Chapter 1 4 02 The Use of Limestone Slurry Scrubbing to Remove Sulfur Dioxide from Power Plant Flue Gases! Protection of the environment through the development of processes that have minimal ecolog- ical impact is one of the most important responsibilities facing chemical engineers. Moreover, it is often necessary to use chemical engineering principles to remedy existing environmen- tal problems. In this chapter, we examine a situation in which a coal-burning power plant is designed so that the impact on its surroundings is minimized. Coalis an abundant and practical source of energy, and it can be a source of raw materials used in chemical production, Coal occurs in various forms,? and the form used in a particular application often depends on its availability in the region of the application. Coal is predomi- nantly carbon, However, it also contains numerous other elements, including metals, nitrogen compounds, and sulfur, as well as hydrocarbon volatile matter that can be burned to produce heat, water, and carbon dioxide (CO;). Coal is burned in many of the world’s power plants to generate electricity. Significant air pollution is produced if the stack gases from coal-fired furnaces are not treated before being released to the atmosphere. Untreated gases contain soot (fine unburned carbon particles), nitrogen oxides (NO,), ash, and sulfur dioxide (S03). Sulfur dioxide emissions from coal‘ired furnaces are regulated in the United States by the Environmental Protection Agency (EPA) and appropriate state and local agencies. Cur- rent EPA standards require that gases released to the atmosphere from new and some existing power plants (some existing plants are subject to a less rigorous standard) contain no more than 520 nanograms SO, per joule of higher heating value of the fuel fed to the furnace (1.2 Th SO,/million Btu). In addition, these plants must remove at least 90% of the SO, released Prepared by Ronald W, Rousseau and Jack Winnick, School of Chemical Engineering, Georgia Tastitute of Technology. Avante, GA; and Norman Kaplan, National Risk Management Research Laboratory, US. Env ronmental Protection Agency, Research Tiangle Park, NC. °RH. Perry and D. W. Green, Eas, Perry's Chemical Engineer" Handbook, 7h Eatin, McGraw-Hill, New York, 1997, pp. 27410276Process Description 603 when burning the coal The emissions standard for some exiting plants may be satisfied by burning low-sulfur coal, by removing sulfur fom the coal prio to combustion, or by removing SO, from the product gases before they are released tothe atmosphere. The emission standard for new plants is more stringent and may only be achieved in practice by removing SO from stack gases. The technology for removing $O, from sack gases is more advanced than that for separating high percentages of sulfur directly from coal, anda large number of stacks desulfurization procestes are available commercially. We examine one of these processes in this case study Commercial processes for $O, removal are classified as regenerative or throwaway, de- pending on whether or not the agent used to remove $O; is reusable. Some throwaway pro- cesses can be modified to produce a saleable product (gypsum) without regeneration ofthe absorbent aateral. Regenerative processes have two miajor steps: the removal of dilute SO, from stack gases by separating agent followed by removal of SO, in concentrated form from the separating agent. which is then recycled tothe first step. An example of such a procedure is the Wellman-Lord process, which frst absorbs the SO, in an aqueous soltion of sodium sulfite (Na,$O3). In the solution, the following reaction occurs: NaSO5 + $0; + HyO + 2 NaHSOs aay Subsequently, the solution is heated and, at the resulting elevated temperature, the process is reversed! 2NaHSO; — Na,SO; + SO; + H,0 42 ‘The regenerated Na;SOs solution is recycled to the absorber, and the concentrated $0; pro- duced is captured and processed further to recover elemental sulfur. ‘Throwaway processes utilize a separating agent to remove SO; from the stack gases fol- owed by disposal of both the SO» in an innocuous form (CaSO, + } HO) and the slurried sep- arating agent, calcium carbonate (CaCO,). Although there are many processes that involve injection of either wet or dry limestone into the power plant furnace, we have chosen to use limestone-slurry serubbing in the present case study. PROCESS DESCRIPTION Five hundred megawatts of electrical power (500 MWe)! is to be generated in the present fa- city. Coal wth properties given in Table 141 is fed at 25°C to a furnace where itis burned vnth 15% excess air, During combustion ofthe coal, sulfur reacts to form $0, and a negligible mount of sulfur trioxide ($0). while carbon and hydrogen are oxiized completely to CO ‘and H,O. Essentially all of the nitrogen in the coal leaves the furnace as Np.’ The ash in the coal leaves the furnace in two streams: 80% leaves as fy ash inthe furnace ive gas, and the remainder leaves the furnace as bottom ash at 900°C. Combustion iris brought into the process at 25°C and 50% relative humidity and sent to a heat exchanger, where its temperature is increased to 315°C by exchanging heat with the fumace fiue gas. It is then fed tothe boiler, where it reacts with coal The fle gas leaves the furnace at 330°C, goes to an electrostatic precipitator where 99.9% of the particulate material [Federal New Source Performance Standards for contol of $O: rom power plant are applicable to elecsie uly steam-generating units that are capable of fring more than 73 MW (250 milion Btuh) heat input of fossil {ue and for which construction or modifieation was commenced after September 18,1978. This regulation was proposedin the Federal Register. Vol. 3, No. 182, Tuesday, Sep. 19, 178.The 320g limit applies t soli fuel, “The notation MWe should be read as megawate of electricity. 5A very small fraction ofthe nitrogen in the coal andlor ai e converted to gassous NO, during combustion, “These ate pollutants that must also be removed from the fe ga or controled by combustion modification, but that technology tot within the scope ofthis cae std604 Chapter 14 The Use of Limestone Slurry Scrubbing to Remove Sulfur Dioxide from Power Plant Flue Gases Table 41 Average Properties of Coal Composition (Ultimate Analysis) Component Dry W% Carbon 52 Hydrogen, 50 Nitrogen 16 Sulfur 35 Onygen 15 Ash 72 ‘Moisture: 4.80 kg/100 kg dy coal HIV. 30,780 Lifkg dey coal (Gee Section 268) Dry coal C, = L046 13/(ke-"C) ‘Ash: C, ~ 0921 KIileg-"C) is removed, and then to the air preheater where it exchanges heat with the combustion air. The flue gas leaves the air preheater and is split into two equal streams, with each being the feed stream to one of two identical scrubber trains. Each of the trains is sized to provess 60% of the flue gas, giving flexibility and partial redundancy should one of the trains require downtime. In each of the scrubber trains, the divided off-gas stream is fed to a scrubber, where it contacts an aqueous slurry of limestone and undergoes adiabatic cooling to 53°C. Sulfur dioxide is absorbed in the slurry and reacts with the limestone: CaCO, +80; + JO = C805. } LO + CO, ass, ‘The solid-tiquid limestone slurry enters the scrubber at 50°C; the liquid portion of the slurry flows at a rate of 15.2 kg liquid/kg inlet gas and the solid-to-liquid ratio in the slurry is 1:9 by weight, The liquid is saturated with CaCO; and CaSO, The cleaned flue gas meets the EPA standard on SO; emissions; it leaves the scrubber saturated with water at 53°C, containing the CO; generated in the scrubbing but none of the entering fly ash. Sulfur dioxide is the only constituent ofthe flue gas that is absorbed in the scrubber. The cleaned flue gasis then reheated to 80°C, blended with the cleaned flue-gas stream from the other train, and sent to the stack where itis released to the atmosphere. ‘The solids in the spent aqueous slurry leaving the scrubber contain unreacted CaCO, fly ash removed from the flue gas, inert materials that enter the process with fresh limestone, and ‘CaSO, formed by the reaction in Equation 14.3. The liquid portion of the slurry is saturated with CaCOy and CaSO, and has a specific gravity of 0.988. The spent slurry is split into two streams, One of these streams is sent to a blending tank where itis mixed with fresh finely ground limestone, makeup water, and a recycle stream whose source will be described shortly. ‘A fresh slurry stream from the blending tank is fed to the top of the scrubber. The other spent slurry stream is sent to a filter where wet solids containing fly ash, inert materials, CaSOy, and CaCO, are separated from a filtrate, which is saturated with the latter two components and is the recycle stzeam fed to the blending tank. The wet solids contain 50.2 wt% liquid that has the same composition as the filtrate. The fresh ground limestone is fed to the blending tank at a rate that is 5.2% in excess of that requited to react with the SO, absorbed from the flue gas, The limestone material fed consists of 92.1% CaCOs and the remainder is inert insoluble material ‘The generation of steam and ts utilization in the production of electricity inthis facility are typical of many power cycles.° The boiler used inthe present situation generates steam at super ‘Sane Tis Generation and Use, 3th Editon, Babcock & Wilcox, New York, 1978,PROBLEMS a4. 142, 143. 144, 44s. 146. 147. 148. 149. sao, aa, Problems 605 critical conditions: 540% and 24.1 MPa absolute. Mechanical work is derived by expanding the steam through a power-generating system of turbines; appropriate reheaters and moisture separators are used to facilitate that operation. The low-pressure steam extracted from the power system contains 27.5% liquid water at 6.55 kPa absolute, Heat is removed from the wet low-pressure steam in a condenser by cooling water that enters the condenser at 25°C and leaves at 28°C. Saturated condensate at 38°C is produced by the condenser and pumped back to the boiler. Problems 14.2 through 14.10 should be solved using a basis of 100kg dry coalimin fed to the furnace. Construct a flowchart of the process and completely label the streams. Show the details of only one ‘rain in the SO, scrubber operation. Estimate the molar flow rate (kmol/min) of each element in the coal (other than those inthe ash) Determine the feed rate (kmol/min) of O, required for complete combustion of the coal IF 15% excess O; is fed to the combustion furnace, estimate the following a) The oxygen and nitrogen feed rates (kmol’min), () Tae mole traction of water in the wel air, the average molecular weight, the dew point and de grees of superheat of the wet ar, and the molar flow rate (kmol/min) of water in the air stream, (©) The air feed rate (kmol/min, standard cubic metersimin, cubic meters/min) Estimate the flow rate (Kg/min and kmol/min) of each component and the composition (mole frac tons) of the furnace flue gos (Ignore the fy ash in calculating mole fractions ) At what rate (kg/min) is ly ash removed from the flue gas by the electrostatic precipitator? ‘The system may be astumed to meet the standard of 90% removal of the SO: released upon com: bustion (a) Determine the flow rate (ka/min and kmol/min) of each component inthe cleaned flue gas leav- ing the serubber. (@) Determine the flow rate (K/min) of slury entering the scrubber. (© Estimate the solid-to-liquid mass ratio in the stury leaving the scrubber. (@) Estimate the feed rate (kp/min) of fresh ground limestone to the blending tank. (©) What are the Dow rates (K/min) of inerts, CaSOs, CaCO, fly ash, and water in the wet solids removed from the filter? What fractions of the CaSOs and CaCO, are dissolved in the liquid portion of the wet solids? (6 Estimate the rate (K/min, L/min) at which the Strate is recycled tothe blending tank. At what rate (kg/min, Limin) is makeup water added to the blending tank? At what rate is heat removed from the furnace? Assuming that all of the heat removed from the furnace is used to generate steam (ie, none is lost to the surroundings), estimate the rate of steam generation inthe power evel. Determine the effect of the percent excess air fed to the boiler furnace by calculating the rate of team generation (kg/imin) for air low rates that are 5% and 25% in excess of that theoretically requized. Speculate on the reason for choosing 15% excess air in the prescribed process by giving ‘one possible reason for not using less air and one for not using more. Determine the temperature of the flue gas as it leaves the heat exchanger (air preheater) following the boiler, Estimate this value for the two alternative air flow rates corresponding to 5% and 25% excess oxygen, ‘Compare the release of SO, inthe scrubbed fue gas (determined in Problem 146) with the EPA limit. ‘of no more than $20 nanograms SO, per joule of heat input to the boiler. (Nore: Ifyou determined that meeting this requirement requires greater than 90% removal of $O;, you would, in practice, have to revise your previous calculations) Power plants of the type described here operate with an ellciency of about 39%; tha is, for each unit of heat released with the combustion of coal, 0.39 unit is converted to electrical energy: From. this effcieney and the specified power output of S00 MWe, determine the following606 Chapter 14 The Use of Limestone Slurry Scrubbing to Remove Sulfur Dioxide {rom Power Plant Flue Gases (2) The coal feed rate (kg/h) (b) The air feed rate (kimol/min, standard cubic metersimin, cubic meters/min). (©) The flow rate of each component in the gas leaving the furnace (kmol/min, kg/min) (@) The rate of steam generation (kg), 14.12, For the required coal feed rate, scale the results from Problem 14.6 to determine for each scrubber train the actual low rates (kg/h) of wet solids and filtrate ftom the filter, the slurry flow rates entering and leaving the serubber, the flow rates of gas (kg/h and m/min) entering and leaving the scrublsr, and the flow rates (kg/h) of fresh water and limestone fed to each blending tank 14.13. Why is the scrubbed flue gas reheated before it is sent tothe stack? 14.14, The following are alternatives by which the scrubbed flue gas can be reheated: (1) bypassing the 14s, 1446, 1447, 1418, 1419, 1420. scrubber with a fraction of the flue gas leaving the air preheater and mixing this stream with cleaned flue gas; (2) burning natural gas and blending the combustion products with the scrubbed flue gas and (3) using steam from the power cycle ether to heat air that is blended with the scrubbed fue gas of to heat the due gat in a heat exchanger. (2) Give a reason for rejecting Alternative 1. (b) In evaluating Alternative 2, assume that the natural gue consists entirely of methane at 25°C and that itis burned adiabatically with 10% excess air that has the same conditions as the air fed to the furnace. If the combustion products are blended with the cleaned flue gas, at what rate would methane would have to be burned to raise the stack-gas temperature to the desired value? (© How much more coal (ke dry coal/h) would have to be burned for Alternative 3 if the amount of heat released by burning coal (kJ/kg dry coal isthe same as determined in Problem 14.77 Suggest two process alternatives by which the heat can be transferred to the flue gas. ‘Assuming that option 2 in Problem 14.14 is used, construct a graph of the velocity of the stack gas (atm, 80°C) versus the diameter of the stack. Cover a range of Velocities from 5 to 15 mis. ‘What isthe flow rate of cooling water (kghh and L/h) required to condense the low-pressure steam, inthe power cycle? ‘The pump used {o transport the steam condensate in the power cycle from the condenser to the boiler has an efficiency of 80% (i¢., 80% of the work done by the pump is on the condensate). What size pump (kW and horsepower) is required for the estimated water flow rate? What assumptions hhave you made in these calculations? We assumed a 39% efficiency for this power plant, meaning that for each unit of heat released with the combustion of coal, 0.39 unit is converted to electrical energy. Using an energy balance around the power-generating system of turbines, reheaters, and condensate separators, estimate an energy efficiency defined as 100 X the electrical energy generated (S00 MWe) divided by the change in enthalpy of the steam flowing through the power-generating system, Why does the EPA standard for new power plants have two criteria? Using your own words, explain them in terms that can be understood by an informed public, Include in your discussion the impact of the regulation oa the use of clean coal, |. I the 520-n9/F criterion had been followed, what would be the emission rate of SO: in ke/day?