Precipitation, sulfate, and

Oxidation and Sulfate Precipitation. As anticipated, most of the oxidation took place in the absorber/scrubber unit. The levels of oxidation in this unit ranged from an equivalent of 5 mole % of the SO2 removed, at O2 concentrations of 5.5 vol. % in the inlet flue gas, to 25 mole % at O2 concentrations of 8%. Oxidation throughout the remainder of the system amounted to an additional 1 to 5% of the SO2 removed. 

Both of these problems, their causes, and impacts have already been discussed. The losses in the cake were addressed in the discussion of cake properties and liquor losses were addressed in the discussion of oxidation and sulfate precipitation. It is reasonable to assume that had the mechanical problems and corresponding impacts on the process operation not been present, the makeup rate could have been limited to the design condition. This was clearly demonstrated during the earlier pilot plant tests where soda ash makeup rates amounted to an equivalent of 5 mole % of the SO2 removed. 

There are numerous variations of the wet process, but all involve an initial step in which the ore is solubilized in sulfuric acid, or, in a few special instances, in some other acid. Because of this requirement for sulfuric acid, it is obvious that sulfur is a raw material of considerable importance to the fertilizer industry. The acid—rock reaction results in formation of phosphoric acid and the precipitation of calcium sulfate. The second principal step in the wet processes is filtration to separate the phosphoric acid from the precipitated calcium sulfate. Wet-process phosphoric acid (WPA) is much less pure than electric furnace acid, but for most fertilizer production the impurities, such as iron, aluminum, and magnesium, are not objectionable and actually contribute to improved physical condition of the finished fertilizer (35). Impurities also furnish some micronutrient fertilizer elements. 

Waste treatment of fluoroborate solutions includes a pretreatment with aluminum sulfate to facditate hydrolysis, and final precipitation of fluoride with lime (18). The aluminum sulfate treatment can be avoided by hydrolyzing the fluoroborates at pH 2 in the presence of calcium chloride at this pH, hydrolysis is most rapid at elevated temperature (19). 

The lignitic coals of the northern United States tend to have low sulfur contents, making them attractive for boilet fuels to meet sulfur-emission standards. However, low sulfur content coals have impaired the performance of electrostatic precipitators. The ash of these coals tends to be high in alkaline earths (Ca, Mg) and alkaUes (Na, K). As a result, the ash can trap sulfur as sulfites and sulfates (see Airpollution control methods). 

The key difference between the brine process and seawater process is the precipitation step. In the latter process (Fig. 6) the seawater is first softened by a dding small amounts of lime to remove bicarbonate and sulfates, present as MgSO. Bicarbonate must be removed prior to the precipitation step to prevent formation of insoluble calcium carbonate. Removal of sulfates prevents formation of gypsum, CaS02 2H20. Once formed, calcium carbonate and gypsum cannot be separated from the product. 

Iron oxide yellows can also be produced by the direct hydrolysis of various ferric solutions with alkahes such as NaOH, Ca(OH)2, and NH. To make this process economical, ferric solutions are prepared by the oxidation of ferrous salts, eg, ferrous chloride and sulfate, that are available as waste from metallurgical operations. The produced precipitate is washed, separated by sedimentation, and dried at about 120°C. Pigments prepared by this method have lower coverage, and because of their high surface area have a high oil absorption. 

The gaseous ammonia is passed through electrostatic precipitators for particulate removal and mixed with the cooled gas stream. The combined stream flows to the ammonia absorber where the ammonia is recovered by reaction with a dilute solution of sulfuric acid to form ammonium sulfate. Ammonium sulfate precipitates as small crystals after the solution becomes saturated and is withdrawn as a slurry. The slurry is further processed in centrifuge faciHties for recovery. Crystal size can be increased by employing one of two processes (99), either low differential controUed crystallization or mechanical size enlargement by continuous compacting and granulation. 

Sulfamic acid and its salts retard the precipitation of barium sulfate and prevent precipitation of silver and mercury salts by alkah. It has been suggested that salts of the type AgNHSO K [15293-60 ] form with elemental metals or salts of mercury, gold, and silver (19). Upon heating such solutions, the metal deposits slowly ia mirror form on the wall of a glass container. Studies of chemical and electrochemical behavior of various metals ia sulfamic acid solutions are described ia Reference 20. 

Barium sulfate [7727-43-7] BaSO, occurs as colorless rhombic crystals, mp 1580 °C (dec) sp gr 4.50 solubihty 0.000285 g/100 g H2O at 30°C and 0.00118 at 100°C. It is soluble in concentrated sulfuric acid, forming an acid sulfate dilution with water reprecipitates barium sulfate. Precipitated BaSO is known as blanc fixe, prepared from the reaction of aqueous solutions of barium sulfide and sodium sulfate. 

Lateritic Ores. The process used at the Nicaro plant in Cuba requires that the dried ore be roasted in a reducing atmosphere of carbon monoxide at 760°C for 90 minutes. The reduced ore is cooled and discharged into an ammoniacal leaching solution. Nickel and cobalt are held in solution until the soflds are precipitated. The solution is then thickened, filtered, and steam heated to eliminate the ammonia. Nickel and cobalt are precipitated from solution as carbonates and sulfates. This method (8) has several disadvantages (/) a relatively high reduction temperature and a long reaction time (2) formation of nickel oxides (J) a low recovery of nickel and the contamination of nickel with cobalt and (4) low cobalt recovery. Modifications to this process have been proposed but all include the undesirable high 760°C reduction temperature (9). 

Typical applications in the chemical field (Beaver, op. cit.) include detarring of manufactured gas, removal of acid mist and impurities in contact sulfuric acid plants, recovery of phosphoric acid mists, removal of dusts in gases from roasters, sintering machines, calciners, cement and lime Idlns, blast furnaces, carbon-black furnaces, regenerators on fluid-catalyst units, chemical-recoveiy furnaces in soda and sulfate pulp mills, and gypsum kettles. Figure 17-74 shows a vertical-flow steel-plate-type precipitator similar to a type used for catalyst-dust collection in certain fluid-catalyst plants. 

In addition to films that originate at least in part in the corroding metal, there are others that originate in the corrosive solution. These include various salts, such as carbonates and sulfates, which may be precipitated from heated solutions, and insoluble compounds, such as beer stone, which form on metal surfaces in contac t with certain specific products. In addition, there are films of oil and grease that may protect a material from direct contact with corrosive substances. Such oil films may be apphed intentionally or may occur naturally, as in the case of metals submerged in sewage or equipment used for the processing of oily substances. 

Environment Electrostatic precipitator receives air from steel blast furnace 50-180°F (10-82°C) high moisture, chlorides, sulfides and sulfate, iron oxides... 

The alcoholic filtrate is evaporated to 50 cc., and 50 g. of barium hydroxide and 150 cc. of distilled water are added (Note 4). The mixture is refluxed for two hours and the excess barium hydroxide is precipitated with carbon dioxide. The barium carbonate is removed by filtration and washed with hot distilled water. A slight excess of sulfuric acid is added to the filtrate to liberate the amino acid from its barium salt, and an excess of barium carbonate is added to remove sulfate ion. The mixture is digested on the steam bath until effervescence ceases, and it is then filtered and the precipitate is washed with hot distilled water. The filtrate and washings are concentrated on the steam bath to a volume of 100 cc., decolorized with i g. of active carbon, filtered, and concentrated to the point of crystallization (about 25 cc.). The amino acid is precipitated by the addition of 150 cc. of absolute alcohol and the product is collected and washed with absolute alcohol. 

However, the fertilizing effect of nitrates (and sulfates) may be counterbalanced by the leaching of potassium, magnesium, calcium, and other nutrients from forest soils. There is little evidence that agricultural crops are being injured by exposures to nitrates in precipitation. The amount of nitrates in rainwater is almost always... 

A mixture consisting of 0.69 g (10.5 mmoles) of zinc-copper couple, 12 ml of dry ether, and a small crystal of iodine, is stirred with a magnetic stirrer and 2.34 g (0.7 ml, 8.75 mmoles) of methylene iodide is added. The mixture is warmed with an infrared lamp to initiate the reaction which is allowed to proceed for 30 min in a water bath at 35°. A solution of 0.97 g (2.5 mmoles) of cholest-4-en-3/ -ol in 7 ml of dry ether is added over a period of 20 min, and the mixture is stirred for an additional hr at 40°. The reaction mixture is cooled with an ice bath and diluted with a saturated solution of magnesium chloride. The supernatant is decanted from the precipitate, and the precipitate is washed twice with ether. The combined ether extracts are washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure and the residue is chromatographed immediately on 50 g of alumina (activity III). Elution with benzene gives 0.62 g (62%) of crystalline 4/5,5/5-methylene-5 -cholestan-3/5-ol. Recrystallization from acetone gives material of mp 94-95° Hd -10°. 

Bromo-A-homo-estra-4y5 0)-diene-3, l-dione (49). A solution of silver perchlorate (0.55 g, 5 mole-eq) in acetone (2 ml) is added to a refluxing solution of monoadduct (48 0.28 g) in acetone (30 ml) containing water (0.5 ml). After being heated at reflux for 25 min the reaction mixture is cooled and the precipitated silver bromide is removed by filtration, yield about 0.11 g. The filtrate is diluted with water (500 ml) and is thoroughly extracted with chloroform. The chloroform extracts are washed with water and saturated salt solution, dried over anhydrous magnesium sulfate, and evaporated at... 

Methoxy-D-Homo-estra-l,3,5(10)-trien-17a-one (96)" (/) Acetic acid (6.4 ml) is added to a stirred solution of estrone methyl ether (93 1.1 g) in ethanol (35 ml) containing potassium cyanide (6 g) at 0°. After being stirred for 1 hr at 0° and 2.5 hr at room temperature, the reactants dissolve and potassium acetate preciptates. Water (65 ml) is added to the reaction mixture and the precipitated solid is collected by filtration. The crude product is dissolved in ethyl acetate and the ethyl acetate solution is washed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. Recrystallization of a portion of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l, 3,5(10)-trien-17j5-ol (94a) as needles mp 158.5°. 

The white cesium fluoroxy sulfate precipitates from the reaction medium and may be kept for several months in the cold (0 to -15 °C) Metal surfaces can cause detonation of the reagent. The reaction scope of cesium fluoroxysulfate seems narrower than that of acetyl hypofluorite because of its limited solubility in organic solvents Cesium fluoroxysulfate has not been prepared with a fluorine-18 label. 

Precipitation involves the alteration of the ionic equilibrium to produce insoluble precipitates. To remove the sediment, chemical precipitation is allied with solids separation processes such as filtration. Undesirable metal ions and anions are commonly removed from waste streams by converting them to an insoluble form. The process is sometimes preceded by chemical reduction of the metal ions to a form that can be precipitated more easily. Chemical equilibrium can be affected by a variety of means to change the solubility of certain compounds. For e.xample, precipitation can be induced by alkaline agents, sulfides, sulfates, and carbonates. Precipitation with chemicals is a common waste stream treatment process and is effective and reliable. The treatment of sludges is covered next. 

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