Potassium purification

The purification train. The oxygen is led from the cylinder through Ordinary flexible rubber condenser tubing to the constant level device A (Fig. 85). This consists of two concentric tubes (approximately 2 cm. and 0-5 cm. respectively, in diameter the inner tube being narrowed and curved at the bottom as shown) immersed in 50% aqueous potassium hydroxide contained in the outer vessel (diameter 3-5 cm.). Then by adjusting the liquid level in A the pressure of oxygen may be kept constant, and at a maximum of about... 

The amino add analysis of all peptide chains on the resins indicated a ratio of Pro Val 6.6 6.0 (calcd. 6 6). The peptides were then cleaved from the resin with 30% HBr in acetic acid and chromatogra phed on sephadex LH-20 in 0.001 M HCl. 335 mg dodecapeptide was isolated. Hydrolysis followed by quantitative amino acid analysis gave a ratio of Pro Val - 6.0 5.6 (calcd. 6 6). Cycll2ation in DMF with Woodward s reagent K (see scheme below) yielded after purification 138 mg of needles of the desired cyc-lododecapeptide with one equiv of acetic add. The compound yielded a yellow adduct with potassium picrate, and here an analytically more acceptable ratio Pro Val of 1.03 1.00 (calcd. 1 1) was found. The mass spectrum contained a molecular ion peak. No other spectral measurements (lack of ORD, NMR) have been reported. For a thirty-six step synthesis in which each step may cause side-reaaions the characterization of the final product should, of course, be more elaborate. 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

Potassium removal is required because the presence of potassium during electrolysis reportedly promotes the formation of the a-Mn02 phase which is nonbattery active. Neutralization is continued to a pH of approximately 4.5, which results in the precipitation of additional trace elements and, along with the ore gangue, can be removed by filtration. Pinal purification of the electrolyte Hquor by the addition of sulfide salts results in the precipitation of all nonmanganese transition metals. 

Once purification of the niobium has been effected, the niobium can be reduced to the metallic form. The double fluoride salt with potassium, K2NbFy, can be reduced using sodium metal. The reaction is carried out in a cylindrical iron vessel filled with alternating layers of K NbF and oxygen-free sodium ... 

The cmde phthaUc anhydride is subjected to a thermal pretreatment or heat soak at atmospheric pressure to complete dehydration of traces of phthahc acid and to convert color bodies to higher boiling compounds that can be removed by distillation. The addition of chemicals during the heat soak promotes condensation reactions and shortens the time required for them. Use of potassium hydroxide and sodium nitrate, carbonate, bicarbonate, sulfate, or borate has been patented (30). Purification is by continuous vacuum distillation, as shown by two columns in Figure 1. The most troublesome impurity is phthahde (l(3)-isobenzofuranone), which is stmcturaHy similar to phthahc anhydride. Reactor and recovery conditions must be carefully chosen to minimize phthahde contamination (31). Phthahde [87-41-2] is also reduced by adding potassium hydroxide during the heat soak (30). 

The iodate is a poison potassium iodide, however, is used in foodstuffs. Thus the iodate must be completely removed frequently by a final reduction with carbon. After re-solution in water, further purification is carried out before recrystallization. Iron, barium, carbonate, and hydrogen sulfide are used to effect precipitation of sulfates and heavy metals. 

The ketene—crotonaldehyde route through polyester with various modifications and improvements is reportedly practiced by Hoechst Celanese, Cheminova, Daicel, Ueno, Chisso, Nippon Gohsei, and Eastman Chemical Company. Differences in thein processes consist mosdy in the methods of polyester splitting and first-stage purification. Production of the potassium salt can be from finished sorbic acid or from a stream in the sorbic acid production route before the final drying step. Several patents on the process for producing sorbic acid and potassium sorbate from this route are given in the hterature. 

Vinyl chloride can be completely oxidized to CO2 and HCl using potassium permanganate [7722-64-7] in an aqueous solution at pH 10. This reaction can be used for wastewater purification, as can ozonolysis, peroxide oxidation, and uv irradiation (42). The aqueous phase oxidation of vinyl chloride with chlorine yields chloroacetaldehyde (43). 

Polyethers are usually found in both the filtrate and the mycelial fraction, but in high yielding fermentations they are mosdy in the mycelium because of their low water-solubiUty (162). The high lipophilicity of both the free acid and the salt forms of the polyether antibiotics lends these compounds to efficient organic solvent extraction and chromatography (qv) on adsorbents such as siUca gel and alumina. Many of the production procedures utilize the separation of the mycelium followed by extraction using solvents such as methanol or acetone. A number of the polyethers can be readily crystallized, either as the free acid or as the sodium or potassium salt, after only minimal purification. 

Methods of Purification. Although carbon dioxide produced and recovered by the methods outlined above has a high purity, it may contain traces of hydrogen sulfide and sulfur dioxide, which cause a slight odor or taste. The fermentation gas recovery processes include a purification stage, but carbon dioxide recovered by other methods must be further purified before it is acceptable for beverage, dry ice, or other uses. The most commonly used purification methods are treatments with potassium permanganate, potassium dichromate, or active carbon. 

Of the four commercial processes for the purification of carbon monoxide two processes are based on the absorption of carbon monoxide by salt solutions, the third uses either low temperature condensation or fractionation, and the fourth method utilizes the adsorption of carbon monoxide on a soHd adsorbent material. AH four processes use similar techniques to remove minor impurities. Particulates are removed in cyclones or by scmbbing. Scmbbing also removes any tars or heavy hydrocarbon fractions. Acid gases are removed by absorption in monoethanolamine, hot potassium carbonate, or by other patented removal processes. The purified gas stream is then sent to a carbon monoxide recovery section for final purification and by-product recovery. 

Direct Reduction with Metals. PoUucite can be directly reduced by heating the ore in the presence of calcium to 950°C in a vacuum (20), or in the presence of either sodium or potassium to 750°C in an inert atmosphere (21). Extraction is not complete. Excessive amounts of the reducing metal is required and the resultant cesium metal is impure except when extensive distiUation purification is carried out. Engineering difficulties in this process are significant, hence, this method is not commerciaUy used. 

FIG. 23-27 CO, in potassium carbonate solutions (<2) equilibrium in 20% solution, (h) mass-transfer coefficients in 40% solutions. (Data cited hy Kohl and Riesenfeld, Gas Purification, Gulf Fuhlishing, 1985.)... 

This group of reagents is commercially available in large quantities some of its members - notably lithium aluminium hydride (LiAlH4), calcium hydride (CaH2), sodium borohydride (NaBH4) and potassium boro-hydride (KBH4) - have found widespread use in the purification of chemicals. 

The purification of diethyl ether (see Chapter 4) is typical of liquid ethers. The most common contaminants are the alcohols or hydroxy compounds from which the ethers are prepared, their oxidation products (e.g. aldehydes), peroxides and water. Peroxides, aldehydes and alcohols can be removed by shaking with alkaline potassium permanganate solution for several hours, followed by washing with water, concentrated sulfuric acid [CARE], then water. After drying with calcium chloride, the ether is distilled. It is then dried with sodium or with lithium aluminium hydride, redistilled and given a final fractional distillation. The drying process should be repeated if necessary. 

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