuric acid to be formed therein. This is in distinct contradistinction to the typical practices of the prior art of flue gas treatment, which was to keep the flu gas temperature high enough that the sulfuric acid did not condense. While this practice limited corrosion of the fl gas stack assembly, thus benefiting the utility operator, meant that the sulfuric acid condensed later in the atmosphere, as a principal cause of acid rain, which is a serious pollutant throughout much of North America and Wes Europe. Patents are known which suggest deliberate condensation of sulfuric acid to remove it from flue gases; see U.S. Patents 4,597,433, 4,676,299, and 4,703,794, all issued to one of the applicants herein. After passage of the flue gases through the firs bed 106 and removal of the fly ash, the flue gases then pa through a second bed of particulates, as indicated at 108. The particulates in the second bed are essentially similar those in the first bed. However, in this case the lime ha been principally removed and the temperature is relatively lower, such that it is possible to condense sulfuric acid in this bed. Again, as indicated, cooling water pipes are provided and are used to control the temperature of the be such that the sulfuric acid does in fact condense and is removed. Preferably the sulfuric acid is removed from the particulates by a vacuum filter, the structure of which is detailed in connection with Figures 5-7. In the third bed, indicated at 110, the particul is preferably an activated aluminous catalyst, that is, an alumina-bearing material wetted with an alkali and dried before use. Any remaining sulphur dioxide in the flue gas stream will react with the alkali to form bisulphites and bisulphates. Nitrous oxides (NO x ) are also removed in this step. The bisulphates are leached from the catalyst in a vacuum filter apparatus, again discussed in connection with Figures 5-7 below, removing the sulphur dioxide therefrom. This can be returned to the flue gas stream prior to the fi bed for reaction to form gypsum and sulfuric acid, all as discussed above. The aluminous catalyst particles can then recirculated as indicated at 112; typically the alkali will remain thereon and is similarly reused. The preferred alka is ammonia introduced into the flue gas stream between the second and third beds. Other catalysts may be employed to condense the S with or without the alkali addition. These could include s high surface area materials as activated charcoal or other carbonaceous material, diato aceous earth, clay, Fuller's earth, or activated silica materials each as silica gel. Polar or non-polar materials may be useful. The flue gas stream having thus had the S0 2 and nitrous oxides removed therefrom is then returned to the conventional duct at 114 by means of an intermediate funnel shaped flow distributor indicated at 116. Figure 2 shows a vertical cross-section of a retrofittable flue gas treatment chamber, that is, a scrubb assembly, according to the invention. A flue gas duct 20, which may be of rectangular cross-sectional shape, is inser between the ends 21 of a conventional cylindrical flue gas exhaust duct. The rectangular duct 20 houses three vertica beds, 1A, IB and 1C shown in horizontal cross-section. Funnel-shaped transition duct members 23 joins th rectangular duct section 20 to the circular ends of the conventional flue gas duct 21. Flue gas distribution vanes ensure that the flue gas flows evenly through beds 1A, IB a lC. An alkali reagent, typically ammonia, is introduc into the flow stream upstream of the third catalyst bed 1C a distributor indicated schematically at 40. A fan 42 is provided between the scrubber of the invention and the stac 44, to ensure high velocity, turbulent flow of the gases through the beds. Complete exposure of the gas, entrained particulates, reactants, etc. in the flue gas stream to the particulates of the beds is thus ensured. Figure 3 is an enlarged vertical cross-section through one of the beds 1A, IB, and 1C, which are of simila structure. Flue gas flow is from left to right in this Figure. Figure 4 is a cross-section orthogonal to Figure 3 as indicated at 3-3 of Figure 4. As shown in Figures 3 and a bed 2 of particles is held in upright position on the upstream side by baffles 3 and on the downstream side by a relatively fine screen 4, e.g., of 10-80 mesh. The bed 2 formed simply by disposing the particulates between the to the baffles 3 and the screen 4. The bed 2, baffles 3, and screen 4 are temperature controlled by contact with vertic coolant water tubes 5 and 6. These tubes are formed of titanium. Baffles 3 are welded to tubes 5; the screen 4 is confined between the tubes 5 and 6. This stainless steel screen 4 is removable and is snugly held between the two vertical rows of water-cooled tubes 5 and 6, which are spa about a foot apart in each row. Thus a tube alternately contacts the screen 4 every six inches. This is shown in horizontal cross-section through the bed of Figure 4. In this manner the particle beds can readily be temperature controlled. For example, the second bed IB is controlled to a temperature range of roughly 220-370° F. t condense the sulfuric acid thereon, one molecule of S0 2 reacting with one or two molecules of water. This process carefully regulated by conventional thermostats in the beds controlling cooling water flow valves. In this bed IB N0 X the flue gas, together with the elements of the particulate catalyzes the formation of sulfuric acid as well-known in t art of manufacture of sulfuric acid. Every cubic inch of flue gas is forced according this invention to travel through the beds of particulates a high velocity, whereby boundary layers of stagnant gas are removed from the particulates, so that oxidation by H 2 0, N0 • and 0 2 in the flue gas is instantaneous. According to this invention, the wire screens themselves, properly prepared, assists in the catalyst function. Typically the louvers 3 each bed are inclined at between about 10 and about 60° to vertical, and are each between about 1 and about 4 inches wide. The overall thickness of each bed is 1-2 inches. Figure 5 is an isometric projection of a vertical cross-section through the base of one of the beds shown in Figures 3 and 4. Figure 6 is a cross-section through the e of the bed and Fig. 7 is an isometric view comparable to bu on a smaller scale than Figure 5, illustrating the overall structure of this bed. A rotating titanium rod 8 with groo 7 extending along its length is mounted in the base of the bed. The particles fall into the grooves 7 along the enti horizontal width of the bed, and are withdrawn by a strong vacuum applied to the base by way of a lift-pipe 10 illustrated in Fig. 6. Fig. 7 shows a vacuum drum filter 13, to which th lift-pipe 10 delivers the particles for washing. The drum filter 13 extends over the entire breadth of the bed, which may be on the order of 10 feet wide. Accordingly the lift- tube 10 is curved at the top of the bed, as shown, and is drilled or slotted to become a horizontal vacuum conveyor of particles to the vacuum drum filter 13. A conventional va pump or steam ejector (not shown) , is provided as a source vacuum applied to the interior of the filter drum 13. Wat jets 12 wet the surface of the filter and the particulates which are accumulated thereon. According to an important aspect of the inventio the vacuum force is used in three ways. First, it operate the vacuum drum filter 13, which is conventional in design except that it preferably uses a porous metal or porous fu ceramic for the drum 15. That is, vacuum is applied to th interior of the tube, to pull the particulates onto its po surface, forming a filter cake. Second, the vacuum force operates the vacuum conveyor system, to withdraw particles from the length of the bottom of the filter bed, lift the particles to the top of the filter bed and distribute them along the length of the of the top of the filter bed. Thi the flue gas drawn through the particles by the vacuum hea the filter cake, and so dries the wetted particles, leachi the absorbed materials from the particulates as fast as th are washed. The acidic filtrate is withdrawn from the interior of the drum in conventional vacuum-drum filtering practice. The lifting and conveying tube 10 may be made o titanium or heavy-wall cast iron pipe, to withstand abrasi as well as acids, since the particles of fly ash may trave speeds of 5 to 50 feet per second. A conveyor structure comprising a rotating groov rod 8 may also be employed at the top of the bed, as shown 8' in Fig. 7. The particles are distributed evenly throug the bed by the rotation of the grooved rod 8. The vacuum drum filter 13 is enclosed by casing 14. As noted, the fi comprises a porous metal or ceramic drum 15 that rotates o hollow shaft 17. Shaft 17 is attached to drum 15 by spoke 16. Vacuum may be applied to the filter and thus to the filter cake 18 of particulates via apertures 19 in the cen of tube 17. The conventional drum filter bearings, motor a vacuum pump which may be employed are not illustrated. To recapitulate, the recirculation of particulate from the bottom of a bed to the top and the leaching of contaminants therefrom is illustrated in Figs. 5, 6 and 7. The grooved rod 8 at the base of the bed is rotated. Particles drop into grooves 7 in rod 8, and are drawn by vacuum along the breadth of the bed to the lift-tube 10. T particles are distributed over the length of drum filter 13 and are wetted by a series of sprays 12 so that a layer of these particles forms a dense filter cake which adheres to face of the drum. As the drum rotates clockwise, additiona sprays apply moisture which passes inwardly through the particles, leaching the acids and salts resulting from flue gas sorption of contaminates by the particles. The liquid filtrate is recovered from inside the drum in the conventio manner. Preferably only the aluminous, activated catalyst employed in the third bed according to this invention need recirculated in an apparatus as shown in Figures 5-7. The beds preceding the bed containing the aluminous material contain fly ash or crushed and sized bottom ash, as noted. These can be flow-through-once beds with the gypsum output going to concrete clinker production or concrete byproducts. In this case, conventional vacuum conveying apparatus long used by the power plant industry for conveying fly ash may b employed to extract particles from one end of the base of th beds. Figure 8 is a plan view of beds IB and 1C showing exemplary manner in which the cooling water tubes 5 and 6 ar joined at their bases beneath the screen 4 to unitize the be structurally as well as cooling it; the structure shown allo the bed to be easily removed from duct 20 for maintenance or replacement. At such time the fine screen 4 can be readil lifted from its snug fit between cooling pipes 5 and 6. T cooling water passed through pipes 5 and 6 may logically b from a boiler plant condenser. Cooling water enters near top of the bed through vertical pipe 26 feeding horizontal distributing pipe 24 and pipes 27 connecting pipe 24 to th tops of vertical pipes 5. Water flows downwardly through pipes 5 to their bottoms, and thence beneath the screen vi horizontal connecting pipes 29 to pipes 6. Water flows thence upwardly to the tops of pipes 6, which are connecte via short pipes 30 to a gathering horizontal pipe 25. Preheated feedwater can then be delivered to a boiler from pipe 25 via vertical pipe 28. An offtake from the system delivers water to the spray pipes 12 of the vacuum drum fi 13 shown in Fig. 7, typically at 200 degree F. Thus Fig. 8 illustrates four novel features. First, the structure shown provides positive cooling of fi bed to condense flue gas acids therein. As noted above, t conventional teaching of the art is to avoid cooling the f gas, to avoid condensation of H2SO in the flue. While th avoids corrosion of the piping of the system, it necessari causes the release of H2SO4 mist into the atmosphere, whic a principal source of acid rain. This is avoided accordin the invention. Second, Fig. 8 illustrates the manner in w the cooling water tubes provide structural support for the bed, while allowing it to be easily repaired or replaced. Third, Fig. 8 shows means to recover the heat energy lost cooling the flue gases to condense the acids, by preheatin the boiler feedwater. Fourth, Fig. 8 shows means for supplying very hot water needed to leach particulates. As noted, after leaching the particulates can be recirculated reused. The preferred activated alumina catalyst used to absorb flue gas contaminates is derived from the skimmings aluminum melting or holding furnaces. A suitable process f producing this activated alumina is described in U.S. Paten Nos. 3,955,969 and 4,050,999. EXAMPLE I A specific example which will aid in understanding the invention is set forth hereinbelow. This example estimates the gas flows in a 100,000 kw power plant burning Kentucky coal having the following typical composition. Analysis Analysis lbs of each ingredient moisture coal as per lb of coal fired Coal Ingredient & ash-free fired carbon C 79.0 63.6 0.636 hydrogen H 5.6 4.5 0.045 nitrogen N 1.7 1.4 0.014 oxygen O 10.1 8.1 0.081 sulphur S 3.6 2.9 0.029 ash 11.2 0.112 water HoO 8.3 0.083 100.0 100.0 1,000 Calculation of consirmption of oxygen per lb coal fired Ingredient consumed by oxygen per lb of Chemical reactions & lbs of oxygen coal fired in boiler molecular weights burned per lb coal 12 32 44 32/12=2.67 1.70 carbon 0.636 C + o 2 -*C0 2 4 32 36 32/4 =8 0.36 hydrogen 0.045 2H 2 + 0 2 --*2H 2 0 32 + 32 64 32/32=1 0.03 sulphur 0.029 SS + 0 2 -* » S0 2 total 2. .09 less oxygen in coal 0. .08 oxygen required for reactions 2. .01 add 24% excess air for complete combustion 0. .48 total lbs oxygen to boiler/lb coal 2.49 Calculation of total flue gas per lb coal fired nitrogen in stack gas above 2.49 x (79/21) (N/0 in air) 9.37 carbon dioxide 0.636 x 44/12 (C0 2 /C)=2.33 less 0 2 1.7 0.63 water in air needed for combustion including 24% excess over theoretical 2.49 x (100/21) air/N) X 0.01657 50% humidity 77F° = 0.196 water in coal per lb coal fired 0.083 water from hydrogen combustion 0.045x(36/4) .405 0.684 0.68 sulphur 0.29X 64/32 (S0 2 /S) less 0 2 =0.03 0.03 total pounds of flue gas per lb coal fired 13.20 total pounds sulphur dioxide per lb coal fired 0.058 Percent of sulphur .dioxide in flue gas 0.058/13.20 xl00=0.45% Calculation of heating value of Coal by Dulonq*s formula: Btu per lb of coal = 14,544 x carbon 62,028 x (hydrogen-oxygen) 4050 x sulphur 8 = 14,544 X 0.636 9,250 62,028 X 0.035 2,171 4050 X 0.029 117 Btu per lb coal fired 11,538 Calculation o^ vnlmne of the gas Assuming a conservative efficiency of 35% for the 100,000 kw plant the Btu converted to kw is 35% x 11,538 x 2,000 = 8,076,600/ton coal. Since 1 kw power is equivalent to 81,959 Btu/day, the coal neede daily is 100,000 x 81,959/ 8,076,600 = 1015 tons or 1410 lbs/min and 23.5 lbs coal/second. Since the total lbs flue gas per lb coal fired is 13.20 (from th above), the lbs flue gas per minute is (1,410 x 13.2 = 18612 and per second 310.2 Calculation of mols of gas and volumes at elevated temperatures (based on one mol of any gas occupying 359 cu.ft. at 32°F.) lbs/lb coal mol mols of volume in cu ft of Gas fired weight gas gas/lb coal 32°F 212°F 400°F 600° 459R 672R 860R 1060R N 2 9 . 37 28 0.355 120 175 225 277 C0- 2.33 44 0.053 19 28 36 44 0.48 32 0.015 12 H 2 0 0.68 18 0.038 14 20 26 32 12.86 Ave 29 0.441 flue gas volumes per lb. coal 158 230 296 365 and at 23.5 lb coal/sec the cu.ft flue gas/sec is: 3 , 713 5 , 405 6 , 956 8 , 578 pilot plant test indicates gas through cascade of activated alumina travels 40 ft/sec so area required is volume/40. At a reaction temperature of 400°F = 174 ft. 2 Hence a 13 x 13 ft square duct will provide adequate reaction area. Calculation of Savings Due to Preheating of Boiler Feedwater From the data of Example I of this Specification the saving is calculated as follows: boiler feedwater is heated as flue gas cools 100°F, from 350° to 250° average specific heat of flue gas at average 300°F is 0.254 Btu/lb flue gas 12.86 lbs. flue gas/lb coal fired from above Calculation of mols of gas and volume at elv. temp. 100 x 0.254 x 12.86 = 326 Btu saved per lb. coal with 11,538 Btu available/lb coal fired = 326/11,538 = 2.82%. If coal costs $30/ton delivered the saving is $0.85 per ton coal fired or per day $0.85 x 1015 tons/day = $862/day Although the foregoing specification refers generally treatment of flue gases from coal-fired power plants, it should be understood that the apparatus and process of the invention is suitable for treating practically any type of flue gas whether generated by burning oil, natural gas, or waste dump materials, or from mineral smelting or paper manufacturing operations. While a preferred embodiment of the invention has been disclosed, those of skill in the art will recognize that ot modifications and improvements can be made thereto without departure from its spirit and scope. The invention is therefore not to be limited by the above disclosure, but: on by the following claims.

Claims: WE CLAIM: 1. Apparatus for removing S0 2 , NOx and other pollutan from a flue gas stream containing these pollutants, comprising: a horizontal housing (20) defining a duct for flo of flue gas therethrough; at least three vertical beds (1A, IB, 1C) of particulates disposed in succession transversely in said du whereby said flue gas flows in succession through each of s beds; means for supplying a particulate material for removing entrained fly ash from said flue gas stream to a first one of said beds; means for supplying a particulate material for removing sulfuric acid from said flue gas stream to a secon one of said beds; a third one of said beds comprising a regenerable particulate catalyst for carrying an alkali reactant thereo for reacting with sulfur dioxide in said flue stream; means (40) for injecting an alkali material into said flue gas stream upstream of said third bed; and means (42) for inducing high velocity turbulent flow of said flue gas through said at least three beds. 2. The apparatus of claim 1 wherein the particulate o one of the first and second beds is formed of ash and slag materials from combustion of coal which do not form fly ash. 3. The apparatus of claim 2 wherein said slag and ash materials are sized prior to disposition in said bed. 4. The apparatus of claim 1 wherein said particulates are confined in a layer between a screen (4) on one side and succession of inclined panels (3) on the other, wherein sai inclined panels are disposed on the upstream side of the particulates and the screen is disposed on the downstream s of the particulates. 5. The apparatus of claim 1 in combination with means (8) for removing particulates from the bottom of the bed. 6. The apparatus of claim 5 in combination with means (10, 13) for recycling said particulates to the top of said bed after removal from the bottom thereof. 7. The apparatus of claim 6 wherein the particulates the first and second beds are formed of a material which combines with lime in fly ash and sulfuric acid to form gypsum, and the material of said third bed is a catalytic material. 8. The apparatus of claim 7 wherein said catalyst is activated aluminous material. 9. The apparatus of claim 8 wherein said activated aluminous material is skimmed from molten aluminum in an aluminum melting furnace. 10. The apparatus of claim 9, wherein said alkali material is gaseous ammonia. 11. The apparatus of claim 10 in combination with filter means for recovering the aluminous catalyst from the process stream after removal of the sulphur dioxide from t flue gas stream. 12. The apparatus of claim 11 wherein said catalyst i selected from the group of materials consisting of alumino materials, carbonaceous materials, clay, diatomaceous earth Fuller's earth, and activated silica. 13. The apparatus of claim 4 wherein said beds compri means (5, 6) for temperature control thereof, to induce removal of said contaminants from said flue gas stream by s particulates of said bed. 14. The apparatus of claim 13 wherein cooling water i supplied to said bed by passage through piping which is in thermal contact with said screen, whereby said piping additionally serves to assist in maintaining the structural integrity of the bed. 15. A scrubber assembly for use in connection wi flue gas streams from power plants containing sulphur dioxide, comprising: a first vertical bed (1A) of particulates disposed in horizontal duct means (20) such that said flue gas passes substantially entirely through said first bed, said first b comprising a particulate material which reacts with fly ash said flue gas stream to remove said fly ash therefrom; a second vertical bed (IB) disposed downstream from sa first bed in said duct means, such that all of said flue ga must pass therethrough, and comprising a bed of a particula material selected to remove sulphur dioxide from said flue stream as sulfuric acid; and a third vertical bed (1C) disposed downstream of said first and second beds in said duct means such that said flue gas stream passes substantially entirely therethrough, said third bed comprising particulates of a catalyst material for removing unreacted sulphur dioxide from said flue gas stream 16. The scrubber of claim 15 further comprising means (40) for introducing gaseous ammonia into said flue gas stream prior to said third bed, whereby said particulates catalyze the reaction between said ammonia and said sulphur dioxide, whereby said sulphur dioxide is substantially remo from said flue gas stream. 17. The scrubber of claim 16 wherein said catalyst is selected from the group consisting of activated aluminous materials, carbonaceous materials, clay, diatomaceous earth materials. Fuller's earth, and activated silica. 18. The scrubber of claim 15 wherein at least said third bed comprises means (8, 10, 13) for recirculating particulates after employment to remove unwanted contaminan from said flue gas stream. 19. The scrubber of claim 15 wherein said means for recycling the particulates comprises means for physically moving said particulates from the bottom of said bed to regeneration means and thence to the top of said bed. 20. The scrubber of claim 19 wherein said means for regenerating the particulates comprises filter means for forming a filter cake of said particulates and for allowin leaching solvent to be passed through the filter cake of particulates, whereby the contaminants are removed from th particulates. 21. The scrubber of claim 20 wherein said particulat are confined in said beds between a screen (4) on the downstream sides of said beds and horizontal louvers (3) o the upstream side of said beds, whereby said flue gases en said beds between said louvers and exit the beds through t screen. 22. The scrubber of claim 21, wherein said beds inclu means (5, 6) for temperature control thereof, such that the pollutant-removal reactions therein are encouraged. 23. The scrubber of claim 22 wherein said temperature controlled in at least said first and second beds to be bel the condensation temperature of sulfuric acid, whereby sulfuric acid is condensed in said beds and may be removed therefrom. 24. The scrubber of claim 23 wherein said beds are water cooled by means of water cooling pipes in thermal contact with and affixed to said screen, whereby said pipes support said screen and maintain the structural integrity o said bed. 25. The scrubber of claim 24 wherein said pipes are formed of titanium material. 26. The scrubber of claim 25 wherein said cooling wat is employed as boiler feedwater after having been heated in said beds. 27. The scrubber of claim 15 wherein said beds are generally rectangular in shape and are disposed in a duct which is rectangular in cross-sectional shape in the vicini of the location of said beds and which comprises tapering duct means for mating said rectangular section of said duct with ends of a preexisting flue gas duct in a power plant, ready retrofitting of said scrubber thereto. 28. A method of removing unwanted pollutants from flu gas streams from power plants, comprising the steps of: passing the flue gas in succession through at least three vertically extending beds (1A, IB, 1C) of particulate said particulates being disposed in a duct (20) such that t flue gas is passed through substantially all of the particulates, a first bed (1A) of particulates comprising a material which reacts with lime and sulphur dioxide and water in the flue gas stream to form gypsum; a second one of the beds (IB) comprising a material reacting with unreacted sulphur dioxide and water in the fl gas stream to form sulfuric acid; a third one of said beds (1C) comprising catalyst material with a dried alkali material thereon, to react wit sulphur dioxide in the flue gas stream; and removing the pollutants from the particulates of the beds. 29. The method of claim 28, comprising the further st of controlling the temperature of at least one of said beds a temperature below the condensation temperature of sulfuri acid. 30. The method of claim 29 further comprising the ste of supplying water used to control the temperature of the b as feedwater in the power plant, thus improving the overall energy efficiency of the power plant. 31. The method of claim 28 comprising the further ste of adding gaseous ammonia to the flue gas stream prior to t third bed, wherein the ammonia reacts with sulphur dioxide present in the flue gas stream, this reaction being catalyz by the particulate material of the third bed, whereby the sulphur dioxide is removed therefrom. 32. The method of claim 31 comprising the additional step of recycling at least the particulate material of the third bed. 33. The method of claim 32 wherein said recycling ste consists of the steps of removing the particulate catalyst from the bed, removing sulphur dioxide therefrom, and returning the thus regenerated catalyst material to the top the bed. 34. Method for removing sulphur dioxide from boiler flue gases, comprising the steps of: passing the flue gases through a vertically extending (IC) of activated alumina particulate catalyst material hav alkali materials absorbed thereon, whereby said sulphur dioxide is absorbed on said particulate bed; removing said particulates from the bottom of said bed; forming a layer of said removed particulates on a permeable member (13) ; wetting the outside surface of said layer of particulates and applying vacuum to the opposite side of the layer of said particulates, to leach sulphur containing compounds from the particulates; and returning the catalyst particulates having thus been regenerated to the top of said bed for reuse. 35. The apparatus of claim 1, further comprising means for controlling the temperature of at least one of said beds to a temperature below the condensation temperature of sulfuric acid. 36. The apparatus of claim 1, further comprising heat exchanger means disposed in said duct upstream of said beds recover heat from said flue gas stream and to cool it to a temperature low enough to encourage condensation of sulfuri acid on said beds. 37. The apparatus of claim 1, wherein said alkali material is ammonia injected into said flue gas stream between said second and third beds.

Inventors: JOHNSON ARTHUR F, SACKETT ROBERT L, JOHNSON, ARTHUR, F., SACKETT, ROBERT, L.
Applicants: JOHNSON ARTHUR F, SACKETT ROBERT L, JOHNSON, ARTHUR, F., SACKETT, ROBERT, L.
Application year: 1989
Main classification: B01J8
IPC codes: B01D53, B01J8, B01J23, C01B17, C01F11