This invention relates to novel adsorbents and substrates and methods for producing same from synthetic hydrotalcite and activated aluminas.
Activated aluminas, made by various procedures, have been widely used as adsorbents and also as substrates for catalytically active materials. Procedures have been developed to manufacture alumina in various forms and properties for use as adsorbents, desiccants, and catalyst substrates.
A common and most widely used activated alumina product is produced by the thermal dehydration or activation of aluminum hydroxides. Such hydroxides include both crystalline and gelatinous aluminum hydroxides. Upon dehydration, water is expelled, leaving behind a porous skeleton of aluminum oxide of high surface area, e.g., such as 50-450 m.sup.2 /g. The pore structure of the alumina and the high surface area are important properties of the alumina influencing its behavior as an adsorbent. The size and geometry of the pores formed during dehydration is related primarily to the molecular structure of the hydroxide and can be altered only by a relatively small extent by varying the methods of hydroxide preparation, forming, dehydration, and other procedures.
However, the major fraction of the pores of dehydrated aluminum hydroxide are of small size, as determined by mercury penetration methods, e.g., such as less than than about 50 .ANG. in diameter. This small size of pores is a major disadvantage of activated alumina for the adsorption of large molecules and also for catalytic uses where the pores can get blocked easily by impurities, by large molecules, by coke, or by other by-products of the reaction.
Activated carbon has been used widely as a multipurpose adsorbent. However, the adsorptive ability of activated carbon is insufficient for adsorption of organic acids such as carboxylic acids and sulfonic acids, decolorization of waste liquors containing acid dyes, and adsorption of alkalies.
La Lande, U.S. Pat. No. 2,413,184, discloses the preparation of adsorbent compositions, more particularly the production of water-insoluble metal aluminates suitable for use as decolorizing adsorbents and catalysts. An alkali metal aluminate is dispersed in sufficient water to dissolve the compound, and then is added to a second solution containing an ammonium salt and a salt of a metal capable of forming a water-insoluble metal aluminate. The mixture then is heated, preferably to its boiling point, for a period of time sufficient to complete the reaction.
Zall, U.S. Pat. No. 3,876,451, discloses activated carbon for the removal of phosphate from waste effluents. The activation of the carbon is accomplished by introducing cations, such as aluminum, manganese, zinc, iron, lithium, or calcium, into the carbon structure. The cations have the ability to react with the phosphates and the waste effluents and thereby fix the phosphates in the carbon material.
Manabe et al, U.S. Pat. No. 4,458,030, disclose an adsorbent composition consisting essentially of 5-95% by weight of hydrotalcite and about 95-5% by weight of activated carbon. The patent discloses that hydrotalcite compounds of magnesium oxide do not show an effective adsorptive power for the adsorption of phenols and amines. Manabe discloses that it has been virtually impossible to remove various substances by adsorption with one type of adsorbent. Rather, complicated and disadvantageous adsorption process steps involving several adsorbing and removing operations have been necessary using different types of adsorbent.
Reichle, U.S. Pat. No. 4,458,026, discloses novel catalyst materials produced as a preparation of Mg/Al/carbonate hydrotalcite which involves the addition of mixed magnesium/aluminum nitrates, sulphates, or chlorides as an aqueous solution to a solution of a stoichiometric amount of sodium hydroxide and carbonate at about 25.degree.-35.degree. C. while stirring over a several-hour period to produce a slurry. The slurry then is heated for about 18 hours at about 50.degree.-200.degree. C. (preferably 60.degree.-75.degree. C.) to allow a limited amount of crystallization to take place. After filtering the solids, and washing and drying, the dry solids are recovered.
Hydrotalcite is a naturally occurring mineral having the formula 6 MgO.Al.sub.2 O.sub.3.CO.sub.2.12 H.sub.2 O or Mg.sub.6 Al.sub.2 (OH).sub.16 CO.sub.3.4 H.sub.2 O. Known deposits of natural hydrotalcite are very limited. Natural hydrotalcite has been found in Snarum, Norway and in the Ural Mountains. Typical occurrences are in the form of serpentines, in talc schists, and as an alteration product of spinel where, in some cases, hydrotalcite has formed as pseudomorphs after spinel.
The upper stability temperature of hydrotalcite is lower than the lower limit for spinel. Spinel and hydrotalcite theoretically never would appear together in stable condition. If equilibrium has been established, the spinel would be completely changed to hydrotalcite. However, naturally occurring hydrotalcite is intermeshed with spinel and other materials.
Natural hydrotalcite is not present as pure product and always contains other minerals such as penninite and muscovite and potentially undesirable minerals such as heavy metals. Conventional practice recognizes that it is practically impossible to remove such impurities from a natural hydrotalcite.
Previous attempts to synthesize hydrotalcite have included adding dry ice or ammonium carbonate (a) to a mixture of magnesium oxide and alpha-alumina or (b) to a thermal decomposition product from a mixture of magnesium nitrate and aluminum nitrate and thereafter maintaining the system at temperatures below 325.degree. C. at elevated pressures of 2,000-20,000 psi. Such a process is not practical for industrial scale production of synthetic hydrotalcite by reason of the high pressures. Furthermore, the high pressure process forms substances other than hydrotalcite, such as brucite, boehmite, diaspore, and hydromagnesite.
Ross and Kodama have reported a synthetic mineral prepared by titrating a mixed solution of MgCl.sub.2 and AlCl.sub.3 with NaOH in a CO.sub.2 free system and then dialyzing the suspension for 30 days at 60.degree. C. to form a hydrated Mg-Al carbonate hydroxide. The mineral product has been associated with the formula Mg.sub.6 Al.sub.2 CO.sub.3 (OH).sub.16.4 H.sub.2 O while having the properties of manasseite and hydrotalcite. X-ray diffraction powder patterns have indicated that the mineral more closely resembles manasseite than hydrotalcite, while the differential thermal analysis curve of the precipitate has been characterized as similar to that given for hydrotalcite.
Kumura et al, U.S. Pat. No. 3,650,704, reports a synthetic hydrotalcite preparation by adding an aqueous solution of aluminum sulfate and sodium carbonate to a suspension of magnesium hydroxide. The suspension then can be washed with water until the presence of sulfate radical becomes no longer observable. The suspension is heated at 85.degree. C. for three hours and dried. The magnesium component starting material is reported as any member of the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, and water-soluble magnesium salts, e.g., such as mineral acid salts including magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium dicarbonate, and bittern. p It is an object of the present invention to produce adsorbents and substrate products from activated aluminas and synthetic hydrotalcite in high purity.
It is another object of this invention to produce adsorbents and substrate products having high mechanical strength, high porosity, low bulk density, and wide pore size distribution.
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