Process Bayer

Furthermore, the production of a sodium chloride-sodium carbonate-mixture poses an additional ecological problem. 

Of a number of hydrazine syntheses based on the oxidation of ammonia with sodium hypochlorite in the presence of ketones (acetone, methyl ethyl ketone) (see Fig. 1.4-4), only that of Bayer A.G. appears to have graduated to a commercial process. 

The two main reactions are the formation and hydrolysis of acetone azine  

The formation of azine is not a means of trapping the hydrazine formed in the Raschig process with acetone, the reaction proceeding by way of two distinct intermediates dimethyl oxazirane and acetone hydrazone, as follows  

Sodium hypochlorite solution (ca. 1.5 mol/L), ammonia and acetone in a molar ratio of 1 15 to 20 2 are reacted together at 35°C. A solution results consisting of 5 to 7% by weight of acetone azine together with sodium chloride and excess ammonia. This ammonia is distilled off and returned to the reaction. Next, the acetone azine-water-azeotrope (b.p. 95°C) is distilled off leaving the sodium chloride solution. Herein lies the essential difference from the Raschig process in which the hydrazine water mixture has to be separated from solid sodium chloride. 

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In 1990, appioximately 66,000 metric tons of alumina trihydiate [12252-70-9] AI2O2 3H20, the most widely used flame retardant, was used to inhibit the flammabihty of plastics processed at low temperatures. Alumina trihydrate is manufactured from either bauxite ore or recovered aluminum by either the Bayer or sinter processes (25). In the Bayer process, the bauxite ore is digested in a caustic solution, then filtered to remove siUcate, titanate, and iron impurities. The alumina trihydrate is recovered from the filtered solution by precipitation. In the sinter process the aluminum is leached from the ore using a solution of soda and lime from which pure alumina trihydrate is recovered (see Aluminum compounds). 

Starch is a polysaccharide found in many plant species. Com and potatoes are two common sources of industrial starch. The composition of starch varies somewhat in terms of the amount of branching of the polymer chains (11). Its principal use as a flocculant is in the Bayer process for extracting aluminum from bauxite ore. The digestion of bauxite in sodium hydroxide solution produces a suspension of finely divided iron minerals and siUcates, called red mud, in a highly alkaline Hquor. Starch is used to settle the red mud so that relatively pure alumina can be produced from the clarified Hquor. It has been largely replaced by acryHc acid and acrylamide-based (11,12) polymers, although a number of plants stiH add some starch in addition to synthetic polymers to reduce the level of residual suspended soHds in the Hquor. Starch [9005-25-8] can be modified with various reagents to produce semisynthetic polymers. The principal one of these is cationic starch, which is used as a retention aid in paper production as a component of a dual system (13,14) or a microparticle system (15). 

Recovery from Bayer Liquor. The significant amount of primary gallium is recovered from the alumina industry. The main source is the sodium aluminate Hquor from Bayer-process plants that produce large quantities of alumina. Several methods have been developed to recover gallium from Bayer Hquor. 

A commercial process which uses hydrothermal leaching on a large scale is the Bayer process for production of aluminum oxide (see Aluminum compounds). This process is used to extract and precipitate high grade alurninum hydroxide (gibbsite [14762-49-3]) from bauxite [1318-16-7] ore. The hydrothermal process step is the extraction step in which concentrated sodium hydroxide is used to form a soluble sodium aluminate complex ... 

A.lkaline Solutions. The most important example of alkaline leach is the digestion of hydrated alumina from bauxite by a sodium hydroxide solution at 160-170°C, ie, the Bayer process (see Aluminumand aluminum alloys). 

Precipitation. The precipitation of aluminum tribydroxide ia the recovery step of the Bayer process is achieved either by loweting the temperature or by diluting the pregnant Hquor and reduciag its pH. Both methods reverse the direction of equation 35, but seeding with previously precipitated crystals is required ia order to initiate nucleation. 

Aluminum. All primary aluminum as of 1995 is produced by molten salt electrolysis, which requires a feed of high purity alumina to the reduction cell. The Bayer process is a chemical purification of the bauxite ore by selective leaching of aluminum according to equation 35. Other oxide constituents of the ore, namely siUca, iron oxide, and titanium oxide remain in the residue, known as red mud. No solution purification is required and pure aluminum hydroxide is obtained by precipitation after reversing reaction 35 through a change in temperature or hydroxide concentration the precipitate is calcined to yield pure alumina. 

Cryolite. Cryofite [15096-52-3] Na AlF, is the primary constituent of the HaH-Hfiroult cell electrolyte. High purity, natural cryofite is found in Greenland, but its rarity and cost have caused the aluminum industry to substitute synthetic cryofite. The latter is produced by the reaction of hydrofluoric acid [7664-39-3] HE, with sodium aluminate [1302-42-7] NaA102, from the Bayer process... 

Thus operating cells need aluminum fluoride [7784-18-17, AIF., rather than cryoHte. Much aluminum fluoride is produced in a fluidized bed by the reaction of hydrofluoric acid gas and activated alumina made by partially calcining the alumina hydrate from the Bayer process... 

Aluminum fluoride is also made by the reaction of fluosiUcic acid [16961 -83-4] H2SiFg, a by-product from phosphoric acid production (see Phosphoric ACID AND THE PHOSPHATES), and aluminum hydroxide from the Bayer process. 

Eigure 1 illustrates the Bayer process as it is practiced in the 1990s. The primary purpose of a Bayer plant is to process bauxite to provide pure alumina for the production of aluminum. World production of Al(OH)2 totaled ca 55 x 10 t in 1988. Practically all of the hydroxide was obtained by Bayer processing and 90% of it was calcined to metallurgical grade alumina (AI2O2). However, about 10% of the bauxite processed serves as feedstock to the growing aluminum chemicals industry. 

Causticization, the reaction of hydrated lime [1305-62-0], Ca(OH)2, with sodium carbonate to regenerate sodium hydroxide and precipitate calcium carbonate, is an important part of the Bayer process chemistry. 

Residue Disposal. The major environmental problem in the Bayer process is disposal of bauxite residue which is effected by marine disposal, lagooning, use of underdrain lakes, or semidry disposal. Marine disposal in oceans or rivers, diluting the alkaline residue by large quantities of water, is environmentally unacceptable. Lagooning behind retaining dikes built around clay-sealed ground is commonly used, but there have been isolated leaks into aquifers. This has motivated installation of underdrains between the residue and clay-sealed, plastic-lined, lake bottom. This design removes the hydraulic head from the lake bottom and improves consoHdation of the residue. 

Alternative Processes. Bayer processing of bauxite is the most economical method for Al(OH)2 and AI2O2 production however, the... 

Small amounts of sodium aluminate are prepared in the lab by fusion of equimolar quantities of sodium carbonate [497-19-8] and aluminum acetate [139-12-8], A1(C2H202)3, at 800°C (4). Other methods involve reaction of sodium hycboxide with amorphous alumina or aluminum [7429-90-5] metal. Commercial quantities of sodium aluminate are made from hydrated alumina, in the form of aluminum hydroxy oxide [24623-77-6], AIO(OH), or aluminum hycboxide [21645-51 -2], Al(OH)3, a product of the Bayer process (5,6) which is used to refine bauxite [1318-16-7], the principal aluminum ore. 

Shaped products used for adsorbent purposes are generally less sophisticated and therefore less expensive than catalytic products. In 1985, it was reported that 10,000 t/yr of activated alumina adsorbents were produced in the United States. North American producers of Bayer process-based activated aluminas include Alcoa, La Roche (formerly Kaiser Chemicals), Discovery, and Alcan. Gel-based activated aluminas are produced by La Roche, Vista, and several of the major catalyst manufacturers. In Europe, principal sources of supply are Rhc ne-Poulenc and Condea. 

Specialty alumina derived from the Bayer process resemble SGA, except for a higher a-Al202 content, which is usually >80%, and a lower surface area, typically <20 m /g. The remaining material is generally sodium P-alurnina (Table 2) formed as a result of the soda contamination common to the process (2—7). The mineralogical and stmctural properties of calcined aluminas are given in Table 2 (3). 

Table 4. U.S. Bayer Process Alumina 1989 Year End Prices...

G. MacZura and R. J. Getty, "Bayer Process Aluminas for Ceramics," 24th Pacific Coast KegionalMeeting of theMCerS, Anaheim, Calif., Oct. 1971. 

Fig. 2. Aluminum tiiliydroxides (a) coarse gibbsite from the Bayer process, x 100 (b) Schm h bayerite, x 10, 000.

Gibbsite is aii important technical product and world production, predominantly by the Bayer process, is more than 50 million metric tons aimuaHy. Alost (90%) is calcined to alumina [1344-28-1 j, Al202, to be used for aluminum production. Tlie remainder is used by the chemical industry as filler for paper, plastics, rubber, and as the starting material for the preparation of various aluminum compounds, alumina ceramics, refractories, polishing products, catalysts, and catalyst supports. 

Alumina. A pure although not necessarily a refractory grade of alumina is obtained from bauxite by the Bayer process. In this process, the gibbsite from the bauxite is dissolved in a caustic soda solution and thus separated from the impurities. Alumina, calcined, sintered, or fused, is a stable and extremely versatile material used for a variety of heavy industrial, electronic, and technical appHcations. 

Purification. Alumina, AI2O3, is produced by the Bayer process (1,9) (see Aluminum COMPOUNDS) which involves digestion foUowed by precipitation and calcination. High purity magnesia is extracted from natural brines and seawater by precipitation and calcination (1,9). 

Alumina produced by the Bayer process is precipitated and then calcined [Krawczyk, Ceramic Forum International, 67(7-8), 342-8 (1990)]. Aggregates are typically 20 to 70 [Lm, and have to be reduced. The standard product is typically made in continuous dry ball or vibra-toiy mills to give a product d o size of 3-7 [Lm, 98 percent finer than 45 [Lm. The mills are lined with wear-resistant alumina blocks, and balls or cylinders are used with an alumina content of 80-92 percent. The products containing up to 96 percent AI9O3 are used for bricks, kiln furniture, grinding balls and liners, high voltage insulators, catalyst carriers, etc. 

Production of A1 metal involves two stages (a) the extraction, purification and dehydration of bauxite, and (b) the electrolysis of AI2O3 dissolved in molten cryolite Na3AlF6. Bauxite is now almost universally treated by the Bayer process this involves dissolution in aqueous NaOH, separation from insoluble impurities (red muds), partial precipitation of the trihydrate... 

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