Calcium aluminates, 5.18

Calcined alumina markets consume slightly less than 50% of the specialty alumina chemicals production (1—8,20,22—115). Worldwide usage is estimated to be about 50% for refractories (qv), 20% for abrasives, and 25% for ceramics (qv). Calcined aluminas are also used in the manufacture of tabular alumina and calcium aluminate cements (CAC). Quantities are estimated to be over 200,000 and 100,000 t, respectively (7). 

Refined calcined alumina is commonly used in combination with high purity limestone [1317-65-3] to produce high purity calcium aluminate cement (CAC). The manufacture, properties, and appHcations of CAC from bauxite limestone, as weU as high purity CAC, has been described (104). High purity CAC sinters readily in gas-fired rotary kiln calcinations at 1600 —1700 K. CAC reactions are considered practically complete when content of free CaO is less than 0.15% andloss on ignition is less than 0.5% at 1373 K. 

Table 3. Characteristics of Calcium Aluminate Cement (CAC) Mineral Constituents ...

Most commercial methanator catalysts contain nickel, supported on alumina, kaolin, or calcium aluminate cement. Sulfur and arsenic are poisons to the catalyst, which can also be fouled by carry-over of solvent from the CO2 removal system. 

Calcium Aluminate Cements. Low purity calcium aluminate [12042-78-3] cements are obtained by sintering or fusing bauxite and lime in a rotary or shaft kiln. A high purity calcium aluminate cement, 2CaO 5AI2O2, capable of withstanding service temperatures of 1750°C can be prepared by the reaction of high purity lime with calcined or hydrated alumina (see Aluminum compounds). 

Portland cement is classified as a hydrauHc cement, ie, it sets or cures in the presence of water. The term Portland comes from its inventor, Joseph Aspdin, who in 1824 obtained a patent for the combination of materials referred to today as Portland cement. He named it after a grayish colored, natural limestone quarried on the Isle of Portland, which his cured mixture resembled. Other types of hydrauHc cements based on calcium materials were known for many centuries before this, going back to Roman times. Portland cement is not an exact composition but rather a range of compositions, which obtain the desired final properties. The compounds that make up Portland cements are calcium siHcates, calcium aluminates, and calcium aluminoferrites (see ). 

The reactions in the regulated-set cements containing Cjj A3CF2 (note mixed notation) as a principal phase resemble those in ordinary Portiand cements. Initial reaction rates are controlled by ettringite formation. Setting occurs with formation of the monosulfate, along with some transitory lower-limed calcium aluminate hydrates that convert to the monosulfate within a few hours. 

Special purpose and blended Portland cements are manufactured essentially by the same processes as ordinary Portland cements but have specific compositional and process differences. White cements are made from raw materials of very low iron content. This type is often difficult to bum because almost the entire Hquid phase must be furnished by calcium aluminates. As a consequence of the generally lower total Hquid-phase content, high burning-zone temperatures may be necessary. Past cooling and occasionally oil sprays are needed to maintain both quaHty and color. 

When calcium aluminate cements are made by the fusion process, the solidified melt must be cmshed and then ground. The material is very hard to grind and power consumption is high. 

Cement. Portland cement, a mixture of calcium siUcate and calcium aluminate minerals, is produduced by the calcination of argillaceous limestone or mixtures of limestone and clay (see Cement). Although other clays can be used, ka olin is preferred because of its alumina and siUca content and low level of impurities. It is especially desirable in the manufacture of white cement and other types requiring careful control of chemical composition. Air-floated ka olin, because of its low cost, is usually used. 

Cement and Concrete Concrete is an aggregate of inert reinforcing particles in an amorphous matrix of hardened cement paste. Concrete made of portland cement has limited resistance to acids and bases and will fail mechanically following absorption of crystalforming solutions such as brines and various organics. Concretes made of corrosion-resistant cements (such as calcium aluminate) can be selected for specific chemical exposures. 

Castable Monolithic Refractories Standard portland cement is made of calcium hydroxide. In exposures above 427°C (800°F) the hydroxyl ion is removed from portland (water removed) below 427°C (800°F), water is added. This cyclic exposure results in spalling. Castables are made of calcium aluminate (rather than portland) without the hydroxide they are not subject to that cychc spaJhng failure. 

Increase in flame temperature often leads to the formation of free gaseous atoms, and for example aluminium oxide is more readily dissociated in an acetylene-nitrous oxide flame than it is in an acetylene-air flame. A calcium-aluminium interference arising from the formation of calcium aluminate can also be overcome by working at the higher temperature of an acetylene-nitrous oxide flame. 

The catalysts used in the process are essentially nickel metal dispersed on a support material consisting of various oxide mixtures such as alumina, silica, lime, magnesia, and compounds such as calcium aluminate cements. When the catalyst is made, the nickel is present as nickel oxide which is reduced in the plant converter with hydrogen, usually the 3 1 H2 N2 synthesis gas ... 

The production of synthesis gas from natural gas and coal is the basis of the 33 000000 tpa methanol production and is also used in the production of ammonia. After removal of sulfur impurities, methane and water are reacted over a nickel oxide on calcium aluminate catalyst at 730 °C and 30 bar pressure. The reaction is highly endothermic (210 kJmol ) (Equation 6.6). 

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