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DESCRIPTION of the SYSTEM
3. 1. Design Calculations for Gas Absorber
3. 2. Calculations of Ca(OH)2 Consumption
3. 3. Filtration of CaSO4 Particulates
4. 4. Mixing and Agitation of Ca(OH)2 mixture
L ITERATURE SURVEY
4. 1. Types and Sources of Air Pollutants
4. 2. Experimental Adsorption Studies
4. 3. Philippine Clean Air Act
5. 1. Desulfurization – Denitrification
by Electron Beam
5. 2. Seawater Scrubbing Process
5. 3. Dry Seletive Catalytic Reductions
5. 4. The Adsorption Process
6. 1. Air Pollution by M. N. Rao & H. V. Rao
6. 2. Stoichiometry by B. I. Bhatt & S. M. Vora
6. 3. Principles of Unit Operations by Alan S. Foust
6. 4. Perry Chemical Handbook
has been labeled by man as “ POLLUTANT”. Burning of fossil fuels such as coal. is a dynamic system that continuously absorbs a wide range of solids. oceans and a receptor such as man. NOx and other pollutant to the atmosphere whereby a chemical reaction with air and water which will result as an acid or any other forms of toxic materials. that it becomes a major concern for the whole mankind. Pollution in the environment have affected human beings. That portion of these substances which interacts with the environment have cause disease. physiological effects or environmental decay. King Edward I issued a royal proclamation punishing any violator which states “Whoever shall be found guilty of burning coal shall suffer the loss of his head“. which was the first significant change in man’s effect to the environment and pollution already exist at that time. animals and plants. cooking and to provide light. Most of these constituents find there ways into a depository such as rivers. SOx. liquid and solid waste. which makes up the largest fraction of the biosphere. . Food and Pharmaceutical Products and other Processing Plants. the attendant pollution problems also increase proportionately. and react with one another both physically and chemically. aesthetic distress. In 1306. liquids and gases from both natural and man-made sources. In 1273.1. In general. the British Parliament passed an Act forbidding the burning of coal in London because it was beginning to pollute the atmosphere. a man was beheaded for violating such proclamation but later such proclamation were disregarded as industrial revolution took place in England. lakes. air and water becomes polluted with different chemicals in the forms of gases. INTRODUCTION The demand for energy in the industrial sector. Atmosphere. oil fuel and natural gas can produced. particularly in Power Plants. Man-made substances travel through air and disperse. Man discover fire for heating. the action of man are the primary cause of pollution and as population increases.
In this way. in recovery-type processes • Acceptance environmental impact. out of a variegated list of probably over 200. NOx and particulate from 3-units 18 tons/hr. is a prime consideration in tackling the gas stream in separate stages. fabrication. • Marketable end product. • Utility-company acceptance.. • Favorable economic impact. substantial differences of opinion exist over whether or not simultaneous removal is wise. Dole Philippines Inc. conceptualize and made a design to treat its emission of SO2. for the design. Bobcock & Wilcox Boiler exhaust gas in order to have a clean environment within their neighborhood in collaboration with Dreva Construction Inc. the obstructive presence of fly ash. With either type of system. is minimized in the SO2 circuit. . • Advance level of development. In some cases. Those processes with the best chances of being commercially applied in the years ahead will meet these criteria: • Technical feasibility. Equipment cost of course. which is not an inert substance. 2. installation and commissioning of the flue gas scrubbing system. followed by SO2 removal. in throwaway processes.In compliance to the Philippine Clean Air Act. BRIEF DISCUSSION of the POLLUTION SYSTEM: Wet removal systems have the ability to scrub both fly ash and SO2 simultaneously from stack gases. A strong trend is noticeable today toward dealing with particulate matter first. Over 50 individual processes have received some degree of interest. dry method can also remove particulate.
and (3) particulate disposal. dissolution of Ca(OH)2. Hydrolysis (thorough wetting) of SO2 to H2SO3. The economizer will act as quencher or to cool down the exhaust gas before entering the scrubbing units. (2) scrubbing liquid. into the reaction tank (integrated sump tank) along with the reacted materials and passed to a V-screen filter provided with a back wash system to remove whatever particulate accumulated in the screen. Cooling down the SO 2 gas temperature it will react rapidly with the spray liquor than when the temperature is high). The sequence of actions embraced by the equations is this: 1. formation and precipitation of CaSO3. . Absorption of SO2. The filtered reacted materials will be pump to the slurry receiving tank and re-circulated back to the scrubber. out the stack. Key reactions within the scrubber are these: Absorption of SO2. Diffusion of SO2 to the gas/liquid interface 2.33ºC from the boiler. Since particulate are burnt carbon it can be drained to a sedimentation tank. where one (1) unit will be on line while the other is on standby after backwashing). The cooled exhaust gas enter the bottom of the absorption column and stripped the SOx and NOx content in the stream of flue gas using and spraying of a solution of water and hydrated lime Ca(OH) 2 which is more expensive than limestone but more efficient. 3. through the scrubber. after cleaning . (it is highly recommended that an economizer is to be installed along the exhaust pipe. through the scrubber and.The proposed project is a design of emission control for the exhaust gas of a bunker fired Package Type Boiler. on how to reduce/minimize SO2/NOx content in the flue gas to 700 ppm and 500ppm in order to meet the requirements of The Philippine Clean Act. Basic system circuitry ( see flow diagrams ). Other constituents in the system may affect these reactions to some extent. Key flow circuits are these: (1) exhaust gas. The economizer is used to preheat the feed water for the boiler to 103ºC and the exhaust gas temperature from the boiler should at 40ºC or higher than the due point of SO2. from the boiler. passage from the reaction tank to in line V-screen filter ( 2-units V-screen filter. SYSTEMS USED: There are three (3) units of Babcock & Wilcox Boiler with a capacity of each unit of 18 tons steam generation/hr/unit. The exhaust gas heat temperature is at 178.
H2SO4 Catalytic oxidation occurs at . Other option is to react CaSO3 by introducing air with the overflow solution in a reaction tank thereby CaSO4 (gypsum) is form. Maintain certain pH so that CaSO3 solution overflow will be directed to the existing WWTP. and 8 are quiet rapid controlling mechanisms. 4. Scrubber addition CaO CaSO3. Less solid waste Double alkali NaOH CaSO4(gypsum) No scaling in scrubber. are either gas diffusion ( step 1 ). 8. CaSO4 probably the least expensive of limestone process to install. 7. and have relatively low capital and operating costs. liquid diffusion ( step 5 ) or dissolving of Ca(OH)2( step 6 ). Diffusion of HSO3 and H ions through the liquid film at the droplet surface interior. 7. They can achieve high SO2-removal efficiencies. 6. At present. therefore. Research indicates that reactions in steps 3. 9.to form HSO3. Reaction of Ca(OH)2 with H+ to give Ca++ and 2H2O-. removal efficiency heavily dependent on limestone selected. Reaction of Ca++ with SO3= to precipitate CaSO3. CaSO4 Improved efficiency at the of lime expense of greater potential for scaling. Dissolving of Ca(OH)2. Dissociation of H2SO3. 5. the lime and limestone SO2-removal processes are the most advanced. although a problem at precipitation stage.4. Leading processes technically feasible for SO2 removal from boiler stack________ Name of processes Reagent used End products Comment Scrubber addition CaCO3 CaSO3. Magnesia scrubbing Magnesium Catalytic oxidation Vanadium H2SO4 Program today processes sulfuric acid at central plant from MgSO3 salts scrubbed out and shipped from power plant.and H+. Smaller scrubbers and liquor flows possible.
Twin actions continually occur: Absorption of SO2 in citrate solution. producing 80% sulfuric acid at the rate of 12 gallons/min. Makeup slurry is also added to the tank. SO2 is reduces to S with natural gas. Equipment size depends primarily on the rate of mass transfer from the gas to the scrubbing medium for optimum SO2 mass transfer the surface area of the limestone must be maximized. The scrubber’s job is to promote intimate mixing of the SO2-laden flue gas and the limestone. An overriding objective is to do both at minimum cost thus it is important to supply a large surface area of limestone per volume of SO2 per unit of time in the scrubber to keep the liquid phase solution amply supplied with calcium ions . Reusable slurry is sent back to the scrubber. The reaction tank-also called a holding. minimum water disposal. the reaction tank and the thickener. yielding discardable precipitates. no stack plume no stack gas reheat. as needed. while resistance of the gas/liquid interface must be minimized. recirculation or delay tank-is the receptacle for the absorbed and reacted materials discharged from the scrubber.850 F. These material are generated when SO2 react chemically with the water and limestone to form new products that are removed from the scrubber with the liquid. Limestone system. Advantage of dry process are minimum water use. The three main components of a limestone scrubbing system are the scrubber. Chemical reaction go to completion (or nearly so) in the reaction tank. regeneration of H2S with sulfur produced. Wellman-Lord/SO2 Reduction Na2SO3 Sulfur Citrate Sodium citrate. Citric acid Sulfur Dry Absorption Char from Sulfur Noncoking coal Wellman-Lord process produces concentrated SO2 by thermal stripping of NaHSO3. which is introduced into the scrubber as a slurry of 5-15% solids content (by weight)-the carrier being water.
Scrubber-system design-wet scrubber for SO2 removal have several design criteria as full scale experience with these units increase improve design will doubtless emerge here are principal criteria: • • • • • • • • • • Sulfur content fuel Ash content fuel SO2 removal efficiency Scrubber type. size and spare capacity System turndown capability Mist eliminator Stack gas reheat Waste disposal System power loss Material of construction The higher the sulfur content of the fuel burned in the power plant the more efficient the SO2 removal system must be. Fuel oil containing 3% sulfur requires about 80% removal from the stack gas. this is meet EPA’s new source – emission standard for coal burning plants of 1.Maximum SO2 transfer can be realize by careful scrubber selection and by balancing gas velocity against gas residence time maximum reactant surface area can be achieved by: • • • • • Large liquid holdup of slurry in the scrubber which depends mainly on the type and characteristic of scrubber selected High slurry recirculation rate on the order of gal per 1000 cu ft of saturated gas High solid content in slurry. Fly ash is removed from the stack gas before SO2 removal the design of scrubbing system can be different beginning with the scrubber itself for example a spray – tower design could be used to obtain 80-90% removal with lower gas pressure drop it would .2 lb of SO2 emission per million Btu. % by weight. This factor together with high circulation rate will also minimize scaling potential is sufficient delay time in the reaction tank arranged Maintaining feed stoichiometry between stoichiometry may be defined here as the molal ratio of alkali (or limestone) feed to SO2 absorbed Reducing the particle size of the limestone good result have been obtained with 80-90% of particle passing through US Mesh which passes 35-micron-size particles.
If fly ash and SO2 are removed simultaneously these scrubber combinations are effective a venturi followed by an absorber a two stage venture a multistage mobile bed absorber remember however that the process chemistry throughout the scrubber system will become more complicated the system generally will be more sensitive to change and wastes-solids requirements will be higher. Cost overall control response. of screen. All these interfaces are designed to boost the rate of absorption. Specific variables to consider are the following: • • • • • • • Liquid-to-gas ratio pH control. Number of stages. the tray offers high liquid holdup and high SO2 . which embrace the gas/liquid interfaces shown. Leading scrubber types. Packed bed. pressure drop. Each type has distinctive features.probably be impractical to select this scrubber with a high fly ash load waste solid design is also influence by separate removal of fly ash and SO2. Compliance with EPA standards entails SO2 removal greater than 80% and fly ash removal greater than 99%. spray tower and spray column. perforated trays or cellulose sections similar to cooling-tower fill: of spray configuration or venturis: or rotating drums laced with chains: or of movable rods. The physical interface may consist of hollow balls porous balls or solid marble sphere. Stoichiometry. Limestone particle size. Each scrubber unit consist of (1) a variable-throat venturi that removes fly ash and provides an initial stage of SO2 removal followed by (2) a counter current tray absorber. For example. Percent solid in slurry. Sprays in the venturi and the absorber drain into separate reaction tank where chemical reaction are allowed to go to completion before recirculating the slurry back to scrubber The major criterion for selecting a scrubber is high Efficiency. Gas/liquid interference. are the venturi. ability to handle slurries without plugging these are the other selection factors. Of all the scrubber parameter. floating bed.
Sprays towers have low pressure drops. On the other hand. which relies on steam for the turbine cycle to supply a heat exchanger at the scrubber outlet. but limited to lowsulfur-oil firing because SO2 emission control may be compromised. but liquid-to-gas ratios of only ( about 10-15 in. With this method. High liquid-to-gas ratios (30-40) are required. (2) flue gas bypassing mixes gas bypassed around the scrubber with scrubber exit gas-an inexpensive technique. true heat recovery is possible. (4)steam injection. H2O ). Several reheating schemes are used (1) Direct-fired burning natural gas or low sulfur oil is convenient and reliable but expensive. It must be reheated to restore its buoyancy and to lessen the chances for condensation which could lead to reheater corrosion stack and fan deterioration and formation of visible plume. Eliminators come in various design. venturi scrubbers operate at high pressure drop (about 15 in. but are typically of open construction and low flow resistance technique under development for controlling mist-eliminator plugging-always a treat. is economical but would require added coal firing and some modification of the turbine. although a large exchanger may be subject to low-temperature. the gas through the scrubber the gas cools the 120130 degree F and become saturated. Efficient combustion minimizes fuel costs Stoichiometric Air: . also. (see attached for mist eliminator construction). but may not provide thorough enough mixing to handle the SO2 from high sulfur fuel at top efficiency. (3) hot-air injection. H2O). Mist eliminator are installed in the scrubber to catch mist carryover in the cleaned gas. using excess heat from the air preheater is inexpensive but may affect heat efficiency of the boiler. (5) recuperative transfer in which a heat exchanger is added to a transfer heat from gas inlet of the scrubber to its outlet. While passing through the scrubber. under sprays are recommended to wash off soft scale. Main disadvantage is the potential for scaling. the mist is collected and returned to the scrubber.removal at relatively low pressure drop.
The dilution coefficient. Air contains 23. H.232 = 2.2% oxygen by mass. . Excess air is always needed for complete combustion.67 kg 2. The per cent excess air supplied is % excess air = WA – WT / WT x 100 where WA is the actual amount of air supplied for complete combustion of 1 kg fuel.67/0. oxygen and sulfur in the fuel as given by the ultimate analysis. It is expressed as a percentage or by the use of a dilution coefficient. hydrogen.3 S Where C.67 C + 8 H + S – O where O is the oxygen in the fuel.The ultimate analysis of the fuel is given by: C + H + O + N + M + A = 1.5 ( H – O/8 ) + 4. Therefore.67 kg 3.67 C kg 2H2 4 kg 1 kg H kg + O2 32 kg 8 kg 8 H kg = 2H2O 36 kg 9 kg 9 H kg S 32 kg 1 kg S kg + O2 32 kg 1 kg S kg = SO2 64 kg 2 kg 2S kg Oxygen required for complete combustion of 1 kg fuel is WO2 = 2. d.67 C kg = CO2 44 kg 3.232 S Or Wt = 11.232 ( H – O/8 ) + 1/0. Complete combustion of fuel cannot be achieved if only the theoretical or stoichiometric air is supplied.232 C + 8/0.0 Oxygen needed for the oxidation processes can be calculated as follows: C 12 kg 1 kg C kg + O2 32 kg 2. O and S are the mass fraction of carbon. theoretically air required for complete combustion of 1 kg fuel is Wt = WO2/0. is d = WA / WT The percentage of excess air varies between 15 to 30% for most large utility boilers.5 C + 34.
6.Combustion products. Nitrogen…………………….6 N2…………………….0022 . Assuming that such a plant has instrument for analyzing flue gas composition and measuring flue-gas temperature the method describe here suffices to tell the operation whether his combustion conditions are proceeding satisfactorily or not while the method is approximate numerous checks have shown the results to be within 2% of those found by using the longer complete methods the operator must know his fuel type and its heating value in Btu/lb as-fired the fuel supplier normally can give this information with satisfactory accuracy. 10.0 % 6..334 Btu/lb Room temperature …………… 36 degree C Flue-gas temperature ………… 205 degree C Flue.9 CO……………………. Flue-gas analysis by volume ( as furnished ): CO2……………………10.0968 O2 = ..0270 N2 = .gas analysis : a Carbon dioxide …………….Every textbook on steam power plants has a complete demonstration on the calculation demonstration on the calculation of fuel combustion such an exhibit usually assumes that complete fuel flue-gas and refuse analyses are available but may plants especially in the smaller capacities do not do not have such complete information and cannot justify the money needed to determine nevertheless to operate these plants economically engineers should calculate combustion performance on a regular basis and use these data to guide day to day operations. Knowing air components by volume to be 6.7 Combustion calculation.6 % c.81.003 S = .9% oxygen 81% nitrogen. Flue-gas analysis by Osrat or similar apparatus is useful in checking efficiency..8543 . 1..9 % d.8713 H2 = .. Carbon monoxide ………… 0. Boiler efficiency (from test) … The combustion equation is: 89. Short-cut calculation methods helps you determine combustion efficiency quickly ( December 2004 – test ) 1. 2. 4. 6.8 O2……………………. Oxygen …………………….034 .8 % b.. 5.1131 .02 Excess Air = 20% . 0. 3. Bunker C Heating value …………………18. Type of fuel ………………….0 % Fuel Analysis: C = . the following example shows how to figure back from the flue-gas components to find out how much air was supplied initially.
43 Mass oxygen supplied = 10.12 + ..7/32 + x Sulfur 3.1x64 + .85.26 therefore g = 4.01 kg Therefore: .5 ( .72 = .458 x = 7.84 = b + d + e + g/2 therefore d = .O/8 ) + 4.13/12 Hydrogen 9.3S Wth = 11.68/2 =b =g Oxygen 2.4 kg/kg fuel Theoretical air required per kg fuel Wth = 11.5C +34.76 kg Mass of air for 100 kg = 333.458 + 5.084 = 10..76x10. ___e___ = 0.32 % Wth 11.14 kg/kg fuel Mass of dry flue gas formed per kg fuel = 13.11 + .5 x .4/32S + 2.452x32 + 3.7/32O2 + xO2 +3.66/2 .5 ( H .08 x 100 = 3.12x44 +.1131 .08 Mass of dry flue gas formed for 100 kg fuel = bCO2 + dSO2 + eO2 + fN2 =7.002x28 = 1387.01 b + d + e +f b + d + e+ f e = 7.4 – 11.43/12C + 11.4/32 =d Nitrogen 3.08 kg/kg fuel Percentage excess air = WA – Wth x 100 = 14.87 kg/kg fuel Mass of water vapor formed per kg fuel = 5.31/2H + 3.66 x 18/100 = 1. WA = 14.8543 + 34.76xN2 bCO2 + dSO2 + eO2 + fN2 +gH2O Equating coefficients: Carbon 87.76/0.027/8 ) + 4.1572 .21/15.3 x 034 Wth = 11.232 = 1440 kg Mass of air supplied per kg fuel.43 x 32 = 333.10 Volumetric analysis: ___b + d___ = 0.76x =f therefore b = 7.
9622kg/liter Volume of Dry flue gas = 31.87 kg/kg fuel x 2.004347 3.089 0.2 0.000 kg of steam/hr.68 75.068 liter/kg steam x 35. The given concentrations of SO2 and NO2. Fuel in liter per hour = .2 100.76.8 kg/hr.4 0. Basing it on the required emission concentrations as given by the clean Air Act.762.47697 mole-% 11.47657 = 28. Inlet Gas Outlet Gas Inlet Liquid Outlet Liquid Quantity Composition Temperature 0. the average molecular weight of the effluent gas is calculated from the given concentrations in weight per cent: Average Molecular Weight of the Gas: Flue Gas O2 N2 CO2 H2O SO2 NO2 % wt 13 73. MW = 100/3. Mass of Dry flue gas = 13.003125 0.4063 2.762.125 100.00 Ave.1.6143 0.380 ltrs/hr. the target percentage removal is calculated: Target % removal of SO2 = 4121 – 700 x 100 = 83 % 4121 To facilitate the evaluation of gas properties./hr Design Calculations for Gas Absorber: ( Based on the removal of SO2 ) .33°C are corrected to the ambient condition of 30°C. x . 2.00019 30°C Design calculation for Gas Absorber: ( based on the removal of SO2 ) The given concentration for SOx and NOx are assumed to be predominantly SO2 and NO2.03 0.380 liters/hr. Gas flow rate = 31.19 5.2444 0.88 7.8 kg.2 9 4.2045 0. which are the based on 178.00215 30°C 30°C 0 30°C 0. = 2. The design calculation are based on these components.00215 (SO2 and NO2) 0.0 MW moles 32 28 44 18 64 46 0.
of SO2.89 Thus . 5 x* = y1 /15.89 = 0.0009 mole fr.mole/hr.5 % Exit mole ratio of SO2: Y2 = 0.8 x 2.000141 =15.0009/0.0.00224 Assume linear.9991 (1. Inlet conc.76 = 2430 lb.89x Calculation of Minimum Liquid Flow rate.12.9) = 0.0009/15.762. y = 0. the following relationships are obtained: When x = 0.2/28.000090 ≈ y2 (mole fr) Limiting flow rate of the liquid is evaluated using the solubility of the gas as the basis: From the solubility data given in Foust. the equation of the equilibrium line for dilute solutions at 30°C is obtained as y* = 15.16.00224/0.L in Ls X in x in G out Gs Y out y out L in Ls X out x out G in Gs Y in y in MATERIAL BALANCE DIAGRAM Flow rate of Inlet Gas = 31. the slope of the equilibrium line.89 = 5. The desired recovery is 82. m = y/x = 0. Assume 90% recovery.000141. y1 = 0.66x10¯ 5 . Fig.
850kg/hr. assume 35% water circulation = 60 cu. Since 64 kg/hr of SO2 needs 56 kg/hr.85cu.535 ) = 125. therefore with the above weight of SO2 = 127 kg/hr. The CaCO3 required = 127/64 x 100 = 198 kg/hr.66x10¯ = 14.474 x18 = 62. of CaO and CO2 = 44 kg/hr. Calculation of CaO Consumption: Main Chemical reactions • SO2(gaseous) • H2SO3 • HSO¯3 = H + SO=3 • CaCO3 (solid) = CaCO3(aquaeous) SO2(aqueous) + H2O H2SO3 HSO¯3 + H+ Ca+ + + CO=3 + H+ = CaHCO+3 • CaHCO+3 = Ca+ + + HCO¯3 • Ca+ + + SO3 + 0.m.070lbs/hr.5 H2O(s) • CaSO3 + ½ O2 = CaSO4 The Molecular Weight of SO2 = 64 The Molecular Weight of CaCO3 = 100.35 = 75 cu. ≈ 3. Calculation of Actual Water flow rate assuming 2 time the minimum. where 1ppm = .m/hr x 1.(L'/V')min.8 kg/hr.9991 ) = 3. x .0009 – 0.5 H2O = CaSO3 • 0.m/hr.00009/5. At 4000ppm. . ≈ 56. L'actual = ( 2 ) ( 62.31)( 243 x 0.474lbmoles/hr. = y1 – y2/x*1 – x2 = 0. Therefore with loss due to evaporation and with the cake. a total of CaCO3 = 100 kg/hr.004 = 127 kg/hr.762./hr.535lbs/hr. ≈ 56.31 L'min = (14. where CaO= 56 & CO2 = 44.0010% so therefore the SO2 within the flue gas is SO2 = 31.
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