Thermal Oxidation for VOC Control Volatile organic compounds (VOCs) generally are fuels that are easily combustible. Through combustion, which is synomonous with thermal oxidation and incincera- tion, the organic compounds are oxidized to CO 2 and water, while trace elements such as sulfur and chlorine are oxidized to species such as SO 2 and HCl. Three combustion processes that control vapor emissions by destroying collected vapors to prevent release to the environment are (a) thermal oxidation — flares, (b) thermal oxidation and incineration, and (c) catalytic oxidation. Each of these processes has unique advantages and disadvantages that require consideration for proper application. For example, flares are designed for infrequent, large volumes of concentrated hydrocarbon emissions, while thermal oxidizers are designed for high-efficiency treatment of continuous, mixed-hydrocarbon gas streams, and cata- lytic oxidizers are designed to minimize fuel costs for continuous, low-concentration emissions of known composition. The design of the basic processes can be modified for specific applications, resulting in the overlap of the distinctions between pro- cesses. For example, ground flares are basically thermal oxidizers without heat recovery that frequently are used for intermittent flow of relatively low volumes of concentrated VOC streams. 13.1 COMBUSTION BASICS As every Boy Scout, Girl Scout, and firefighter knows, combustion requires the three legs of the fire triangle illustrated in Figure 13.1. The oxidizer and fuel composition, i.e., air-to-fuel ratio, is critical to combustion. If the fuel concentration in air is below the Lower Flammability Limit (LFL), also known as the Lower Explosive Limit (LEL), the mixture will be too lean to burn. If it is above the Upper Flammability Limit (UFL), it will be too rich to burn. Fuels with a wide range of flammability limits burn more easily than those with a narrow range. With a narrow range, the flame is more unstable since the interior of the flame can easily be starved for air. The heating value of the fuel — the amount of heat released by the combustion process — is determined by the heat of combustion and the concentration of the hydrocarbons in the gas stream. Values for the heat of combustion for common organic compounds are provided in Table 13.1. The heat of combustion is the same as the heat of reaction for the oxidation reaction, and therefore can be calculated from the heats of formation of the reactants and products. It is the net chemical energy that is released by the oxidation reaction when the reactants begin at 25ºC and after the reaction products are cooled to 25ºC. That the reactants are first heated to the ignition temperature and the exhaust gases are hot does not affect the value 13 9588ch13 frame Page 191 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC for the heat of combustion, because the value includes the energy recovered by cooling the exhaust gases. Indeed, the “higher heating value” includes the energy recovered when water vapor is condensed to liquid at 25ºC, while the lower heating value is based on water remaining in the gaseous state. The flame temperature is determined by a heat balance including the energy produced by combustion, absorbed by the reactant gases, released to the exhaust gases, and lost to the surroundings by radiation. Therefore, factors such as the combustion air temperature, composition of the exhaust gases, and configuration of the combustion chamber affect the peak flame temperature. Despite exposure to flame in the presence of oxygen, not all of a hydrocarbon pollutant will react. The destruction efficiency of VOC pollutants by combustion depends on the three Ts: temperature (typically 1200 to 2000ºF), time (typically 0.2 to 2.0 s at high temperature), and turbulence. The required destruction efficiency often is expressed as 9s. Two 9s is 99% destruction efficiency, and five 9s is 99.999% destruction efficiency. Some VOCs burn easily and do not require extremely high destruction efficiency. Others, especially chlorinated hydrocarbons, do not burn as easily, and the required high destruction efficiency demands a good combination of high temperatures, adequate residence time at high temperature, and turbulence to promote mixing for good combustion of the entire gas stream. Table 13.2 lists the relative destructability for some common VOCs. 13.2 FLARES Flaring is a combustion process in which VOCs are piped to a remote location and burned in either an open or an enclosed flame. Flares can be used to control a wide variety of flammable VOC streams, and can handle large fluctuations in VOC con- centration, flow rate, and heating value. The primary advantage of flares is that they have a very high turndown ratio and rapid turndown response. With this feature, they can be used for sudden and unexpected large and concentrated flow of hydro- carbons such as safety-valve discharges as well as venting-process upsets, off-spec product, or waste streams. FIGURE 13.1 “Fire triangle.” 9588ch13 frame Page 192 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC Flares cannot be used for dilute VOC streams, less than about 200 BTU/scf, without supplemental fuel because the open flame cannot be sustained. Adding supplemental fuel, such as natural gas or propane, increases operating cost. Flam- mable gas sensors can be used to regulate supplemental fuel. TABLE 13.1 Heat of Combustion for Various Compounds Compound Lower Heating Value (BTU/lb) Acetaldehyde 10,854 Acetone 12,593 Acetylene 20,776 Ammonia 7992 Benzene 17,446 Butane 19,697 Carbon monoxide 4347 Chlorobenzene 11,772 Chloroform 1836 Cyclohexane 18,818 Dichloroethane 4990 Ethane 20,432 Ethanol 12,022 Ethylbenzene 17,779 Ethylene 20,295 Ethylene dichloride 5221 Ethylene glycol 7758 Formaldehyde 7603 Heptane 19,443 Hexane 19,468 Hydrogen 51,623 Hydrogen sulfide 6545 Methane 21,520 Methanol 9168 Methyl ethyl ketone 13,671 Methylene chloride 2264 Naphthalene 16,708 Octane 19,227 Pentane 19,517 Phenol 13,688 Propane 19,944 Propylene 19,691 Styrene 17,664 Toluene 17,681 Trichloroethane 3682 Trichloroethylene 3235 Vinyl chloride 8136 Xylene 17,760 9588ch13 frame Page 193 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC 13.2.1 E LEVATED , O PEN F LARE The commonly known flare is the elevated, open type. Elevated, open flares prevent potentially dangerous conditions at ground level by elevating the open flame above working areas to reduce the effects of noise, heat, smoke, and objectionable odors. The elevated flame burns freely in open air. A simplified flow schematic of an elevated, open flare system is shown in Figure 13.2. The typical system consists of TABLE 13.2 Relative Destructability of VOC Pollutants by Combustion VOC Relative Destructability Alcohols High Aldehydes Aromatics Ketones Acetates Alkanes Chlorinated hydrocarbons Low FIGURE 13.2 Simplified flare schematic. 9588ch13 frame Page 194 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC a header to collect waste gases, some form of assist to promote mixing (frequently steam is used), and an elevated burner tip with a pilot light. A typical burner tip is shown in Figure 13.3. Atmospheric combustion air is added by turbulence at the burner tip. Although flares have a very high turndown velocity, exit velocity extremes determine the size of the flare tip. Maximum velocities of 60 ft/s and 400 ft/s are used for waste streams with heating values of 300 BTU/scf and 1,000 BTU/scf, respectively, to prevent blowout of the flame. A correlation for maximum velocity with heating value is provided by Equation 13.1: (13.1) where V max = maximum velocity, ft/s B v = net heating value, BTU/scf The design volumetric flow should give 80% of the maximum velocity. FIGURE 13.3 Steam assisted smokeless flare tip. (Courtesy of Flare Industries, Inc.) log max10 1214 852 V B v () = + () 9588ch13 frame Page 195 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC 13.2.2 S MOKELESS F LARE A SSIST Mixing and complete combustion can be improved at the flare tip either by steam- assist, air-assist, or pressure-assist mechanisms. As shown in Figure 13.4, the sup- plemental assist can have a dramatic positive effect on preventing the production of black smoke. A large part of the effect can be attributed to turbulence that draws in combustion air. The water molecules in steam-assisted flare headers may contribute additional benefits. They may separate hydrocarbon molecules which would prevent polymer- ization and formation of long-chained oxygenated compounds that burn at a reduced rate. And they may react directly with hot carbon particles through the water–gas reaction, forming CO, CO 2 , and H 2 from soot. FIGURE 13.4 Steam-assisted flare: (a) steam off, (b) steam on. (Courtesy of John Zink Company, LLC.) 9588ch13 frame Page 196 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC Steam typically is added at a rate of 0.01 to 0.6 lb steam per lb of vented gas, depending on the carbon content of the flared gas. Typical refinery flares use about 0.25 lb steam per lb of vent gas, while many general VOC streams use about 0.4 lb steam per lb of vent gas. A useful correlation is 0.7 lb steam per lb of CO 2 in the flared gas. Steam assist can produce a loud, high-frequency (above 355 Hz) jet noise in addition to the noise produced by combustion. Noise is reduced by using multiple small jets and by acoustical shrouding. Air assist is accomplished by using a fan to blow air into an annulus around the flare gas stack center channel. The turbulent air is then mixed at the burner tip. Due to the fan power requirement, air assist is not economical for high gas volumes, but is useful where steam is not available. Pressure assist relies on high pressure in the flare header and high pressure drop at the burner tip. This approach cannot be used with variable flow, greatly reducing the number of viable applications. 13.2.3 F LARE H EIGHT The required height of an elevated, open flare is determined primarily by limitation on thermal radiation exposure, although luminosity, noise, dispersion of combustion products, and dispersion of vented gases during flameout also are considerations. The maximum heat intensity for a very limited exposure period of 8 s is 1500 to 2000 BTU/h-ft 2 . This may give one just enough time to seek shelter or quickly evacuate the area. Most flares are designed for extended exposure at a maximum heat intensity of 500 BTU/h-ft 2 . The distance from the center of the flame to an exposed person is determined using Equation 13.2: (13.2) where D = distance from center of flame, ft τ = fraction of radiated heat that is transmitted (assume 1.0, but could be less for smoky or foggy conditions) F = fraction of heat that is radiated, function of gas composition, burner diameter, and mixing (typical values are 0.1 for H 2 in a small burner to 0.3 for C 4 H 10 in a large burner) R = net heat release, BTU/h K = allowable radiation, BTU/h-ft 2 The distance from the center of the flame to an exposed person takes into account not only the height of the flare tip, but also the length of the flame and the distortion of the flame in windy conditions. The length of the flame is determined by: (13.3) where L = flame length, feet D FR K 2 4 = τ π log . log . 10 10 0 457 2 04LR= () − 9588ch13 frame Page 197 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC Elevated flare stacks typically are supported in one of three ways: (1) self- supporting; (2) guy-wires; and (3) derrick. Self-supported stacks tend to be smaller, shorter stacks of about 30 to 100 ft, although stacks of 200 ft or more are possible, depending on soil conditions and the foundation design. Tall stacks can be supported more economically with the aid of guy-wires. Gas piping temperature fluctuations that cause expansion and contraction must be considered. A derrick structure is relatively expensive, but can be used to support the load of a very tall stack. 13.2.4 G ROUND F LARE It is possible to enclose a flare tip with a shroud and bring it down to ground level. In an enclosed ground flare, the burners are contained within an insulated shell. The shell reduces noise, luminosity, heat radiation, and provides wind protection. These devices also are known as once-through thermal oxidizers without heat recovery. This type of flare often is used for continuous-flow vent streams but can be used for intermittent or variable flow streams when used with turndown and startup/shutdown controls. A common application is vapor destruction at fuel loading terminals where the vapor flow is intermittent, but predictable. Enclosed ground flares provide more stable combustion conditions (temperature, residence time, and mixing) than open flares because combustion air addition and mixing is better controlled. Maintenance is easier because the flare tip is more accessible. But a disadvantage is that ground flares cannot be used in an electrically classified area because it creates an ignition source at ground level. Temperatures are generally controlled within the range of 1400 to 2000°F using air dampers. They may use single or multiple burner tips within a refractory-lined steel shell. Multiple burners allow the number of burners in use to be staged with the gas flow. Staging can be accomplished by using liquid seal diplegs at different depths or by using pressure switches and control valves. A ground flare enclosure that contains multiple burner tips typically is sized for about 3 to 4 million BTU per hour per square foot of open area within the refractory lining of the enclosure. 1 The height of the enclosure depends on the flame length, which is a function of a single burner size, rather than the total heat release. A typical height for 5 MMBTU/h burner tips is about 32 ft. 13.2.5 S AFETY F EATURES Flashback protection must be provided to avoid fire or explosion in the flare header. Protection is provided by keeping oxygen out of the flare header using gas seals, water seals, and/or purge gas, and by using flame arrestors and actuated check valves. Gas seals keep air from mixing with hydrocarbons in the vertical pipe of an elevated flare. Two types of gas seals, a dynamic seal and a density seal, are shown in Figure 13.5. A density or molecular seal forces gas to travel both up and down to get through the seal, like a P-trap water seal, and high-density (high-molecular weight) gas cannot rise through low-density gas in the top of the seal. A low purge flow of natural 9588ch13 frame Page 198 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC gas, less than 1 ft/s, ensures that the gas in the top of the seal is more buoyant than air, and can keep the oxygen concentration in the stack below 1% with winds up to 20 mph. Density seals are recommended in larger flares with tips greater than 36 in. diameter. 2 A dynamic gas seal is designed to provide low resistance to upward flow and high resistance to air flowing downward. Natural gas can be used for purge flow at about 0.04 ft/s to keep the oxygen concentration in the flare stack below 6%. Nitrogen also can be used as purge gas, and eliminates the possibility of burn-back into the flare tip at low flow rates. After high-temperature gas is flared, the stack is filled with hot gas that will shrink upon cooling, and that can tend to draw air into the stack. The purge flow compensates for the reduction in volume, and the required purge rate may be governed by the rate of cooling during this period. Flame arrestors and liquid-seal drums also are used to prevent flashback into the flare header. Liquid-seal drums have the advantage of avoiding the potential for being plugged by any liquids that might collect and congeal in the system. And they can be used as a back-pressure device to maintain positive pressure in the flare header. A disadvantage is the possibility of freezing if the liquid seal contains water. Steam coils can be used to heat the seal. Hydrocarbon liquids must be kept out of flare stacks to prevent burning liquid droplets from being emitted from the stack. Knockout drums are used to separate and collect any liquid droplets larger than about 300 to 600 µ m before gases are sent to the flare. They may be of either horizontal or vertical design. Generally, knockout drums are designed based on American Petroleum Institute (API) Recom- mended Practices. 3 FIGURE 13.5 Types of gas seals. (Courtesy of Flare Industries, Inc.) 9588ch13 frame Page 199 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC 13.3 INCINERATION An incinerator, or to be politically correct, a thermal oxidizer, burns VOC-containing gas streams in an enclosed refractory-lined chamber that contains one or more burners. The incoming waste hydrocarbon vapor can be co-fired with natural gas or propane to maintain consistently high oxidation temperatures. A ground flare is one type of incinerator. Discussed below are thermal oxidizers that are designed for high destruction efficiency with heat recovery built-in to reduce fuel consumption cost. Heat recovery may be achieved with recuperative heat exchangers, with a regener- ative design that employs ceramic beds, or by heating process fluids or generating steam. An advantage of thermal oxidation in an incinerator is the high destruction efficiency that can be obtained by proper control of the combustion chamber design and operation. If temperatures are maintained above 1800°F, greater than 99% hydrocarbon destruction is routinely achievable. 4 This efficiency is due to the increased residence time, consistently high temperature, and thorough mixing (the three Ts: time, temperature, and turbulence) in the combustion chamber. Thermal oxidizers can be costly to install because of required support equipment, including high pressure fuel supplies (for example, natural gas), and substantial process-control and monitoring equipment. In addition, public perception of a new “incinerator” can make it difficult to locate and permit a new unit. 13.3.1 R ECUPERATIVE T HERMAL O XIDIZER A recuperative thermal oxidizer uses a shell-and-tube type heat exchanger to recover heat from the exhaust gas and preheat the incoming process gas, thereby reducing supplemental fuel consumption. A schematic of a recuperative thermal oxidizer is shown in Figure 13.6. Recuperative heat exchangers with a thermal energy recovery efficiency of up to 80% are in common commercial use. 13.3.2 R EGENERATIVE T HERMAL O XIDIZER A regenerative thermal oxidizer uses ceramic beds to absorb heat from the exhaust gas and uses the captured heat to preheat the incoming process gas stream. Destruc- tion of VOCs is accomplished in the combustion chamber, which is always fired and kept hot by a separate burner. This system provides very high heat recovery of up to 98%, and can operate with very lean process gas streams because supplemental heat requirements are kept to a minimum with the high heat recovery. The gas steam may contain less than 0.5% VOC, and have a low heat value of less than 10 BTU/scf. A two-chamber regenerative thermal oxidizer in shown schematically in Figure 13.7. The incoming process gas passes through the warm ceramic bed and is preheated to almost the temperature of the combustion chamber. Figure 13.7 shows a typical inlet gas temperature of 100ºF exiting the first chamber at approximately 1430ºF. The combustion chamber provides time, temperature, and turbulence, with the combusted gases exiting at approximately 100 to 170ºF through the second ceramic bed. Heat is recovered in the second ceramic bed. When the process gas exit temperature reaches approximately 170ºF, valves switch the direction of flow 9588ch13 frame Page 200 Wednesday, September 5, 2001 9:55 PM © 2002 by CRC Press LLC [...]... Pressure-Relieving and Depressuring Systems, API Recommended Practice 521, 4th ed., Washington, D.C., 1997 4 U.S Environmental Protection Agency, Handbook — Control Technologies for Hazardous Air Pollutants, EPA-62 5-6 -9 1-0 14, Research Triangle Park, NC, 1991 5 Pitts, D M., Regenerative thermal oxidizers: structured packing improves performance, Chem Eng., 106(1), 113, 1999 6 Clean Air Compliance Handbook, ... switched to become an outlet bed A schematic of the three-chamber design is shown in Figure 13. 9 This figure shows that the purge gas can be treated process exhaust gas, which will be free of VOC Large and small three-chamber designs are shown in Figures 13. 10 and 13. 11 Figure 13. 12 shows a seven-chamber regenerative thermal oxidizer Five- and seven-chamber oxidizers are used not to improve VOC destruction... Press LLC 9588ch13 frame Page 202 Wednesday, September 5, 2001 9:55 PM FIGURE 13. 8 Two-chamber regenerative oxidizer emissions rapid-cycling valves and extensive ductwork The valves must be designed for very low leakage since any leakage contaminates the treated exhaust gases with untreated process gas Critical high-efficiency systems use zero-leakage valves with an air purge between double-seal surfaces... for more efficient thermal energy recovery.5 © 2002 by CRC Press LLC 9588ch13 frame Page 204 Wednesday, September 5, 2001 9:55 PM FIGURE 13. 11 Small three-chamber regenerative thermal oxidizer (Courtesy of Smith Environmental Corp.) FIGURE 13. 12 Seven-chamber regenerative thermal oxidizer (Courtesy of Smith Environmental Corp.) 13. 3.3 RECUPERATIVE VS REGENERATIVE DESIGN SELECTION Recuperative heat recovery... by CRC Press LLC 9588ch13 frame Page 205 Wednesday, September 5, 2001 9:55 PM FIGURE 13. 13 Loading random media (Courtesy of Smith Environmental Corp.) FIGURE 13. 14 Installing structured media (Courtesy of Geoenergy International Corp.) • Fan power, based on pressure drop and gas flow • Maintenance costs, affected by valve cycling and fouling of the heat exchanger or packing 13. 4 CATALYTIC OXIDATION... contain multiple gas passages It can provide up to 67% higher bulk density and up to 440% higher surface area © 2002 by CRC Press LLC 9588ch13 frame Page 203 Wednesday, September 5, 2001 9:55 PM FIGURE 13. 9 Three-chamber regenerative flow schematic FIGURE 13. 10 Three-chamber regenerative thermal oxidizer (Courtesy of Smith Environmental Corp.) than random packing, making structured packing a superior heat...9588ch13 frame Page 201 Wednesday, September 5, 2001 9:55 PM FIGURE 13. 6 Recuperative thermal oxidizer flow schematic FIGURE 13. 7 Two-chamber regenerative flow schematic so that the incoming gas passes through the freshly warmed bed By cycling the valves quickly, as often... Catalytic oxidation can be used as a “polishing” step, following a recovery unit (e.g., lean oil absorption or other VOC control system) which removes the majority of the hydrocarbon Given a constant flow of low-concentration vapor feed material, catalytic incinerators can provide economical high-efficiency VOC destruction REFERENCES 1 Leite, O C., Safety, noise, and emissions elements round out flare guidelines,... up of ceramic saddles of the same type that are used as packing material in packed scrubbers Figure 13. 13 shows random packing being loaded into a new bed Random packing is less expensive and easier to install compared to structured ceramic packing But structured ceramic packing, as shown in Figure 13. 14, can be used and exhibits lower pressure drop and a lower propensity to fouling with particulate... gases with untreated process gas Critical high-efficiency systems use zero-leakage valves with an air purge between double-seal surfaces If the VOC emissions from a two-chamber bed are measured, the concentration would vary as shown in Figure 13. 8 Intermittent spikes in the VOC concentration would occur each time the valves switch the direction of flow, because untreated process gas would be present in the . Air Pollutants , EPA-62 5-6 -9 1-0 14, Research Triangle Park, NC, 1991. 5. Pitts, D. M., Regenerative thermal oxidizers: structured packing improves perfor- mance, Chem. Eng. , 106(1), 113, . combustion can be improved at the flare tip either by steam- assist, air- assist, or pressure-assist mechanisms. As shown in Figure 13. 4, the sup- plemental assist can have a dramatic positive effect. small three-chamber designs are shown in Figures 13. 10 and 13. 11. Figure 13. 12 shows a seven-chamber regenerative thermal oxidizer. Five- and seven-chamber oxidizers are used not to improve VOC