Limestone, absorption

Volesky, A. F, Niagara Limestone Absorption of Pu from Salt Solutions, paper submitted to Argonne Center for Educational Affairs, Spring, 1976, Argonne National Laboratory, Argonne, Illinois 60439. 

Desulfurize the flue gas. A whole range of processes have been developed to remove SO, from flue gases, such as injection of limestone into the furnace, absorption into wet limestone after the furnace, absorption into aqueous potassium sulfite after the furnace, and many others.However, the byproducts from many of these desulfurization processes cause major disposal problems. 

Pulverized lime or limestone injected into flue gas (often through burner). SO2 absorbed on soHd particles. High excess alkah required for fairly low SO2 absorption. Finer grindings lime preheat, flue gas humidification benefit removal. Particulate collected in baghouse. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

CO2 is also recovered economically from the flue gases resulting from combustion of carbonaceous fuels, from fermentation of sugars and from the calcination of limestone recovery is by reversible absorption either in aqueous Na2COi or aqueous ethanolamine (Girbotol process). 

One way to control gaseous pollutants like SO2 and SO3 is to remove the gases from fuel exhaust systems by absorption into a liquid solution or by adsorption onto a solid material. Absorption involves dissolving the gas in a liquid while adsorption is a surface phenomenon. In each case, a subsequent chemical reaction can occur to further trap the pollutant. Lime and limestone are two solid materials that effectively attract sulfur dioxide gas to their surfaces. The ensuing chemical reaction converts the gaseous pollutant to a solid nontoxic substance that can be collected and disposed or used in another industry. 

Throwaway processes generally remove sulfur dioxide by absorption into a lime or limestone slurry or a clear solution. Figures 3-5 show general diagrams for these processes (22,23,24, 25). 

In wet scrubbing of SOp from boiler flue gas by limestone slurry, the concentration of dissolved species in the scrubbing liquor that can react with incoming SOp gas is very low, about one to two m-mole/1. This is far below the SOp make-per-pass in the scrubber, typically about 10 m-mole of SOp absorbed per liter of liquor for one pass through the scrubber. Therefore, the SOp absorption rate is largely dependent upon the slow rate of limestone dissolution into the liquor passing through the scrubber. 

Although, as described by Bjerle et alS13 liquid jet-type absorbers are also used, one relatively recent application of mass transfer in agitated tanks with chemical reaction is the absorption of pollutants from flue gases and, in particular, the scrubbing of sulphur dioxide by a slurry containing fine limestone particles. In this case, the concentration of sulphur dioxide is usually very low and the mechanism of the absorption is complicated due to the presence of solids in the liquid phase where the rate of solid dissolution may significantly affect the absorption rate. 

Further work on the absorption of sulphur dioxide by Uchida et aln5> has shown that the absorption rate changes with the surface area of the limestone particles which in turn varies with the size and the number of particles, and that the rate of dissolution plays a very important role on the absorption. It was further found the absorption rate does not vary significantly with temperature and that the reactions involved may be considered as being instantaneous. 

Uchida, S., Moriguchi, H., Maejima, H., Koide, K. and Kageyama, S. Can. J. Chem. Eng. 56 (1978) 690. Absorption of sulphur dioxide into limestone slurry in a stirred tank reactor. 

Iron oxide is always present as an impurity in glass. It is introduced through the natural raw materials such as sand and limestone. Another source is from trap iron mixed in the cullet and abraded metal from the handling of batch. All of this adds up to several hundred parts per million which causes light absorption at the ends of the spectrum rather than the middle and causes a yellow-green color in the glass. This can be overcome by a process known as decolorization. There are two types chemical and physical decolorizing. )... 

Chemical scrubbing systems for SO/ absorption fall into two broad categories (a) Disposable systems and (b) regenerative systems. Typical of systems in use for a number of years are those that use an aqueous slurry of an insoluble caldum compound, which can be discarded after use. Disposable 02-removal systems use aqueous slurries of finely ground materials, such as lime, limestone or dolomite, to produce a mixture of insoluble sulfites and sulfates. On passing through the scrubber, S02 from the waste gas dissolves to form sulfurous acid S02 ... 

In addition to the works introduced above, Berman et al. also studied the absorption of S02 with limestone and NaOH-enhanced limestone suspensions as the absorbents [124] in a reactor of the same type as that shown in Fig. 7.5. The main results obtained include the following ... 

National Dust Collector, developed a process based on dry limestone injection in the boiler. By 1972, the Combustion Engineering process had been installed on five boilers, but these installations proved inadequate owing mainly to boiler plugging, low sulfur dioxide absorption, and reduced particulate collection efficiency in the electrostatic precipitator. 

The high capital investment cost of the Asahi process is due to the necessity for large absorbers, evaporators, crystallizers, dryers, rotary kiln crackers and screw decanter separators. The major operating and maintenance costs are electricity, fuel oil, steam and chemicals such as soda ash, EDTA and limestone. The requirement for consumption of large amounts of utilities is associated with the operation principle and design of the Asahi process. According to the economic evaluation, equipment required for N0X and SO2 absorption (such as packed-bed absorbers) accounts for 20% of total direct capital investment for treatment of dithionate ion (such as evaporator, crystallizer, dryer, and cracker) it accounts for about 40% and for treatment of nitrogen-sulfur compounds (such as screw decanter and cracker) it accounts for only 2%. 

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