Barium production

Barium metal and most barium compounds are highly poisonous. A notable exception is barium sulfate which is nontoxic because of its extreme iasolubihty ia water. Barium ion acts as a muscle stimulant and can cause death through ventricular fibrillation of the heart. Therefore, care must be taken to avoid contact with open areas of the skin. Workers must wear respirators (of type approved for toxic airborne particles), goggles, gloves, and protective clothing at all times. The toxic barium aluminate residue obtained from barium production is detoxified by reaction with a solution of ferrous sulfate and converted iato nontoxic barium sulfate. According to OSHA standards, the TWA value for Ba and Ba compounds ia air is 0.5 mg/m. ... 

Sulfide Solution Concentration. Tire by-product of the black ash process has considerable bearing on the ultimate economic viabiUty of barium production. It is desirable to be able to vary by-products to rnaxiaiize earnings. Sodium sulfide [1313-82-2 Na2S, sold as 60% flake, and sodium bisulfide [16721-80-5] NaHS, sold as 45% solution or as 70% flake, are t)-q)ically co-produced. 

Barite occurs in abundance in Alaska, Arkansas, California, Georgia, Missouri, Nevada, and Tennessee as well as in Canada and Mexico. This substance was produced at 38 mines in seven U.S. states in 1973. Total U.S. production for 1973 was 1,104,000 tons, a figure which represented 23% of world production. Nevada supplied 50% of this total with Missouri ranking second in domestic production of barite ore. Domestic production levels for 1969 were much lower at 603,000 tons (Davis 1972). A list of barium production and processing facilities in the United States along with the production or processing volume for each are provided in Table 4-1. 

The composition of BaCl2 dissociation products in atmospheric-pressure plasma is shown in Fig. 7-52. The initial concentration of BaCl2 is 4.8 mol/kg. Calcium formation takes place at temperatures exceeding 3500 K. The energy cost of barium production from its chloride is shown in Fig. 7-53. The minimal energy cost is 19.7 eV/atom in the case of absolute quenching, which can be achieved at a specific energy input 17.4eV/mol, and... 

Figure 7-52. Barium production by direct decomposition of its dichloride (BaCl2) in atmospheric-pressure thermal plasma. Composition of products (1) BaCl2 (2) BaCl (3) Cl x 0.1 (4) Ba+, (5) Ba.

When exposed to sunlight, it is converted to a white insoluble resin, disacryl. Oxidized by air to propenoic acid small amounts of hy-droquinone will inhibit this. Bromine forms a dibromide which is converted by barium hydroxide into DL-fructose. The acrid odour of burning fats is due to traces of propenal. It is used in the production of methionine and in controlled polymerization reactions to give acrolein polymers. ... 

The reaction mechanism for these products is not clearly understood, but the introduction of organo-metallic compounds (barium or iron salts in colloidal suspension) has been shown to have a beneficiai action on the combustion of diesel fuel in engines and reduce smoke. However, these products cause deposits to form because they are used in relatively large proportions (on the order 0.6 to 0.8 weight %) to be effective. 

Zinc is also used extensively to galvanize other metals such as iron to prevent corrosion. Zinc oxide is a unique and very useful material for modern civilization. It is widely used in the manufacture of paints, rubber products, cosmetics, pharmaceuticals, floor coverings, plastics, printing inks, soap, storage batteries, textiles, electrical equipment, and other products. Lithopone, a mixture of zinc sulfide and barium sulfate, is an important pigment. 

The reaction is used for the chain extension of aldoses in the synthesis of new or unusual sugars In this case the starting material l arabinose is an abundant natural product and possesses the correct configurations at its three chirality centers for elaboration to the relatively rare l enantiomers of glucose and mannose After cyanohydrin formation the cyano groups are converted to aldehyde functions by hydrogenation m aqueous solution Under these conditions —C=N is reduced to —CH=NH and hydrolyzes rapidly to —CH=0 Use of a poisoned palladium on barium sulfate catalyst prevents further reduction to the alditols... 

Tetrahydrofurfuryl alcohol reacts with ammonia to give a variety of nitrogen containing compounds depending on the conditions employed. Over a barium hydroxide-promoted skeletal nickel—aluminum catalyst, 2-tetrahydrofurfur5iarnine [4795-29-3] is produced (113—115). With paHadium on alumina catalyst in the vapor phase (250—300°C), pyridine [110-86-1] is the principal product (116—117) pyridine also is formed using Zn and Cr based catalysts (118,119). At low pressure and 200°C over a reduced nickel catalyst, piperidine is obtained in good yield (120,121). 

Another use for cryoHte is in the production of pure metal by electrolytic refining. A high density electrolyte capable of floating Hquid aluminum is needed, and compositions are used containing cryoHte with barium fluoride to raise the density, and aluminum fluoride to raise the current efficiency. 

Fillers (qv) are occasionally used in flexible slab foams the two most commonly used are calcium carbonate (whiting) and barium sulfate (barytes). Their use level may range up to 150 parts per 100 parts of polyol. Various other ingredients may also be used to modify a flexible foam formulation. Cross-linkers, chain extenders, ignition modifiers, auxiHary blowing agents, etc, are all used to some extent depending on the final product characteristics desired. 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Economics. As with the alkyl tin stabilizers, the market pricing of the mixed metal stabilizers tend to be directed by the particular appHcation. The calcium—zinc and barium—cadmium packages are typically used at 2.0—4.0 parts per hundred of PVC resin (phr) in the formulation. These completely formulated products are sold for 2.50— 4.40/kg for the Hquid products and 3.20— 6.50/kg for the soHds and pastes. The higher efficiency products aimed at rigid appHcations tend toward the higher end of the cost range. 

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

Inorganic Methods. Before the development of electrolytic processes, hydrogen peroxide was manufactured solely from metal peroxides. Eady methods based on barium peroxide, obtained by air-roasting barium oxide, used dilute sulfuric or phosphoric acid to form hydrogen peroxide in 3—8% concentration and the corresponding insoluble barium salt. Mote recent patents propose acidification with carbon dioxide and calcination of the by-product barium carbonate to the oxide for recycle. 

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