Pollution control systems

Utilities cause a great deal of pollution. They would cause much more if it were not for application of pollution control technology. I briefly outline pollution control systems here for sulfur oxides, nitrogen oxides, and particulates.(25) Volatile Organic Compounds (VOCs) are also emitted as pollution, and are discussed last.

There are four common ways to try to eliminate the other effluents of combustion: by precombustion technology, by combustion technology, by postcombustion technology, or by use of a combined cycle gas turbine at low cost to try to avoid the installation of a whole host of treatment technologies. So far, utilities and industry in the U.S. have spent over $40 billion on pollution control.(26) Between 1970 and the present, SO2 emissions have dropped by more than 70% and particulate emissions have dropped by more than 90%.(26)

Precombustion cleaning

About 40% of all U.S. coal (70% of eastern and midwestern coal) requires cleaning before use to remove impurities and improve combustion. Physical cleaning can remove 30% to 50% of pyrites (iron-bound sulfur). Chemical and biological cleaning (seen as very promising) are in their infancy.(27,28) A plant built by Encoal, a subsidiary of Shell Oil, refines coal while cleaning it.(29) Coal, 1 kt/d of it, is cooked to turn it into more valuable hydrocarbons. It is pyrolysed to get a gas that can be condensed to liquid like heavy fuel oil. The remaining coal has a higher heating content than before treatment because of the loss of water (5.75 MJ/kg vs. 4.0 MJ/kg).(29) This technique does not reduce nitrogen oxide emission.

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Cleaning during combustion

This method is not of much use for reducing sulfur emissions, but is essential for reducing nitrogen oxide (NOx) emission. Recall from Ch. 7 that the formation of most nitrogen oxides is an endothermic process. Therefore, it takes place primarily at high temperatures where sufficient activation energy is available from the surroundings. While high temperatures are desirable for complete burning of the fuel, they necessarily produce large fractions of NO x. Some ingenuity has gone into reconciling these apparently contradictory desires. Low-NOx burners are now standard equipment in most power plants in America.

Fig. E14.1.1 Low NOx burner system. There are several combustion zones. (U.S. Fossil Energy Program, Department of Energy)

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It is possible to decrease NOx emissions through several methods in the combustion and postcombustion stages.(30) Staged combustion control adjusts the amount of oxygen available at places within the combustion zone; this is standard practice for coal-fired systems, and it reduces NOx by 25% to 50%. High-tech low-NOx burners work by decreasing the amount of air available in the primary combustion zone, making this region rich in fuel and deficient in oxygen. Without enough oxygen, the nitrogen in coal is not broken up to combine with oxygen. The combustion temperature is kept very low to prevent ambient air molecules from forming the NOx. Complete combustion of the coal is achieved by secondary low-temperature combustion zones. Also used is reburning,(27,28,31) which burns the coal in stages (natural gas may be introduced at later stages of burning). The overfire air technique involves injection of air above the flame, which helps burning be more complete at lower temperatures. These methods can remove about half the nitrogen oxides normally present in flue gas.

Flue gas recirculation involves mixing of flue gas into the air supply to the boiler; this causes lowered combustion temperatures and reduces NOx formation by 12% to 25%. About 75% of U.S. coal-fired power plants are using burners such as these to meet the Clean Air Acts requirements.

Postcombustion cleaning

Most power plants in operation choose one or more methods of postcombustion cleaning for sulfur removal. In some of these methods, NOx may also be removed. Virtually all must remove particulates after burning.

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Particulates

The simplest postcombustion particle cleaning device is an electrostatic precipitator. In the electrostatic precipitator, electrodes or thin wires are held at high potential difference (high voltage). Near the wires surface, gas molecules can be ionized, and electrons hit other gas molecules after being accelerated in the potential, ionizing them. This releases more electrons, ionizing more gas molecules, and so on. The electrons move toward the positive wire (or electrode); the positive ions move to the negative wire (or electrode). By this process, particles in the smoke precipitate onto the negative electrode with a high efficiency as smoke rises through a chimney (Fig. E14.1.2 a). The first control systems for particulates were electrostatic; these have been replaced by fabric filtering.

a.

b.

Fig. E14.1.2 a. In a smokestack in which there is a potential difference (a voltage) between metal plates or grids, charged particles are drawn to these surfaces and attach. The smoke particulates are removed. b. In a baghouse, the motor drives the bags back and forth to loosen the soot and other particulates that are trapped in the bags.

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The other particulate technology is construction of fabric containers that catch particules (called baghouses, see Fig. E14.1.2 b). These are enclosed fabric structures, essentially vacuum cleaner bags through which effluent must pass before it can escape up the stack. The bags hold the particles, which attach to the bag walls. When the bags are shaken, the particles fall off and are caught in a basin that is emptied every so often. Neither technique helps to control gases in the effluent, which may later cause acids to form in the atmosphere. Fabric filters can reduce emissions to below 0.01 kg/GJ.(26)

Sulfur

There are two ways of removing, or scrubbing, sulfur from the power plants gaseous effluent. These are wet scrubbing and dry scrubbing. The wet scrubber process uses equipment to mix lime or limestone and water and to spray the mixture directly into the flue gases causing a reaction that takes sulfur out of the exhaust gas. The dry scrubber process uses a rotary atomizer to atomize the lime or limestone into the flue gases.

The most common large-scale combustion technology to deal with stack effluent involves wet scrubbing. The smoke is bubbled through a limestone (CaCO3) slurry, where water and the sulfur dioxide (SO2) in the flue gas produce sulfurous acid (H2SO3). Wet scrubbers usually operate with liquid pH levels between 5 to 9 to maintain high efficiency removal. Calcium carbonate is changed to calcium sulfate as the sulfuric acid and limestone interact and so a large proportion (typically 90%+) of the sulfur dioxide is trapped in the form of calcium sulfate. This method allows removal of significant amounts of mercury as well (in systems other than the one discussed, which uses limestone, the resulting sulfur compounds may be sulfites). The resulting sludge, which has a volume greater than the coal ash, is then disposed of in huge holding ponds. The waste material is liquid and nonreactive. Scrubbers are expensive to operate,(30) and sludge disposal is a problem, too.

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Some wet scrubbers produce a corrosive liquid.(30) Everything must somehow be disposed of, and has no known use.

Figure E14.1.3 shows a wet scrubber. One operational problem with wet scrubbing is that the slurry lowers its temperature through evaporation, bringing the flue gas to temperatures below the operating temperatures of many other systems in the plant. In addition, wet scrubbers are inefficient for small particle control.

Fig. E14.1.3 A limestone wet scrubber. (Ref. 25)

Of potential importance is dry scrubbing, which eliminates the wet sludge problem. In this technique, chemicals are added to the flue gases in solid or liquid (atomized) form to

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make dry, stable salts. Some settle out, bringing heavy metals with them as well, and the rest may be caught in baghouses.(30)

Fig. E14.1.4 A schematic of a spray-dryer scrubber. (Ref. 25)

There are two general approaches: the spray-dryer scrubber and the dry-injection scrubber. The most common dry scrubber, the lime spray-drying process, may be used for plants burning lower-sulfur coals. Figure E14.1.4 shows a spray-dryer scrubber schematically. A lime slurry is mixed with the hot flue gas in a spray dryer where it reacts with SO2. By recapturing sorbent at the bottom of the spray dryer removed in a particulate control device, dry scrubbers can remove up to 96 percent of SO 2. Furnace sorbent injection puts a calcium-based absorber in the furnace, where calcium sulfate is formed by adsorption on the surfaces of the microscopic alkaline particles such as calcium hydroxide, giving 35% to 55% sulfur removal. Lime can also be injected. Problems include

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duct fouling, highly alkaline waste, and effects on precipitators.(28,31) Dry scrubbers are more complex mechanically than wet scrubbers and require much more maintenance.(25)

Figure E14.1.5 shows a dry-injection scrubber schematically. While the dry-injection scrubber may be used on smaller systems, its efficiency is much lower (45% vs. 90%+).

Fig. E14.1.5 A schematic of a dry-injection scrubber. (Ref. 25)

The Office of Fossil Energy, U.S. Department of Energy, has promoted many Clean Coal projects for utilities. However, industrial emissions do not come only from utilities. One supported project tested a new type of scrubber for a cement kiln that uses coal as fuel. Dragon Products Companys cement plant in Thomaston, Maine was a typical, dirty, cement plant, emitting a lot of sulfur. Dragon discarded dust from the kiln and had to pay to get rid of it.(32)

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This waste cement kiln dust, formed into a water-based slurry, was used in the project as a chemical to absorb sulfur dioxide and chlorine emissions from flue gas before they escaped into the air. Sulfur dioxide reacts with potassium in the kiln dust to form potassium sulfate. Figure E14.1.6 shows the schematic of the Dragon plant.

Fig. E14.1.6 The Dragon Products Company cement plant project. (U.S. Fossil Energy Program, Department of Energy)

The potassium sulfate stays dissolved and remains in the liquid as the slurry undergoes separation into liquid and solid fractions. The solid part, a thickened slurry still containing the alkali, is returned to the kiln as feedstock. The liquid part of the slurry is heated with low-temperature waste heat in the flue gas, evaporating the water and recovering dissolved alkali metal salts. Because the temperature is low, low-cost fiberglass material can be used. So, what was once waste cement kiln dust is no longer waste. Waste heat has

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10

been used. Water from slurry is recovered and reused. Little sulfur is emitted from the plant. Dragon saved money and the environment.(32)

The Dragon story is not atypical. The TVA installed pollution control equipment in its coal-fired plants reluctantly because it was so expensive. It now sells 1.2 Mt/yr of calcium sulfate to a company that makes gypsum (and goes into wallboard). Between the gypsum and fly ash, which is used to make concrete, and coal slag, used in abrasives, the TVA makes $8 million per year.(33) FirstEnergy and Seminole Electric Cooperative also market calcium sulfate from their scrubbers.(33)

Sulfur emission reductions from plants that install control technology allow the operators to sell sulfur emission permits. Under the Clean Air Act Amendments, utilities were allowed to trade these permits, so overall sulfur reduction turned out to be considerably less expensive than had been expected.(34) The permits run around $170 per ton, and many highly-polluting plants are continuing to emit sulfur courtesy of the trading scheme (that is, selective higher emissions, but with much lower overall emissions).(34,35)

A study of the efficacy of government regulation as opposed to government support only for research found that regulation is a better stimulus to action. It seems that market creation is stimulated by regulatory actions. According to Taylor, Rubin, and Hounshell, with greater technology adoption, both new and existing systems experience notable efficiency improvements and capital cost reductions.

Nitrogen oxides

Thermal denoxification is still in the development stage. Chemicals such as ammonia or urea are put into the combustion zone or downstream effluent, causing chemical reactions

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11

in which the NOx becomes harmless N2. Non-catalytic technologies can reduce NOx by 20 to 60%, while addition of catalysts can eliminate more NOx. The specific catalysts are normally proprietary. A honeycomb arrangement of tungsten or vanadium compounds surrounds the flue gas, which is sent through several channels in the honeycomb, one stack after another. NOx reduction efficiencies as high as 75 to 90% are possible with this technique.

Asymmetrically located airflow nozzles at the top of the combustion region create turbulence that can lead to more complete combustion. An example of this is the Rotating Opposed Fire Air system of Mobotec USA. Mobotec installed its systems mostly in Sweden, but is selling more of them in the United States.(26)

Computer modeling is helping combustion engineering firms design internal baffles and turning vanes for more efficient combustion. For example, Todd Combustion Group, using its COOLflow modeling technology, was able to redesign several units of NRG Energys El Segundo generating plant and achieve a 22% reduction in NOx and a 65% reduction in CO.(26)

According to Robert Swanekamp, the industry expert writing in Ref. 26, the most popular industry choice for reduction of nitrogen oxides from coal-fired plants is the combination of low-NOx burners with overfire air systems providing turbulent mixing and assuring more complete combustion. The Babcock & Wilcox Company is perhaps the most experienced supplier of such systems. One of their recent boilers releases just 0.035 kg/GJ consistently.(26)

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12

The combined-cycle gas turbine solution

Other ways to reduce emissions include fluidized-bed combustion (mixing pulverized coal with limestone and suspending the mixture on jets of air as discussed in Chapter 11), switching to fuels with a lower sulfur content, or cleaning coal before use by crushing and centrifuging the coal.(36,37) In fluidized-bed integrated coal combustion systems, the gas from the coal is cleaned before further combustion. If one switches to coal or oil with a smaller amount of sulfur, the amount of sulfur escaping the flue is reduced. The physical cleaning of coal cannot yet provide sulfur reductions of the size possible through desulfurization of flue gases; in combination with effluent control, however, it shows promise. Fluidized bed systems can reduce sulfur dioxide and nitrogen oxides by over 90%. Costs of retrofitting are $10 to $30 per kilowatt.(27,28) Fig. E14.1.7 shows a schematic of a fluidized-bed system.

Fig. E14.1.7 The Nucla Fluidized Bed System, supported by the DOE Clean Coal Technology Program, helped pioneer fluidized bed technology at utility scale. (U.S. Fossil Energy Program, Department of Energy)

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13

Plants such as Cool Water (Chapter 11) have met strict reduction criteria by gasifying the coal first, then cleaning the gas rather than cleaning the coal. The integrated gasification combined cycle (IGCC) technology is nearly mature and promises great reductions in emissions (except for CO2). Integrated gasification combined cycle systems first turn coal into a gas (Ch. 11) that can be cleaned of its impurities, virtually to the same levels as natural gas. Then the gas is burned in a gas turbine to generate one source of electricity. The gas turbine exhaust is hot enough to create steam in a second boiler to drive a steam turbine and generate a second source of electricity. Improved versions of IGCC might eventually double todays efficiencies, and even current versions are much cleaner than conventional coal plants.

Fig. E14.1.8 Tampa Electric Companys Gasification Power Plant is an example of an IGCC power plant. (U.S. Fossil Energy Program, Department of Energy)

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14

Though Cool Water is no longer running, its technology survives in plants such as the Tampa Electric Companys gasification power plant, built on a restored phosphate strip mine, which is shown schematically in Fig. E14.1.8. It, too, has achieved clean running, as is shown in Fig. E14.1.9, where its emissions are compared to a typical older power plant.

Fig. E14.1.9 Tampa Electric Companys Gasification Power Plant is one of the worlds cleanest and most fuel efficient coal plants. (U.S. Fossil Energy Program, Department of Energy)

Integrated gasification fuel cells are using gas from a gasifier to drive a molten carbonate fuel cell. A fuel cell changes chemical fuel energy continuously to electrical energy at a fixed temperature (see Chapter 7 and Extension 15.7, Hybrids and electric cars). In the fuel cell, the fuel (for example, hydrogen) and the oxidant (for example, oxygen) are brought together to produce electricity. Efficiencies of each stage are typically 60%, for an overall efficiency near 50%.(31) Recall that typical thermal power plants operate at about 33% efficiency, so these technologies represent a huge increase in efficiency.

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15

One proof that emissions in general are being reduced by the utility industry is the existence of peregrine falcon nests on some smokestacks, first noticed at plants run by Xcel Energy. The falcons seem to like their neighborhood, and studies showed negligible differences between falcons nesting on smokestacks and normal falcons.(26) Falcons nesting on smokestacks and other tall structures at several sorts of utility plants were studied closely by zoologists to make certain that there was no hidden damage occurring.

VOCs

VOCs are formed when incomplete combustion of carbon-based fuels occurs. The best way to prevent VOC pollution is to make sure the combustion chamber is hot enough and that air leaks are minimized so that the combustion is oxygen-limited and temperature fluctuations with the combustion chamber are avoided

If this is not totally possible (and in the real world, it is not), then other methods must be adopted. Possible methods of eliminating VOCs are thermal oxidation, catalytic oxidation, adsorption, condensation and refrigeration, and biological oxidation.(25)

Thermal oxidation means passing exhaust gases through a very hot chamber500 to 1000 Cabove the temperature at which the VOCs spontaneously ignite. These systems are bulky, energy inefficient, and costly. It is expensive to heat the combustion chamber to such a high temperature. However, it will get rid of virtually all VOCs.

Catalytic oxidation can take place at lower temperatures300 to 550 C. Platinum, palladium, and ceramic materials are popular catalysts. Catalytic oxidation systems are

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16

less bulky and costly than thermal oxidation systems. However, catalyst surfaces must be available to make the reactions go, and just as lead poisons automobile catalytic converters, impurities in the flue gas such as zinc and tin can render the apparatus worthless. These catalytic system developments are especially important in light of the trend of switching from coal-fired to natural gas-fired utility generators, because gas is burned at higher temperatures, where NOx is readily formed. The catalytic burners are well-placed to be the system of choice in these applications.(38)

Adsorption is limited in its usefulness. In practice, it is used when the chemical in the flue gas is recovered, or when it is baked out as part of a further process of removal. Adsorption does not work well for molecular masses below about 50 times that of a hydrogen atom or above about 200 times that of a hydrogen atom (molecular masses are measured in unified atomic mass units, u: 1 u = 1.67 x 10-27 kg; this is about the mass of a hydrogen atom).

In condensation and refrigeration, the gases are passed over a cold surface, on which they deposit by condensation. Such systems are generally used if the exhaust stream contains only VOCs, and no other wastes.

Tiny bacteria are well-known to be capable of running industrial processes. Such small organisms can take the VOCs out as a liquid in which they live. They hold great future promise, but much developmental work remains.

Multiple pollutant emissions reduction

We have not yet mentioned mercury, which has become a focus of attention (see Extension 14.2, Heavy metals). Since mercury will have to be dealt with given the

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17

context of mandated reductions in the other pollutants (and perhaps, ultimately, carbon dioxide as well), a multipurpose reduction approach might be the best one to adopt.

Powerspan Corporations multipollutant reduction electro-catalytic oxidation technology (known as ECO) is viewed in the industry as promising. FirstEnergy, a company that runs generating stations in Ohio and Pennsylvania, is working with Powerspan on ECO development.(26)

ECO consists in three steps. First, the effluent is led through a gas reactor, which oxidizes the pollutants. Then the effluent goes through a wet electrostatic precipitator system for collecting acid mists and other fine particles. Finally, this effluent is treated to recover valuable byproducts.(26) Pilot tests of an ECO syatem showed strong reductions in NOx, SO2, PM 2.5 , and mercury. Emissions of PM2.5 were reduced by over 96% in the tests, and the mercury was undetectable in the waste stream. (26)