CRYSTALLINE 3-LAYER LITHIUM ALUMINATES

Abstract: Ion exchange resins in the base form (e.g., DOWEX MWA-1-OH ion exchange resin) which contain crystalline Al(OH)₃ (e.g. gibbsite, and/or bayerite, and/or norstrandite) are treated with hot, concen­ trated LiX aqueous solutions (where X is anion) to prepare 3-layer crystalline LiX·2Al(OH)₃·nH₂O in the resin.

Description: The present invention concerns a process for preparing a 3-layer crystalline LiX·2Al(OH)₃·nH₂O in a macroporous ion exchange resin. U.S. Patents 4,116,858 and 4,159,311 disclose that an ion exchange resin may be saturated with aqueous AlCl₃ solution and that reaction with NH₄OH converts the AlCl₃ in situ to Al(OH)₃. This so-formed amorphous Al(OH)₃ is then reacted with LiX, where X is halide, at elevated temperature to form crystalline LiX·2Al(OH)₃ which is useful in selectively recovering Li⁺ values from aqueous solutions, e.g., Li-containing brines. U.S. Patents 4,116,856 and 4,221,767 disclose that improvements in the above discussed formation of crystalline LiX·2Al(OH)₃ are found by reacting amorphous Al(OH)₃, or crystalline hydrous alumina (e.g., nor­ strandite, bayerite, gibbsite or mixtures of these) with LiOH to form LiOH·2Al(OH)₃·nH₂O which is then reacted with LiX to form the crystalline LiX·2Al(OH)₃, where X is halide. Various forms of alumina, Al₂O₃, are known, some of which occur as natural minerals, some of which are hydrated, and some of which are crystalline. The Handbook of Chemistry shows the following: Norstrandite is a crystalline hydrous alumina, as are gibbsite and bayerite. The teachings in U.S. Patent 4,116,856 dis­ close that crystalline hydrous alumina (e.g., nor­ strandite and/or bayerite) dispersed in ion exchange resin is not converted back to its original LiX·2Al(OH)₃·­ nH₂O form by treatment with LiX unless the hydrous alumina is first, or simultaneously, reacted with LiOH. Surprisingly, the present invention shows that crystalline hydrous aluminas can be reacted directly with lithium salts to form crystalline lithium salt aluminates if the correct ranges of temperature and concentration are employed. Ion exchange resins in the base form which contain incorporated amounts of crystalline Al(OH)₃ of the bayerite or norstrandite variety are reacted with hot, concentrated LiX aqueous solutions to prepare 3-layer crystalline LiX·2Al(OH)₃·nH₂O (where X is anion) without solubilizing the Al(OH)₃. Specifically, the present invention concerns a process for preparing crystalline 3-layer LiX·2Al(OH)₃·­ nH₂O in a macroporous ion exchange resin, which comprises: reacting a composite of a microporous ion exchange resin, which is in its base form and which contains crystalline Al(OH)₃ dispersed therein; by mixing the said composite with hot, concentrated aqueous solution of LiX, where X is an anion; thereby converting the crystalline Al(OH)₃ in the resin to crystalline 3-layer LiX·2Al(OH)₃·nH₂O. Compounds made in accordance with the present process are useful in selectively removing Li⁺ values from aqueous solution and are also useful in exchanging of the anion (X) with other anions in aqueous solution. Of special interest is the removal of Li⁺ values from natural brines, e.g., Smackover brine, and from ore leachings, e.g., Spodumene ore. Crystalline hydrous aluminas are reacted with lithium salts under the influence of elevated tempera­ ture and sufficient concentration to form lithium aluminates, designated here as LiX·2Al(OH)₃·nH₂O where X is an anion characterized as an anion which will form acids when in molecular combination with hydrogen or will form salts when in molecular combination with metal ions. It will be understood, of course, that the lithium aluminates will normally contain some waters of hydration, designated as nH₂O in the above formula. The anion may have a valence or 1, 2, or 3. When the beginning hydrous alumina is amorphous, such as when freshly prepared by ammonia precipitation of Al(OH)₃ from AlCl₃ solution, the reaction to form lithium aluminates may be done using relatively weak solutions of the lithium salt (up to about 10%) and at relatively low temperatures (e.g., 20°C-40°C), then when heated at, e.g., about 50°C or higher, the lithium aluminate becomes crystallized as a 3-layer crystal. In accordance with generally accepted practice, all solution concentrations in this dis­ closure are percent by weight, unless noted otherwise. However, when the beginning hydrous alumina is crystalline (such as bayerite, gibbsite, norstrandite, or boehmite), then the relatively low temperature treatment with lithium salt does not appear to form an appreciable amount (if any) of lithium aluminate within a reasonable length of time. It has now been found, surprisingly, that when heated at elevated temperature of preferably about 85°C-120°C, the mixture of crystalline hydrous alumina and lithium salt forms lithium aluminate. Along with this higher temperature, it is necessary that the lithium salt solution be of a relatively high concen­ tration, preferably above about 12%, most preferably above about 20% or may be at the saturation limit of the lithium salt, especially if it is only slightly soluble. The combination of high temperature and high concentration is particularly effective in forcing the lithium salt into the layers of the hydrous alumina crystals, which in some cases gives a crystallographic unit cell having two layers of lithium salt and two layers of hydrous alumina and in other cases gives a crystallographic unit cell having three layers of lithium salt and three layers of hydrous alumina. As used herein, the expressions "2-layer" and "3-layer" refer to the number of layers bounded on both sides by the aluminate layers into which the subject Li compounds are intercalated. It will be realized, of course, that the crystals of lithium aluminates are normally present as aggregates or stacks of a plurality of unit cells rather than each unit cell standing as a separate physical entity. The lithium aluminates discussed here have two crystal structures, e.g., those of 2-layer crystal­ lographic unit cells and those of 3-layer crystallo­ graphic unit cells. The 3-layer lithium aluminates have a 3-fold screw axis oriented parallel to the c-axis of the lithium aluminate crystal. The 2-layer lithium aluminates have a 2-fold axis of rotation oriented parallel to the c-axis, as determined by the x-ray crystal studies. For purposes of discussion and description in this disclosure, 2-layer lithium aluminates and 3-layer lithium aluminates are graphically illustrated as follows: The heating of the mixture of an aqueous solution of lithium salt and hydrous alumina crystals may be performed in an open vessel, in a closed vessel, or at reflux. If performed in an open vessel where water vapor can escape, or if reduced pressure is applied to remove water vapor, the resulting increase in concentration of the lithium salt is beneficial in that the higher concentration tends to help drive the lithium salt into the alumina layers. In those instances wherein water vapor is allowed to escape, a low concentration (generally less than about 10%) lithium salt may be employed at the outset, then the increase in concentration which results from water loss can be sufficient to drive the lithium salt into the hydrous alumina. The preferred lower ratio of lithium salt to hydrous alumina, Al(OH)₃, in the mixture is about 0.5 moles of Li to 1 mole of Al. The upper limit of Li to Al is the saturation point of the lithium salt solution. The lithium salts for reaction with the hydrous alumina can be at least one of the group exempli­ fied by LiCl, LiBr, LiI, LiNO₃, LiClO₄, LiClO, LiSCN, LiOOCH, LiC₂H₃O₂, and the like. Stated another way the X in LiX may be any anion of a halo acid (excluding F), a mineral acid or inorganic acid, or an organic acid which is stable under reaction conditions. Virtually any water soluble lithium salt would be expected to be within the purview of this invention so long as the anion is not so large as to preclude entering the interstices of the alumina crystal. Reaction of lithium salt with some forms of hydrous alumina, such as bayerite or norstrandite, produces 3-layer lithium aluminates. In contrast to the 2-layer LiCl·2Al(OH)₃·nH₂O crystal, the 3-layer LiCl·2Al(OH)₃·nH₂O crystal, whether in neat form or supported on or within a substrate, is stable in H₂O if there is as much as about 50 ppm Li⁺ in the solution. The 3-layer LiOH·2Al(OH)₃·nH₂O, formed by reacting the 3-layer LiX·2Al(OH)₃·nH₂O with LiOH, can be neutralized with an acid to form 3-layer lithium aluminate contain­ ing anions of the acid. The porous substrate into which the crystalline hydrous alumina can be loaded may be an inert material, such as an inorganic or organic material. For certain uses and reasons, the substrate is prefer­ ably a macroporous resin such as an ion exchange resin as taught in U.S. Patents 4,116,858 and 4,116,856. In the preparation of composites of lithium aluminates in ion exchange resins it is found that the use of hot, concentrated LiX (where X is halide or other anion) to convert crystalline Al(OH)₃ to crystal­ line LiX·2Al(OH)₃·nH₂O can give somewhat different results, depending on the form of the resin and the crystalline form of the Al(OH)₃. In the absence of a substrate, such as an ion exchange resin, the treatment with hot, concentrated LiX aqueous solution yields 3-layer crystalline LiX·2Al(OH)₃·nH₂O if the crystal­ line Al(OH)₃ is of the bayerite or norstrandite variety, but the treatment yields 2-layer crystalline LiX·2Al(OH)₃·nH₂O if the crystalline Al(OH)₃ is of the gibbsite variety. If the Al(OH)₃ is amorphous, then the treatment yields 3-layer crystalline LiX·2Al(OH)₃·nH₂O. If the substrate is an inert material, having no ion exchange capability of its own, then the treatment yields the same results as if no substrate is used. If the substrate is an ion exchange resin in its acid form, such as DOWEX MWA-1-Cl ion exchange resin, then the treatment still gives 3-layer crystalline LiX·2Al(OH)₃·­ nH₂O from bayerite or norstrandite and gives 2-layer crystalline LiX·2Al(OH)₃·nH₂O from gibbsite. If, however, the resin is in its base form, e.g., DOWEX MWA-1-OH ion exchange resin, then bayerite or nor­ strandite yields 3-layer crystals and gibbsite also yields 3-layer crystals of LiX·2Al(OH)₃·nH₂O. It appears that having the resin in its base form causes the crystalline Al(OH)₃, even the gibbsite variety, to become solubilized to an extent which caues the resultant treatment with hot concentrated LiX to yield 3-layer crystals of LiX·2Al(OH)₃·nH₂O. The examples which follow are to illustrate particular embodiments; the invention is not limited to the particular embodiments illustrated, but is limited only by the claims. Example 1 A 50-gram portion of gibbsite is mixed and reacted with 200 ml of 20% LiCl aqueous solution at 115°C for about 2 hours. The product obtained is 2-layer LiCl·2Al(OH)₃·nH₂O as determined by x-ray dif­ fraction data. Example 2 A 200-ml portion of a macroporous ion ex­ change resin in bead form (DOWEX MWA-1-Cl, a Trade­ mark of The Dow Chemical Company) containing gibbsite within its pores is mixed and reacted with about 500 ml of 20% LiCl solution at about 105°C under reflux for about 2-3 hours. The reaction product obtained is 2-layer LiCl·2Al(OH)₃·nH₂O as determined by x-ray diffraction data. Example 3 A 200-ml portion of the same resin as in Example 2 above, but containing bayerite within its pores, is mixed and reacted with about 500 ml of 20% LiCl aqueous solution at about 105°C under reflux for about 2-3 hours. The reaction product obtained is 3-layer LiCl·2Al(OH)₃·nH₂O as determined by x-ray diffraction data. Example 4 About 200 ml of the same resin as above, but containing norstrandite within its pores, is refluxed with about 500 ml of 20% LiCl aqueous solution for about 2-3 hours. The reaction product obtained is 3-layer LiCl·2Al(OH)₃·nH₂O as determined by x-ray diffraction data. Example 5 A composite of 2-layer lithium aluminate/­ resin is prepared by mixing and reacting DOWEX MWA-1-Cl ion exchange resin, containing gibbsite in the pores, with a 20% aqueous soution of LiCl at about 105°C. The composite is prepared for use as a Li⁺ value absorber by substantially "unloading" (i.e., regenera­ ting) Li⁺ values from the crystal by washing it with a 1000 ppm Li⁺ solution at 90°C. The so-regenerated composite is useful for extracting Li⁺ values from a Li⁺-containing natural brine (Smackover brine) until the 2-layer crystal is again loaded with Li⁺ values. Regeneration with 1000 ppm Li⁺ solution at 90°C creates no gibbsite, indicating the 2-layer crystal remains intact. In contrast thereto, regenerat­ ing with water containing no Li⁺ values, or containing only about 300 ppm Li⁺ values causes degeneration of the 2-layer crystal to gibbsite, which contaminates the Li-containing effluant from the wash column. Example 6 This example demonstrates the synthesis of a base form of macroporous ion exchange resin composite containing 3-layer crystalline LiCl·2Al(OH)₃·nH₂O wherein the 3-layer aluminate crystal is derived from crystalline Al(OH)₃, instead of amorphous Al(OH)₃, using a procedure which does not solubilize the crystalline Al(OH)₃. A 200 ml. portion of DOWEX MWA-1-OH ion ex­ change resin containing about 3.28 mmoles (per ml. of resin) of Al(OH)₃, gibbsite, is placed in about 200 ml. of concentrated LiCl aqueous solution (about 5M conc.). The mixture is placed in an 80°C oven for about 48 hours. The Al(OH)₃ is completely converted to 3-layer crystalline LiCl·2Al(OH)₃·nH₂O with no loss of Al(OH)₃ into the liquid phase, i.e., no solubilization of the Al(OH)₃. Also, there is no apparent breakage of the resin and the solution remains clear.

Claims: 1. A process for preparing crystalline 3-layer LiX·2Al(OH)₃·nH₂O in a macroporous ion exchange resin, which comprises: reacting a composite of a macroporous ion exchange resin, which is in its base form and which contains crystalline Al(OH)₃ dispersed therein; by mixing the said composite with hot, con­ centrated aqueous solution of LiX, where X is an anion; thereby converting the crystalline Al(OH)₃ in the resin to crystalline 3-layer LiX·2Al(OH)₃·nH₂O. 2. The process of Claim 1 wherein the crystal­ line Al(OH)₃ is of the gibbsite and/or bayerite and/or norstrandite variety. 3. The process of Claim 2 wherein the crystal­ line Al(OH)₃ is of the gibbsite variety. 4. The process of Claim 1 wherein the hot LiX aqueous solution is at a temperature of at least about 70°C. 5. The process of Claim 4 wherein the hot LiX aqueous solution is at a temperature in the range of about 85°C to about 120°C. 6. The process of Claim 1 wherein the con­ centration of the LiX in the aqueous solution is at least about 20% of the saturation concentration by weight. 7. The process of Claim 1 wherein the LiX in the aqueous solution is LiCl and the concentration of the LiCl solution is at least about 8% by weight. 8. The process of Claim 1 wherein the ratio of lithium salt to hydrous alumina, Al(OH)₃, in the mixture is about 0.5:1 (mole Li/mole Al) to the saturation point of the Li salt solution. 9. The process of Claim 1 wherein X is the anion of a halo acid (excluding F), a mineral acid, an inorganic acid, or an organic acid, pro­ viding it is stable under the reaction conditions and not so large as to preclude entering the inter­ stices of the alumina crystal.

Inventors: BURBA III, JOHN LESLIE
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1985
Main classification: B01J47
IPC codes: C01F7, B01J39, C01D15, B01J47, B01J41, B01J20