Limestone reaction

Acidic gases, limestone reaction with, 15 33 Acidic halide catalysts, 12 167 Acidic hydrolysis, 10 502. See also Acid hydrolysis... 

The decrease in molar volume during calcination of CaC03 to CaO has the effect of increasing the porosity of the sorbent which is important to the efficient utilization of limestone. The gas-solid reaction between S02 and limestone sorbent consists of a number of steps (2.) diffusion of gaseous S02 through the pores of the calcined limestone, reaction of 02 with CaO to form calcium sulfate (CaSO,), and diffusion of S02 through the calcium sulfate product layer to react with additional CaO in the particle. Unfortunately, the sulfation reaction ... 

Figure 1.8. An example of a deep-well injection facility. Monsanto s facility near Pensacola, Florida, injects acidic waste streams more than 1000 ft deep into the Lower Limestone of the Floridian Aquifer. Observed reactions include dissolution of limestone, reactions among the wastes under higher pressure and temperature, and suppression of microbial activities (Boulding, 1990).

Use data in Appendix H to evaluate the thermodynamic equilibrium constant at 298.15 K for the limestone reaction... 

The circulating bed media may be coal ash particles or limestone particles, depending on the process desulfurization needs—the limestone reaction conversions in this cyclic oxidizing-reducing environment may have reaction heat effects that influence the process performance. 

In recent years, considerable attention has been devoted to the understanding of S02-limestone reaction mechanism. Kinetics of this reaction is complicated by the changes in the pore structure, in surface area and by the variations of diffusional effects during the reaction. In this manuscript, emphasis is given to the mechanism of SOj-limestone reaction in a dry system and a detailed review of literature is presented. In the second part, kinetics of S02-activated soda reaction is discussed and applications to flue gas desulfurization are summarized. 

The capture of SO2 by limestone in a dry system is a high temperature process. Calcination step requires a temperature level over 750 C. It was reported by Ferguson and Rissman (1970) that, the major reaction product of SOs-calcined limestone reaction was CaSOj below 500 °C. On the other hand, CaS04 was the major product over 500 C. 

The calcination of limestone, reaction (21.14), is highly reversible at room temperature. Thus, a high temperature must be used and C02(g) must be continuously removed from the kiln to prevent the reverse reaction. 

Rainwater for instance will pick up atmospheric COg and react with calcium carbonate (limestone) to form a soluble substance, calcium bicarbonate. This reaction gives water its natural hardness . 

Any lead(II) sulphate formed in this process is converted to lead(II) silicate by reaction with the quartz. The oxide produced is then mixed with limestone and coke and heated in a blast furnace. The following reactions occur ... 

The process of extraction requires first smelting (to obtain the crude metal) and then refining. In smelting, iron ore (usually an oxide) is mixed with coke and limestone and heated, and hot air (often enriched with oxygen) is blown in from beneath (in a blast furnace). At the lower, hotter part of the furnace, carbon monoxide is produced and this is the essential reducing agent. The reduction reactions occurring may be represented for simplicity as ... 

Reaction (13.4) is exothermic and reversible, and begins at about 700 K by Le Chatelier s Principle, more iron is produced higher up the furnace (cooler) than below (hotter). In the hotter region (around 900 K), reaction (13.5) occurs irreversibly, and the iron(II) oxide formed is reduced by the coke [reaction (13.6)] further down. The limestone forms calcium oxide which fuses with earthy material in the ore to give a slag of calcium silicate this floats on the molten iron (which falls to the bottom of the furnace) and can bo run off at intervals. The iron is run off and solidified as pigs —boat-shaped pieces about 40 cm long. 

Disposal. Fluorine can be disposed of by conversion to gaseous perfluorocarbons or fluoride salts. Because of the long atmospheric lifetimes of gaseous perfluorocarbons (see Atmospheric models), disposal by conversion to fluoride salts is preferred. The following methods are recommended scmbbing with caustic solutions (115,116) reaction with soHd disposal agents such as alumina, limestone, lime, and soda lime (117,118) and reaction with superheated steam (119). Scmbbing with caustic solution and, for dilute streams, reaction with limestone, are practiced on an industrial scale. 

Formation of emissions from fluidised-bed combustion is considerably different from that associated with grate-fired systems. Flyash generation is a design parameter, and typically >90% of all soHds are removed from the system as flyash. SO2 and HCl are controlled by reactions with calcium in the bed, where the lime-stone fed to the bed first calcines to CaO and CO2, and then the lime reacts with sulfur dioxide and oxygen, or with hydrogen chloride, to form calcium sulfate and calcium chloride, respectively. SO2 and HCl capture rates of 70—90% are readily achieved with fluidi2ed beds. The limestone in the bed plus the very low combustion temperatures inhibit conversion of fuel N to NO. ... 

The calcium oxide product is supplemented with fresh limestone and returned to the fluidized bed. Two undesirable side reactions can occur in the regeneration of spent lime leading to the production of calcium sulfide ... 

Normally, lithium hydride ignites in air only at high temperatures. When heated it reacts vigorously with CO2 and nitrogen. With the former, lithium formate is obtained. Reaction at high temperature with nitrogen produces lithium nitride. Therefore, dry limestone or NaCl powders are used to extinguish LiH fires. Lithium hydride reacts exothermically with moist air and violently with water. 

The term lime also has a broad coimotation and frequently is used in referring to limestone. According to precise definition, lime can only be a burned form quicklime, hydrated lime, or hydraiflic lime. These products are oxides or hydroxides of calcium and magnesium, except hydraiflic types in which the CaO and MgO are chemically combined with impurities. The oxide is converted to a hydroxide by slaking, an exothermic reaction in which the water combines chemically with the lime. These reversible reactions for both high calcium and dolomitic types are Quicklime... 

Silica and Alumina. The manufacture of Pordand cement is predicated on the reaction of lime with siUca and alumina to form tricalcium sihcate [12168-85-3] and aluminate. However, under certain ambient conditions of compaction with sustained optimum moisture content, lime reacts very slowly to form complex mono- and dicalcium siUcates, ie, cementitious compounds (9,10). If such a moist, compact mixture of lime and siUca is subjected to steam and pressure in an autoclave, the lime—silica reaction is greatiy accelerated, and when sand and aggregate is added, materials of concrete-like hardness are produced. Limestone does not react with siUca and alumina under any circumstances, unless it is first calcined to lime, as in the case of hydrauhc lime or cement manufacture. 

Theory of Calcination. The reversible reaction involved in the calcination and recarbonation of lime—limestone is one of the simplest and most fundamental of all chemical reactions. In practice, lime burning can be quite complex, however, and many empirical modifications are often necessary for efficient performance. 

Some limestones, more often the coarse crystalline types, can never be calcined successfully. Such stone tends to decrepitate during preheating or calcination into fine particles that interfere with this pyrochemical reaction. The adaptabiflty of a stone for calcination can only be ascertained with surety by empirical methods. Possibly the greatest influence on lime quaflty is the size gradation of limestone. Narrow gradations, such as... 

Drying a.nd Calcination. The simplest pyrometaHurgical operation is the evaporation of free water and the decomposition of hydrates and carbonates. A typical reaction is the decomposition of pure limestone [1317-65-3] CaCO, to calcium oxide [1305-78-8] and carbon dioxide ... 

This reaction is strongly endothermic, and the equHibrium pressure of COg, equal to the equHibrium constant of the reaction, increases exponentiaHy with temperature (see Lime and limestone). 

At about the same time that the Birkeland-Eyde process was developed, the Frank-Caro cyanamide process was commercialized (14). In this process limestone is heated to produce lime, which then reacts with carbon in a highly energy-demanding reaction to give calcium carbide. Reaction with N2 gives calcium cyanamide [150-62-7] which hydrolyzes to ammonia and calcium carbonate (see Cyanamides). 

Refined calcined alumina is commonly used in combination with high purity limestone [1317-65-3] to produce high purity calcium aluminate cement (CAC). The manufacture, properties, and appHcations of CAC from bauxite limestone, as weU as high purity CAC, has been described (104). High purity CAC sinters readily in gas-fired rotary kiln calcinations at 1600 —1700 K. CAC reactions are considered practically complete when content of free CaO is less than 0.15% andloss on ignition is less than 0.5% at 1373 K. 

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