Lime/limestone additives

Lime is among a family of chemicals which are alkaline in nature and contain principally calcium, oxygen and, in some cases, magnesium. In this grouping are included quicklime, dolomitic lime, hydrated lime, dolomitic hydrated lime, limestone, and dolomite. The most commonly used additives are quicklime and hydrated lime, but the dolomitic counterparts of these chemicals (i.e., the high-magnesium forms) are also widely used in wastewater treatment and are generally similar in physical requirements. 

The possible reactions taking place within the wet lime/limestone SO2 removal system have been studied. Our conclusions relative to the controlling reactions are based on consideration of theoretical equations in light of operating experience in both field and pilot systems. Because there is considerable difference in operating conditions required to provide adequate SO2 removal in the absence of scale or deposit formation when utilizing lime or limestone as additives, the chemical reactions of the systems are treated separately. The essential reactions governing these systems are ... 

The Air Quality Control Systems (AQCS) using lime/limestone wet scrubbing have three basic types of chemical process equipment (1) scrubbers, (2) reaction tanks, and (3) solid-liquid separators, in addition to several auxiliary pieces of equipment such as pumps, demisters, and reheaters. The SO2 in the flue gas is transferred into the liquid in the scrubber, the sulfur in the liquid is converted to solid calcium sulfite, and calcium sulfate in the reaction tanks and solid calcium sulfite and sulfate are separated from the liquid and disposed from the solid-liquid separators such as clarifiers, vacuum filters, and ponds. 

Buffer Additives for Lime/Limestone Slurry Scrubbing... 

Buffer additives are attractive for enhancing SO2 removal and/or CaC03 utilization in lime/limestone slurry scrubbing processes for flue gas desulfurization. This work was sponsored by EPA to provide experimental data on commercial synthesis, gas/liquid mass transfer enhancement, and oxidative degradation of useful buffer additives. 

Lime/limestone slurry scrubbing is the dominant commercial technology for flue gas desulfurization 0.). SO2 is absorbed at 50-55°C and pH 5.5-6.0 in an aqueous slurry of excess CaC03 and product solids. The CaS03/CaS04 product is disposed of as solid waste. With greater than 500-1000 ppm SO2 in the flue gas, SO2 absorption is controlled by liquid-film mass transfer resistance because of the limited solubility of SO2 gas and alkaline solids. Additives that buffer between pH 3 and pH 5.5 enhance S02 absorption by providing dissolved alkaline species for reaction with SO2 (8). 

This paper summarizes the results of tests conducted from July 1978 through March 1981 at the EPA, 10-MW equivalent, lime/limestone wet-scrubbing FGD test facility, during which adipic acid as an additive was tested and shown to be a powerful scrubber additive for improving SO2 removal. The optimum concentration of adipic acid is only 700 to 1500 ppm at a scrubber inlet pH of 5.2 or higher. SO2 removal efficiencies in excess of 90 percent and reliable operation were demonstrated in four long term, limestone/adipic acid runs. Factorial tests were also conducted to characterize SO2 removal as a function of gas and slurry flow rates, pH, and adipic acid concentration. Intermediate duration optimization runs and favorable economics are also reported. 

In either the lime/limestone or sodium sulfite/lime scrubbing processes, the hydrated calcium sulfite and calcium sulfate can be of some environmental concern when the issue of disposal arises. This has, more than anything else, promoted efforts to develop alternate dry scrubbing procedures for the removal of sulfm dioxide. And the dry systems have the additional advantage of reducing the pumping requirements necessary for the wet systems. 

Lakes that have been acidified by acid rain can be neutralized by liming, the addition of limestone (CaCO ). How much limestone in kilograms is required to completely neutralize a 3.8 X Iff L lake with a pH of 5.5 ... 

Calcium. Calcium is the fifth most abundant element in the earth s cmst. There is no foreseeable lack of this resource as it is virtually unlimited. Primary sources of calcium are lime materials and gypsum, generally classified as soil amendments (see Calcium compounds). Among the more important calcium amendments are blast furnace slag, calcitic limestone, gypsum, hydrated lime, and precipitated lime. Fertilizers that carry calcium are calcium cyanamide, calcium nitrate, phosphate rock, and superphosphates. In addition, there are several organic carriers of calcium. Calcium is widely distributed in nature as calcium carbonate, chalk, marble, gypsum, fluorspar, phosphate rock, and other rocks and minerals. 

The chemical and physical properties of limestone vary tremendously, owing to the nature and quantity of impurities present and the texture, ie, crystallinity and density. These same factors also exert a marked effect on the properties of the limes derived from the diverse stone types. In addition, calcination and hydration practices can profoundly influence the properties of lime. 

Of the removal processes that have attained commercial status, the current favorite employs a shiny of lime or limestone. The activity of the reagent is promoted by the addition of small amounts of carboxylic acids such as adipic acid. The gas and the shiny are contacted in a spray tower. The calcium salt is discarded. A process that employs aqueous sodium citrate, however, is suited for the recoveiy of elemental sulfur. The citrate solution is regenerated and recycled. (Kohl and Riesenfeld, Gas Purification, Gulf, 1985, p. 356.)... 

SONOX A process for simultaneously removing S02 and NOx from flue-gas. A slurry of lime or limestone, with a proprietary nitrogen-based additive, is injected into the furnace. Developed by Ontario Hydro (the largest electricity supplier in North America) and marketed by Research-Cottrell. 

For applications where the ionic strength is as high as 6 M, the ion activity coefficients can be calculated using expressions developed by Bromley (4 ). These expressions retain the first term of equation 9 and additional terms are added, to improve the fit. The expressions are much more complex than equation 9 and require the molalities of the dissolved species to calculate the ion activity coefficients. If all of the molalities of dissolved species are used to calculate the ion activity coefficients, then the expressions are quite unwieldy. However, for the applications discussed in this paper many of the dissolved species are of low concentration and only the major dissolved species need be considered in the calculation of ion activity coefficients. For lime or limestone applications with a high chloride coal and a tight water balance, calcium chloride is the dominant dissolved specie. For this situation Kerr (5) has presented these expressions for the calculation of ion activity coefficients. 

When alumina is combined with the silica, forming a natural clay, a much more compact and fusible compound is formed with the lime than when the silica is alone. Indeed, it has been observed as a general principle, that tire point of fusion is materially affected by the relation and number of bases the whole materials contain thus, a more liquid scoria is obtsined by the addition of a limestone containing magnesia than with a pure limestone. But experience is against the use of a magnesieu limestone, because it deteriorates the iron produced, while the purity of the metal iB the primary consideration. That which contains much silica should also be used sparingly, as silica combines with the iron and injures its quality, -The purest limestones are the most suitable for flux. Common marble is nearly a pnre carbonate of lime but is too rare and expensive to be used as a flux. 

---