Aluminum compounds

In the early 1950s Karl Ziegler then at the Max Planck Institute for Coal Research in Germany was studying the use of aluminum compounds as catalysts for the oligomer ization of ethylene... 

Corundum. Comndum [1302-75-5] (see Aluminum compounds) is a naturally occurring massive crystalline mineral composed of aluminum oxide. It is an impure form of the gems mby and sapphke. Prior to 1900 comndum was an important abrasive for the production of grinding wheels. Today it is mainly employed as a loose abrasive for grinding and polishing optical lenses. Almost all the world s supply of comndum now comes from Africa, primarily from Zimbabwe. 

See Adsorption, LIQUID separation Aluminum compounds, aluminum oxide (alumina) Carbon, activated carbon Ion exchange Molecular sieves Silicon... 

Physical Properties. Physical properties of importance include particle size, density, volume fraction of intraparticle and extraparticle voids when packed into adsorbent beds, strength, attrition resistance, and dustiness. These properties can be varied intentionally to tailor adsorbents to specific apphcations (See Adsorption liquid separation Aluminum compounds, aluminum oxide (alumna) Carbon, activated carbon Ion exchange Molecular sieves and Silicon compounds, synthetic inorganic silicates). 

Traditional adsorbents such as sihca [7631 -86-9] Si02 activated alumina [1318-23-6] AI2O2 and activated carbon [7440-44-0], C, exhibit large surface areas and micropore volumes. The surface chemical properties of these adsorbents make them potentially useful for separations by molecular class. However, the micropore size distribution is fairly broad for these materials (45). This characteristic makes them unsuitable for use in separations in which steric hindrance can potentially be exploited (see Aluminum compounds, aluminum oxide (ALUMINA) Silicon compounds, synthetic inorganic silicates). 

Sohd sorbent materials have the abiUty to adsorb water vapor until an equiUbrium condition is attained. The total weight of water that can be adsorbed in a particular material is a function of the temperature of the material and of the relative humidity of the air (see Adsorption). To regenerate the sorbent, its temperature must be raised or the relative humidity lowered. The sohd sorbents most commonly used are siUca (qv), alumina (see Aluminum compounds), and molecular sieves (qv). 

Hydrolysis. Aluminum alkoxides are hydrolysed using either water or sulfuric acid, usually at around 100°C. In addition to the alcohol product, neutral hydrolysis gives high quaUty alumina (see Aluminum compounds) the sulfuric acid hydrolysis yields alum. The cmde alcohols are washed and then fractionated. 

Aqueous solutions of caustic soda aie highly alkaline. Hence caustic soda is ptimatily used in neutralization reactions to form sodium salts (79). Sodium hydroxide reacts with amphotoric metals (Al, Zn, Sn) and their oxides to form complex anions such as AlO, ZnO. SnO ", and (or H2O with oxides). Reaction of AI2O2 with NaOH is the primary step during the extraction of alumina from bauxite (see Aluminum compounds) ... 

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). 

Aluminum chloride hydroxide [1327-41 -9] also called polyaluminum chloride or PAG, is made by partial hydrolysis of aluminum chloride to form a mixture of polymeric species. It is more expensive than alum on a weight basis, but has advantages over alum such as not lowering the pH as much and better cost-effectiveness in some appHcations. Residual aluminum in the water is said to be lower and performance in cold water is better (6,7). It is sold as a solution (see Aluminum compounds, polyaluminum cm ORiDEs). 

Sodium aluminate [1302-42-7] is another source of soluble aluminum made by leaching bauxite with caustic soda. As with alum, the active species are really its hydrolysis products which depend on the chemistry of the system to which it is added. It tends to raise the pH. It is available both as a soHd and as a solution (see Aluminum compounds, aluminates). 

Mag nesia. ndAlumina. Suspension. A mixture of salts, available as Maalox, Mylanta, Gelusil, and Aludrox, contains magnesium hydroxide [1309-42-8] Mg(OH)2, and variable amounts of aluminum oxide in the form of aluminum hydroxide and hydrated aluminum oxide, ie, 2.9—4.2% magnesium hydroxide and 2.0—2.4% aluminum oxide, Al O, for a mixture of 4.9—6.6% combined magnesium hydroxide and aluminum oxide. This mixture may contain a flavoring and antimicrobial agents in a total amount not to exceed 0.5% (see Aluminum compounds, aluminum oxide). 

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 ... 

Under equiUbrium conditions, magnesium can contain as much as 12.7% aluminum in soHd solution at the eutectic temperature. However, the slow diffusion of aluminum to the grain boundary leads to a coring effect in primary crystals and a hard-phase magnesium—aluminum compound(17 12)... 

Some nut trees accumulate mineral elements. Hickory nut is notable as an accumulator of aluminum compounds (30) the ash of its leaves contains up to 37.5% of AI2O2, compared with only 0.032% of aluminum oxide in the ash of the Fnglish walnut s autumn leaves. As an accumulator of rare-earth elements, hickory greatly exceeds all other plants their leaves show up to 2296 ppm of rare earths (scandium, yttrium, lanthanum, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The amounts of rare-earth elements found in parts of the hickory nut are kernels, at 5 ppm shells, at 7 ppm and shucks, at 17 ppm. The kernel of the Bra2d nut contains large amounts of barium in an insoluble form when the nut is eaten, barium dissolves in the hydrochloric acid of the stomach. 

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

Dicyclopentadiene is also polymerized with tungsten-based catalysts. Because the polymerization reaction produces heavily cross-Unked resins, the polymers are manufactured in a reaction injection mol ding (RIM) process, in which all catalyst components and resin modifiers are slurried in two batches of the monomer. The first batch contains the catalyst (a mixture of WCl and WOCl, nonylphenol, acetylacetone, additives, and fillers the second batch contains the co-catalyst (a combination of an alkyl aluminum compound and a Lewis base such as ether), antioxidants, and elastomeric fillers (qv) for better moldabihty (50). Mixing two Uquids in a mold results in a rapid polymerization reaction. Its rate is controlled by the ratio between the co-catalyst and the Lewis base. Depending on the catalyst composition, solidification time of the reaction mixture can vary from two seconds to an hour. Similar catalyst systems are used for polymerization of norbomene and for norbomene copolymerization with ethyhdenenorbomene. 

Alkoxides of nonmetals are described in articles about the corresponding compounds (see Boron COMPOUNDS, Boron oxides Silicon compounds). Metal alkyls, in which the alkyl group is bound direcdy to the metal, are also discussed elsewhere (see Aluminum compounds). 

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