Title of Invention	A METHOD FOR PRODUCING CRYSTALLINE CALCIUM HEXABORATE TETRAHYDRATE
Abstract	An improved method is provided for producing crystalline calcium hexaborate tetrahydrate, synthetic nobleite, by the reaction of boric acid and lime in an aqueous slurry. Reaction conditions include boric acid to water molar ratios of greater than 0.25:1, lime to boric acid molar ratios in the range of 0.05-0.15:1 and temperatures in the range of 85°-105°C. A novel crystalline product is produced having a unique crystal habit resulting in improved physical properties. Dehydration of this product produced a novel amorphous, anhydrous product having similar crystal habit and physical properties.

Title of Invention

A METHOD FOR PRODUCING CRYSTALLINE CALCIUM HEXABORATE TETRAHYDRATE

Abstract

An improved method is provided for producing crystalline calcium hexaborate tetrahydrate, synthetic nobleite, by the reaction of boric acid and lime in an aqueous slurry. Reaction conditions include boric acid to water molar ratios of greater than 0.25:1, lime to boric acid molar ratios in the range of 0.05-0.15:1 and temperatures in the range of 85°-105°C. A novel crystalline product is produced having a unique crystal habit resulting in improved physical properties. Dehydration of this product produced a novel amorphous, anhydrous product having similar crystal habit and physical properties.

Full Text	This invention in general relates to a method for producing crystalline calcium hexaborate tetrahydrate and more particularly to an improved method for producing crystalline calcium hexaborate tetrahydrate, a synthetic form of the mineral nobleite, by the reaction of boric acid and lime in an aqueous slurry. BACKGROUND OF THE INVENTION Calcium borates have many industrial applications. They are used as a source of boron in fiberglass manufacture when the desired glass composition requires that sodium addition be limited, such as for textile fiberglass. They are also useful as fire retardant agents in such materials as plastics and rubber polymers, cellulosics, resins and oils, etc. Further, they are useful in the manufacture of steel and ceramics. Many different calcium borate compositions are known, both natural and synthetic; they are most commonly formed as hydrated compounds. Naturally occurring calcium borates which are commonly used commercially include colemanite, which has the chemical composition 2CaO.3B2O3.5H2O, and ulexite, a mixed sodium-calcium borate of the composition Na20.2CaO.5B2O3.16H2O. Disadvantages of these naturally occurring calcium borate minerals include the presence of mineral impurities,the need for fine grinding when very fine particle sizes are needed, such as to achieve fine dispersions in polymeric resins for fire retardant applications, and in the case of ulexite, the presence of sodium and substantial water content. The borate contents of colemanite and ulexite are about 51% B2O3 and 43% B2O3, respectively. 1A Known synthetic calcium borates include the tetrahydrate and hexahydrate forms of calcium metaborate, CaO.B2O3.4H2O and CaO.B2O3.6H2O, which contain about 35% and 30% B2O3, respectively. Although these synthetic compositions have the potential of being of higher purity, since they lack the mineral impurities found in naturally occurring colemanite and ulexite, they are relatively low in borate content by comparison. Synthetic gowerite, consisting of calcium hexaborate pentahydrate (CaO.3B2O3.5H2O), contains about 59% B2O3/ which is substantially higher in borate content than the calcium metaborate compositions. However, gowerite tends to. 1B crystallize in a coarse, granular form, thus requiring grinding to achieve the fine particle sizes needed for many applications. Calcium hexaborate tetrahydrate, which has the formula CaO 3B2O34H2O, has the same ratio of boron to calcium as synthetic gowerite, but contains less water. At 62% B2O3 it has a higher borate content than gowerite, the calcium metaborates and (he minerals colemanite and ulexite. It is known to occur in nature as the mineral nobleite, although it is not found in commercially exploitable quantities. Various methods for producing synthetic forms of the minerals nobleite and gowerite are known. For example synthetic nobleite can be produced by the hydrothermal treatment of meyerhofferite (2CaO 3B2O37H2O) in boric acid solution for 8 days at 85°C. See U.S. Patent No. 3,337,292. Ditte, Acad. Sci. Paris Copies rendus, 77, 783-785 (1873), described the formation of lime borates by reaction of Iceland spar (calcite) with a saturated boric acid solution. The resultant salt was described as small needles of "a hydrated lime borate" .which contains "3BoO2, CaO and 4HO, which can be written as (2BoO2 CaO HO)(BoO2, 3HO)." Subsequently, Erd, McAllister and Vlisidis, American Mineralogist, 46 , 560-571 (1961), suggested the Ditte product was nobleite. Erd et al also synthesized nobleite by stirring CaO and boric acid in water for 30 hours at 48°C. and then holding the product at 68°C for 10 days. Kemp, The Chemistry of Borates, Part I, page 70 (1956), reported that an aqueous solution of boric acid kept at 40°C for 3 weeks deposits a mixture of CaO-3B2O3 4H2O and 2CaO-3B2O39H2O. Kemp also reported that CaO.3B2O38H2O decomposes to form CaO.3B2O3.4H2O. According to Supplement to Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Volume V. Part A: Boron-Oxygen Compounds, pages 550-551 (1980), CaO-3B2O3.4H2O occurs as a solid phase in the systems Na2O-CaO-B2O3-H2O and CaO-NaCl-B2O3-H2O at 25°C and pH 5.5-6.5. Hydrothermal treatment of meyerhofferite in boric acid solution at 85-250°C produced crystals of both the tetrahydrate and pentahydrate together with gineritc (2CaO-7B2O3-8H2O). Mellor further reported that nobleite is a stable phase in the CaO-B2O3-H2O system at 25°C and at 45°C and is also formed from an aqueous mixture of lime (CaO 2 and boric acid at 60°C. Also, Mellor reports on page 551 that CaO.3B2O3.5H2O (gowerite) is formed from lime and boric acid in aqueous media at 100°C. Lehmann et al, Zeitshrift fur Anorqanische und Allgemeine Chemie, Volume 346, pages 12-20, (1966), teach that the formation of gowerite from CaO, H3BO3 and water is favored by a relatively high temperature (100°C), and higher CaO concentration, whereas nobleite formation is predominantly formed in more dilute solutions with lower CaO content and at lower temperature (60°C}. In contrast to the teachings of the art, it has been discovered that the reaction of boric acid and lime in an aqueous mixture at high temperature will produce nobleite instead of gowerite provided that the reactants, and boric acid in particular, are present at sufficiently high concentration in the reaction slurry, and the molar ratio of lime to boric acid ( CaO:H3BO3) added is within specific limits. SUMMARY OF THE INVENTION Accordingly, the present invention provides, a method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. The method of this 3 invention results in a rapid reaction rate, high product yield and favorable product characteristics such as fine particle size distribution, rapid filtration and good flow and bulk handling properties. Further, there is provided a novel crystalline calcium hexaborate tetrahydrate composition having a distinctive crystal habit. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate produced at low temperature (approximately 22°C). Figure 2 is a photomicrograph of calcium hexaborate tetrahydrate produced at high temperature (approximately 95°C) by the improved method of this invention. 3A DETAILED DESCRIPTION OF THE INVENTION The method of this invention comprises reacting high concentrations of boric acid and lime in water at high temperature, such as in the range of 85° to 105°C, to form crystalline calcium hexaborate tetrahydrate. The preferred reaction temperatures are near the boiling point of the slurry, and preferably in the range of from 95° to 101°C. The concentration of the reactants is important to the production of calcium hexaborate tetrahydrate according to the process of this invention. In particular, a high ratio of boric acid to water in the reaction mixture will produce nobleite rather than gowerite at the high temperature conditions of this invention. Boric acid, which is highly soluble in water at high temperatures, should be added in quantities which are substantially greater than the solubility limit, in order to produce nobleite at these temperatures. The molar ratio of boric acid to water (H3BO3:H2O) in the starting mixture should be greater than 0.25:1, such as in the range of from 0.25 to 0.5:1 and preferably in the range of from 0.3 to 0.45:1. This is substantially higher than the solubility limit of boric acid at temperatures of 80° to 100°C which ranges from 0.07 to 0.11 moles of H3BO3 per mole of water. The molar ratio of lime to boric acid (CaO:H3BO3) in the starting mixture is in the range of from 0.05 to 0.15:1, and preferably 0.1 to 0.13:1. As used herein, lime includes calcium oxide such as burnt lime and quick lime, calcium hydroxide such 4 as hydrated lime, slaked lime and lime hydrate, and calcium carbonate, including calcite and limestone. It appears to be beneficial to have a high concentration of undissolved solids in the reaction mixture such as would provide at least 25% by weight undissolved solids in the final product slurry and preferably at least 30% by weight. If the solids concentration is too low, this may lead to the formation of gowerite instead of the desired nobleite. The method of this invention may be used in producing calcium hexaborate tetrahydrate in a batch, continuous or semi-continuous process. In a batch process, the boric acid and lime may be combined in water and heated at the required temperature range to initiate the reaction. Alternatively, a mother liquor recycled from previous runs or freshly prepared mother liquor may be used as the reaction media. In a continuous or semi-continuous process, the desired product is continuously removed from the reaction vessel and the remaining mother liquor is recycled by adding additional boric acid and lime and heating the reactants at the reaction temperatures. The reaction is essentially complete within one hour, although small improvements in the product B2O3 analysis may be attained by heating the reaction mixture for up to about 4 hours. When calcium oxide or calcium hydroxide are used as reactants, the reaction occurs as a noticeable exotherm within about 15 to 25 minutes, during which time the majority of the starting materials are converted to the desired product. 5 Preferably, the reaction mixture is agitated, such as by stirring, during the reaction period. After the reaction is completed, the nobleite product is separated from the hot mother liquor such as by filtration or centrifugation or other suitable mean of solid-liquid separation. The wet solids may be washed, such as with water, to remove any entrained mother liquor, and subsequently dried to provide a crystalline calcium hexaborate tetrahydrate. If a product with higher B2O3 content is desired, the calcium borate tetrahydrate can be dehydrated by heating at a temperature of at least 325°C, preferably in the range of 450°C to 550°C to produce a novel amorphous, anhydrous calcium hexaborate, CaO.3B2O3, which contains about 79% B2O3. The production of nobleite by the method of this invention has a number of advantages over the previously known methods. The reaction time is substantially reduced from as long as several weeks at low temperatures, to as short as less than an hour at the temperatures of this invention. Also, the high concentration of reactants provides a higher yield of product per unit volume of the reaction mixture. Substantially pure nobleite can be produced under the preferred conditions of this invention, while under the conditions outside of this region, nobleite is partially or totally replaced by the formation of gowerite during the reaction. It has been further discovered that the product of the method of this invention has a unique crystal habit not found in nobleite formed at low concentrations and temeratures.Nobleite, as found in nature and as synthesized at room temperature, is 5A distinguished by a platy morphology. Although it is monoclinic, the platelets have a pseudohexagonal form. The platelets are commonly found in aggregates that arc stacked or arranged sub parallel to the 100 plane. The large thin crystals have been found in sizes up to a centimeter in length and have a hexagonal aspect, while the smaller crystals are more rhombic shaped and may form drusy coatings. See also Erd, McAllister and Vlisidis, American Mineralogist-46 , 560-571 (1961). Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate crystals formed at room temperature, obtained by scanning electron microscopy at a magnification of 5500x. Although the crystalline form of the calcium hexaborate tetrahydrate produced by the process of this invention is also composed of platelets, the crystal habit or arrangement of these platelets is very distinctive and unique. Individual thin platelets, are arranged in nearly spherical radial clusters. Figure 2 is a photomicrograph of the crystalline product of this invention obtained by scanning electron microscopy at a magnification of 3000x and shows the unique crystal habit of the product produced according to the method of this invention. Particle size analysis of the crystalline product of this invention indicates a relatively small mean particle size distribution, typically of about 90% less than 75 micrometers in diameter. This small mean particle diameter is advantageous for many applications where a fine dispersion of the solids is required, such as for fire retardant applications in polymeric resins. Yet it is easy to filter, facilitating the separation of the solid product from the mother liquor, which then can be recycled back into the process. Further, the spherical shape of the crystal habit results in excellent handling and flow properties of the dried solids despite the extremely fine particle size distribution. It was also found that the crystalline product docs not have a significant tendency toward caking. The product dehydrates in three distinct stages, losing water at about 91°, 177° and 312°C. It was found to melt at a temperature of about 927°C. The anhydrous calcium borate product produced by dehydration of the product is less hygroscopic than most dehydrated metal borate compounds. EXAMPLES The following examples illustrate the novel methods and compositions of this invention. EXAMPLE 1 Boric acid (1,448 grams) and 31.7 grams of calcium hydroxide (Ca(OH)2) were combined in 5.00 liters of deionized water in a stirred flask to make up a batch of synthetic mother liquor. This mixture was stirred and heated to 95°C and two batches, each of 2,089 grams of boric acid and 417 grams of calcium hydroxide, were added over a period of about six minutes to give a final reaction slurry (33% undissolved solids) containing a lime to boric acid (CaO:H3BO3) molar ratio of 0.13:1 and a boric acid to water (H3BO3H2O) molar ratio of 0.33:1. There was a slight drop in temperature after the addition of each batch, followed by a final exotherm which raised the temperature to boiling (1010C). The resultant reaction mixture was stirred at about 95° to 100°C for 3 hours and samples of the solid product and liquor were taken for analysis after each hour. The results are shown in Table 1. The reaction slurry was diluted with warm water and filtered to give a filter cake of product which was washed with cold water to remove adhering liquor. The resultant crystalline product was dried and determined to be substantially pure nobleite by X-ray diffraction analysis, titration and thermogravimetric analysis (TGA). Figure 2 is a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 3000x. 7 TABLE 1 Reaction Time Weight % B2O3 in solids Weight % CaO in solids Molar Ratio CaO/B2O3 in solids Weight % B2O3 in liquor Weight %CaO in liquor 1 Hour 61.69 15.90 0.320 10.82 0.29 2 Hours 61.84 15.94 0.320 9.08 0.24 3 Hours 62.11 15.96 0.319 8.90 0.24 Theoretical 62.00 16.62 0.333 The crystalline nobleite product had a very fine particle size distribution with more than 90% by weight passing a 200 mesh (74 micrometer) lest sieve and 70% by weight passing a 325 mesh (45 micrometer) test sieve. The particle size distribution is shown in Table 2. TABLE 2 U.S. Mesh Opening Size (micrometers) Weight % Retained Cum. Weight % Passing 80 180 0.93 99.07 100 150 0.19 98.88 140 105 1.10 97.78 200 75 3.82 93.96 325 45 22.84 71.12 EXAMPLES 2-13 Synthetic mother liquors were prepared by combining boric acid, lime (in the form of calcium hydroxide) and deionized water in a stirred flask. These mixtures were heated to a temperature of 95°C and additional boric acid and lime were added to the reaction mixtures in up to four batches. The reaction mixtures were stirred at 95°C for 3 to 4 hours following the final addition of boric acid and lime. At the end of the reaction time the slurry was filtered and washed to recover the solid product. The 8 molar ratios of reactants, namely boric acid:water (BA/Water) and lime:boric acid (CaO/BA), are shown in Table 3 below along with the product B2O3 analyses and mineralogical results. The mineralogy of the crystalline product was generally determined by X-ray diffraction and microscopy. The nobleite/gowerite ratio was estimated for some of the products from X-ray diffraction data. TABLE 3 Example No. Mole Ratios of Reactants Product Analyses BA/Water CaO/BA %B2O3 Mineralopv 2 0.43 0-09 63.3 Nobleilc 3 0.33 0.13 62 Nobleitc 4 0.30 0.14 62.2 Nablcitc + Gowcritc (92/8)' 5 0.30 0.14 61.4 Nobleite 6 0.23 0.11 62.1 Nobleitc + Gowerite (94/6) 7 0.20 0.15 59.1 Nobicite + Gowcritc 8 0.17 0.09 59.1 G owe rite 9 0.12 0.12 59.4 Nobleilc + Gowcrite 10 0.12 0 12 58.9 Goweritc 11 0.10 0.14 58.2 Gowcritc 12 0.06 0.09 58.3 Gowcritc 13 0.04 0.16 41.3 Sibirskite As shown in the Examples of Table 3, substantially pure nobleitc, having a high B2O3 analysis, is produced when the boric acid/water molar ratio is above about 0.25 and the lime/boric acid molar ratio is less than about 0.15. When the boric acid/water ratio is reduced and/or the lime/boric acid ratio is increased, the boric oxide content of the product decreases and the nobleite product is replaced by gowerite. 9 EXAMPLES 14-17 The following reactions were carried out using calcium carbonate as the source of lime. Example 14 was carried out by a procedure similar to Example I above, wherein a synthetic mother liquor was made by mixing boric acid, calcium carbonate and deionized water in a stirred flask and after heating to 95°C additional boric acid and calcium carbonate were added. In examples 15-17 deioniz.ed water and calcium carbonate were combined and, after heating to 95°C, boric acid v/as added. Substantial foaming of the reaction mixtures was observed as a result of CO2 gas released by the reaction of the boric acid and calcium carbonate. This resulted in a drop in temperature from 95°C.to about 63-66°C. The reaction mixtures were reheated to 95°C within 15 to 20 minutes. The reaction mixtures were stirred continuously and the temperatures controlled at about 95°C for about 3 to 3.5 hours after the final reagent additions. At the end of the reaction period the slurries were filtered and the solids washed to remove entrained solution. The mole ratios of the reactants and the chemical and mineralogical analyses of the solid products are summarized in Table 4. TABLE 4 Example No. Mole Ratio of Reactants Product Analyses BA/water CaO/BA %B2O3 Mineralogy 14 0 33 0.13 62 2 Nobleite 15 0.33 0.16 60 5 Nobleite 16 0.33 0.13 62.3 Nobleite 17 0.24 0.21 55.6 Nobleite+Calcite 10 EXAMPLE 18 (Comparative) Boric acid (40 grams) and 8 grams of hydrated lime were added to 200 grams of water to give a reaction mixture containing a boric acid to water molar ratio of 0.06:1 and a lime to boric acid molar ratio of 0.17:1. The mixture was stirred initially and then allowed to sit at room temperature (approximately 22°C) over a seven day period. The resulting solid product was recovered and determined to be nobleite by X-ray diffraction analysis. Figure 1, a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 5500x, shows the product as consisting of stacked aggregates of hexagonal platelets. The above example shows that while synthetic nobleite can be formed at low ratios of boric acid to water at low temperatures, long reaction times are required. Further, the crystal habit of the resultant product is more like that described for natural nobleite than the spherical radial clusters obtained by the process of the present invention as illustrated in Example 1. EXAMPLE 19 A 5.9 kilogram sample of synthetic nobleite containing product from Examples 1, 3 and 5 was distributed into several stainless steel pans and heated in an oven at 500°C for about 17 hours. The residual water content of the dehydrated product was determined to be less than 0.5% by weight by thermogravimetric analysis. This product was observed to have the same free-flowing properties characteristic of the nobleite product prior to dehydration. This is attributed to the particle form or habit which was confirmed by scanning electron microscopy to resemble the crystal habit of the hydrate prior to dehydration except that there are generally some openings of the radial platelets making up the spherical radial clusters. Despite this characteristic particle form or habit which is residual from the crystalline form existing prior to dehydration. X-ray diffraction analysis indicated that the dehydrated product is essentially amorphous. 11 Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims. 12 WE CLAIM: 1. A method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. 2. A method as claimed in claim 1, wherein said molar ratio of boric acid to water is in the range of from 0.3 to 0.45:1. 3. A method as claimed in claim 1, wherein said molar ratio of lime to boric acid is in the range of from 0.1 to 0.13:1. 4. A method as claimed in claim 1, wherein said temperature is in the range of from 95° to 101°C. 5. A method as claimed in claim 1, wherein source of said lime is calcium carbonate. 6. A method as claimed in claim 1, wherein said lime is hydrated lime. 7. A method as claimed in claim 1, wherein said crystalline calcium hexaborate tetrahydrate is dehydrated by heating at a temperature above 325°C. 8. A method as claimed in claim 7, wherein said temperature is in the range of from 450°C to 550°C. 13 14 9. A method for producing crystalline calcium hexaborate tetrahydrate, substantially as herein described, particularly with reference to the foregoing examples and the accompanying drawings. This invention in general relates to a method for producing crystalline calcium hexaborate tetrahydrate and more particularly to an improved method for producing crystalline calcium hexaborate tetrahydrate, a synthetic form of the mineral nobleite, by the reaction of boric acid and lime in an aqueous slurry. BACKGROUND OF THE INVENTION Calcium borates have many industrial applications. They are used as a source of boron in fiberglass manufacture when the desired glass composition requires that sodium addition be limited, such as for textile fiberglass. They are also useful as fire retardant agents in such materials as plastics and rubber polymers, cellulosics, resins and oils, etc. Further, they are useful in the manufacture of steel and ceramics. Many different calcium borate compositions are known, both natural and synthetic; they are most commonly formed as hydrated compounds. Naturally occurring calcium borates which are commonly used commercially include colemanite, which has the chemical composition 2CaO.3B2O3.5H2O, and ulexite, a mixed sodium-calcium borate of the composition Na20.2CaO.5B2O3.16H2O. Disadvantages of these naturally occurring calcium borate minerals include the presence of mineral impurities,the need for fine grinding when very fine particle sizes are needed, such as to achieve fine dispersions in polymeric resins for fire retardant applications, and in the case of ulexite, the presence of sodium and substantial water content. The borate contents of colemanite and ulexite are about 51% B2O3 and 43% B2O3, respectively. 1A Known synthetic calcium borates include the tetrahydrate and hexahydrate forms of calcium metaborate, CaO.B2O3.4H2O and CaO.B2O3.6H2O, which contain about 35% and 30% B2O3, respectively. Although these synthetic compositions have the potential of being of higher purity, since they lack the mineral impurities found in naturally occurring colemanite and ulexite, they are relatively low in borate content by comparison. Synthetic gowerite, consisting of calcium hexaborate pentahydrate (CaO.3B2O3.5H2O), contains about 59% B2O3/ which is substantially higher in borate content than the calcium metaborate compositions. However, gowerite tends to. 1B crystallize in a coarse, granular form, thus requiring grinding to achieve the fine particle sizes needed for many applications. Calcium hexaborate tetrahydrate, which has the formula CaO 3B2O34H2O, has the same ratio of boron to calcium as synthetic gowerite, but contains less water. At 62% B2O3 it has a higher borate content than gowerite, the calcium metaborates and (he minerals colemanite and ulexite. It is known to occur in nature as the mineral nobleite, although it is not found in commercially exploitable quantities. Various methods for producing synthetic forms of the minerals nobleite and gowerite are known. For example synthetic nobleite can be produced by the hydrothermal treatment of meyerhofferite (2CaO 3B2O37H2O) in boric acid solution for 8 days at 85°C. See U.S. Patent No. 3,337,292. Ditte, Acad. Sci. Paris Copies rendus, 77, 783-785 (1873), described the formation of lime borates by reaction of Iceland spar (calcite) with a saturated boric acid solution. The resultant salt was described as small needles of "a hydrated lime borate" .which contains "3BoO2, CaO and 4HO, which can be written as (2BoO2 CaO HO)(BoO2, 3HO)." Subsequently, Erd, McAllister and Vlisidis, American Mineralogist, 46 , 560-571 (1961), suggested the Ditte product was nobleite. Erd et al also synthesized nobleite by stirring CaO and boric acid in water for 30 hours at 48°C. and then holding the product at 68°C for 10 days. Kemp, The Chemistry of Borates, Part I, page 70 (1956), reported that an aqueous solution of boric acid kept at 40°C for 3 weeks deposits a mixture of CaO-3B2O3 4H2O and 2CaO-3B2O39H2O. Kemp also reported that CaO.3B2O38H2O decomposes to form CaO.3B2O3.4H2O. According to Supplement to Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Volume V. Part A: Boron-Oxygen Compounds, pages 550-551 (1980), CaO-3B2O3.4H2O occurs as a solid phase in the systems Na2O-CaO-B2O3-H2O and CaO-NaCl-B2O3-H2O at 25°C and pH 5.5-6.5. Hydrothermal treatment of meyerhofferite in boric acid solution at 85-250°C produced crystals of both the tetrahydrate and pentahydrate together with gineritc (2CaO-7B2O3-8H2O). Mellor further reported that nobleite is a stable phase in the CaO-B2O3-H2O system at 25°C and at 45°C and is also formed from an aqueous mixture of lime (CaO 2 and boric acid at 60°C. Also, Mellor reports on page 551 that CaO.3B2O3.5H2O (gowerite) is formed from lime and boric acid in aqueous media at 100°C. Lehmann et al, Zeitshrift fur Anorqanische und Allgemeine Chemie, Volume 346, pages 12-20, (1966), teach that the formation of gowerite from CaO, H3BO3 and water is favored by a relatively high temperature (100°C), and higher CaO concentration, whereas nobleite formation is predominantly formed in more dilute solutions with lower CaO content and at lower temperature (60°C}. In contrast to the teachings of the art, it has been discovered that the reaction of boric acid and lime in an aqueous mixture at high temperature will produce nobleite instead of gowerite provided that the reactants, and boric acid in particular, are present at sufficiently high concentration in the reaction slurry, and the molar ratio of lime to boric acid ( CaO:H3BO3) added is within specific limits. SUMMARY OF THE INVENTION Accordingly, the present invention provides, a method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. The method of this 3 invention results in a rapid reaction rate, high product yield and favorable product characteristics such as fine particle size distribution, rapid filtration and good flow and bulk handling properties. Further, there is provided a novel crystalline calcium hexaborate tetrahydrate composition having a distinctive crystal habit. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate produced at low temperature (approximately 22°C). Figure 2 is a photomicrograph of calcium hexaborate tetrahydrate produced at high temperature (approximately 95°C) by the improved method of this invention. 3A DETAILED DESCRIPTION OF THE INVENTION The method of this invention comprises reacting high concentrations of boric acid and lime in water at high temperature, such as in the range of 85° to 105°C, to form crystalline calcium hexaborate tetrahydrate. The preferred reaction temperatures are near the boiling point of the slurry, and preferably in the range of from 95° to 101°C. The concentration of the reactants is important to the production of calcium hexaborate tetrahydrate according to the process of this invention. In particular, a high ratio of boric acid to water in the reaction mixture will produce nobleite rather than gowerite at the high temperature conditions of this invention. Boric acid, which is highly soluble in water at high temperatures, should be added in quantities which are substantially greater than the solubility limit, in order to produce nobleite at these temperatures. The molar ratio of boric acid to water (H3BO3:H2O) in the starting mixture should be greater than 0.25:1, such as in the range of from 0.25 to 0.5:1 and preferably in the range of from 0.3 to 0.45:1. This is substantially higher than the solubility limit of boric acid at temperatures of 80° to 100°C which ranges from 0.07 to 0.11 moles of H3BO3 per mole of water. The molar ratio of lime to boric acid (CaO:H3BO3) in the starting mixture is in the range of from 0.05 to 0.15:1, and preferably 0.1 to 0.13:1. As used herein, lime includes calcium oxide such as burnt lime and quick lime, calcium hydroxide such 4 as hydrated lime, slaked lime and lime hydrate, and calcium carbonate, including calcite and limestone. It appears to be beneficial to have a high concentration of undissolved solids in the reaction mixture such as would provide at least 25% by weight undissolved solids in the final product slurry and preferably at least 30% by weight. If the solids concentration is too low, this may lead to the formation of gowerite instead of the desired nobleite. The method of this invention may be used in producing calcium hexaborate tetrahydrate in a batch, continuous or semi-continuous process. In a batch process, the boric acid and lime may be combined in water and heated at the required temperature range to initiate the reaction. Alternatively, a mother liquor recycled from previous runs or freshly prepared mother liquor may be used as the reaction media. In a continuous or semi-continuous process, the desired product is continuously removed from the reaction vessel and the remaining mother liquor is recycled by adding additional boric acid and lime and heating the reactants at the reaction temperatures. The reaction is essentially complete within one hour, although small improvements in the product B2O3 analysis may be attained by heating the reaction mixture for up to about 4 hours. When calcium oxide or calcium hydroxide are used as reactants, the reaction occurs as a noticeable exotherm within about 15 to 25 minutes, during which time the majority of the starting materials are converted to the desired product. 5 Preferably, the reaction mixture is agitated, such as by stirring, during the reaction period. After the reaction is completed, the nobleite product is separated from the hot mother liquor such as by filtration or centrifugation or other suitable mean of solid-liquid separation. The wet solids may be washed, such as with water, to remove any entrained mother liquor, and subsequently dried to provide a crystalline calcium hexaborate tetrahydrate. If a product with higher B2O3 content is desired, the calcium borate tetrahydrate can be dehydrated by heating at a temperature of at least 325°C, preferably in the range of 450°C to 550°C to produce a novel amorphous, anhydrous calcium hexaborate, CaO.3B2O3, which contains about 79% B2O3. The production of nobleite by the method of this invention has a number of advantages over the previously known methods. The reaction time is substantially reduced from as long as several weeks at low temperatures, to as short as less than an hour at the temperatures of this invention. Also, the high concentration of reactants provides a higher yield of product per unit volume of the reaction mixture. Substantially pure nobleite can be produced under the preferred conditions of this invention, while under the conditions outside of this region, nobleite is partially or totally replaced by the formation of gowerite during the reaction. It has been further discovered that the product of the method of this invention has a unique crystal habit not found in nobleite formed at low concentrations and temeratures.Nobleite, as found in nature and as synthesized at room temperature, is 5A distinguished by a platy morphology. Although it is monoclinic, the platelets have a pseudohexagonal form. The platelets are commonly found in aggregates that arc stacked or arranged sub parallel to the 100 plane. The large thin crystals have been found in sizes up to a centimeter in length and have a hexagonal aspect, while the smaller crystals are more rhombic shaped and may form drusy coatings. See also Erd, McAllister and Vlisidis, American Mineralogist-46 , 560-571 (1961). Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate crystals formed at room temperature, obtained by scanning electron microscopy at a magnification of 5500x. Although the crystalline form of the calcium hexaborate tetrahydrate produced by the process of this invention is also composed of platelets, the crystal habit or arrangement of these platelets is very distinctive and unique. Individual thin platelets, are arranged in nearly spherical radial clusters. Figure 2 is a photomicrograph of the crystalline product of this invention obtained by scanning electron microscopy at a magnification of 3000x and shows the unique crystal habit of the product produced according to the method of this invention. Particle size analysis of the crystalline product of this invention indicates a relatively small mean particle size distribution, typically of about 90% less than 75 micrometers in diameter. This small mean particle diameter is advantageous for many applications where a fine dispersion of the solids is required, such as for fire retardant applications in polymeric resins. Yet it is easy to filter, facilitating the separation of the solid product from the mother liquor, which then can be recycled back into the process. Further, the spherical shape of the crystal habit results in excellent handling and flow properties of the dried solids despite the extremely fine particle size distribution. It was also found that the crystalline product docs not have a significant tendency toward caking. The product dehydrates in three distinct stages, losing water at about 91°, 177° and 312°C. It was found to melt at a temperature of about 927°C. The anhydrous calcium borate product produced by dehydration of the product is less hygroscopic than most dehydrated metal borate compounds. EXAMPLES The following examples illustrate the novel methods and compositions of this invention. EXAMPLE 1 Boric acid (1,448 grams) and 31.7 grams of calcium hydroxide (Ca(OH)2) were combined in 5.00 liters of deionized water in a stirred flask to make up a batch of synthetic mother liquor. This mixture was stirred and heated to 95°C and two batches, each of 2,089 grams of boric acid and 417 grams of calcium hydroxide, were added over a period of about six minutes to give a final reaction slurry (33% undissolved solids) containing a lime to boric acid (CaO:H3BO3) molar ratio of 0.13:1 and a boric acid to water (H3BO3H2O) molar ratio of 0.33:1. There was a slight drop in temperature after the addition of each batch, followed by a final exotherm which raised the temperature to boiling (1010C). The resultant reaction mixture was stirred at about 95° to 100°C for 3 hours and samples of the solid product and liquor were taken for analysis after each hour. The results are shown in Table 1. The reaction slurry was diluted with warm water and filtered to give a filter cake of product which was washed with cold water to remove adhering liquor. The resultant crystalline product was dried and determined to be substantially pure nobleite by X-ray diffraction analysis, titration and thermogravimetric analysis (TGA). Figure 2 is a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 3000x. 7 TABLE 1 Reaction Time Weight % B2O3 in solids Weight % CaO in solids Molar Ratio CaO/B2O3 in solids Weight % B2O3 in liquor Weight %CaO in liquor 1 Hour 61.69 15.90 0.320 10.82 0.29 2 Hours 61.84 15.94 0.320 9.08 0.24 3 Hours 62.11 15.96 0.319 8.90 0.24 Theoretical 62.00 16.62 0.333 The crystalline nobleite product had a very fine particle size distribution with more than 90% by weight passing a 200 mesh (74 micrometer) lest sieve and 70% by weight passing a 325 mesh (45 micrometer) test sieve. The particle size distribution is shown in Table 2. TABLE 2 U.S. Mesh Opening Size (micrometers) Weight % Retained Cum. Weight % Passing 80 180 0.93 99.07 100 150 0.19 98.88 140 105 1.10 97.78 200 75 3.82 93.96 325 45 22.84 71.12 EXAMPLES 2-13 Synthetic mother liquors were prepared by combining boric acid, lime (in the form of calcium hydroxide) and deionized water in a stirred flask. These mixtures were heated to a temperature of 95°C and additional boric acid and lime were added to the reaction mixtures in up to four batches. The reaction mixtures were stirred at 95°C for 3 to 4 hours following the final addition of boric acid and lime. At the end of the reaction time the slurry was filtered and washed to recover the solid product. The 8 molar ratios of reactants, namely boric acid:water (BA/Water) and lime:boric acid (CaO/BA), are shown in Table 3 below along with the product B2O3 analyses and mineralogical results. The mineralogy of the crystalline product was generally determined by X-ray diffraction and microscopy. The nobleite/gowerite ratio was estimated for some of the products from X-ray diffraction data. TABLE 3 Example No. Mole Ratios of Reactants Product Analyses BA/Water CaO/BA %B2O3 Mineralopv 2 0.43 0-09 63.3 Nobleilc 3 0.33 0.13 62 Nobleitc 4 0.30 0.14 62.2 Nablcitc + Gowcritc (92/8)' 5 0.30 0.14 61.4 Nobleite 6 0.23 0.11 62.1 Nobleitc + Gowerite (94/6) 7 0.20 0.15 59.1 Nobicite + Gowcritc 8 0.17 0.09 59.1 G owe rite 9 0.12 0.12 59.4 Nobleilc + Gowcrite 10 0.12 0 12 58.9 Goweritc 11 0.10 0.14 58.2 Gowcritc 12 0.06 0.09 58.3 Gowcritc 13 0.04 0.16 41.3 Sibirskite As shown in the Examples of Table 3, substantially pure nobleitc, having a high B2O3 analysis, is produced when the boric acid/water molar ratio is above about 0.25 and the lime/boric acid molar ratio is less than about 0.15. When the boric acid/water ratio is reduced and/or the lime/boric acid ratio is increased, the boric oxide content of the product decreases and the nobleite product is replaced by gowerite. 9 EXAMPLES 14-17 The following reactions were carried out using calcium carbonate as the source of lime. Example 14 was carried out by a procedure similar to Example I above, wherein a synthetic mother liquor was made by mixing boric acid, calcium carbonate and deionized water in a stirred flask and after heating to 95°C additional boric acid and calcium carbonate were added. In examples 15-17 deioniz.ed water and calcium carbonate were combined and, after heating to 95°C, boric acid v/as added. Substantial foaming of the reaction mixtures was observed as a result of CO2 gas released by the reaction of the boric acid and calcium carbonate. This resulted in a drop in temperature from 95°C.to about 63-66°C. The reaction mixtures were reheated to 95°C within 15 to 20 minutes. The reaction mixtures were stirred continuously and the temperatures controlled at about 95°C for about 3 to 3.5 hours after the final reagent additions. At the end of the reaction period the slurries were filtered and the solids washed to remove entrained solution. The mole ratios of the reactants and the chemical and mineralogical analyses of the solid products are summarized in Table 4. TABLE 4 Example No. Mole Ratio of Reactants Product Analyses BA/water CaO/BA %B2O3 Mineralogy 14 0 33 0.13 62 2 Nobleite 15 0.33 0.16 60 5 Nobleite 16 0.33 0.13 62.3 Nobleite 17 0.24 0.21 55.6 Nobleite+Calcite 10 EXAMPLE 18 (Comparative) Boric acid (40 grams) and 8 grams of hydrated lime were added to 200 grams of water to give a reaction mixture containing a boric acid to water molar ratio of 0.06:1 and a lime to boric acid molar ratio of 0.17:1. The mixture was stirred initially and then allowed to sit at room temperature (approximately 22°C) over a seven day period. The resulting solid product was recovered and determined to be nobleite by X-ray diffraction analysis. Figure 1, a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 5500x, shows the product as consisting of stacked aggregates of hexagonal platelets. The above example shows that while synthetic nobleite can be formed at low ratios of boric acid to water at low temperatures, long reaction times are required. Further, the crystal habit of the resultant product is more like that described for natural nobleite than the spherical radial clusters obtained by the process of the present invention as illustrated in Example 1. EXAMPLE 19 A 5.9 kilogram sample of synthetic nobleite containing product from Examples 1, 3 and 5 was distributed into several stainless steel pans and heated in an oven at 500°C for about 17 hours. The residual water content of the dehydrated product was determined to be less than 0.5% by weight by thermogravimetric analysis. This product was observed to have the same free-flowing properties characteristic of the nobleite product prior to dehydration. This is attributed to the particle form or habit which was confirmed by scanning electron microscopy to resemble the crystal habit of the hydrate prior to dehydration except that there are generally some openings of the radial platelets making up the spherical radial clusters. Despite this characteristic particle form or habit which is residual from the crystalline form existing prior to dehydration. X-ray diffraction analysis indicated that the dehydrated product is essentially amorphous. 11 Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims. 12 WE CLAIM: 1. A method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. 2. A method as claimed in claim 1, wherein said molar ratio of boric acid to water is in the range of from 0.3 to 0.45:1. 3. A method as claimed in claim 1, wherein said molar ratio of lime to boric acid is in the range of from 0.1 to 0.13:1. 4. A method as claimed in claim 1, wherein said temperature is in the range of from 95° to 101°C. 5. A method as claimed in claim 1, wherein source of said lime is calcium carbonate. 6. A method as claimed in claim 1, wherein said lime is hydrated lime. 7. A method as claimed in claim 1, wherein said crystalline calcium hexaborate tetrahydrate is dehydrated by heating at a temperature above 325°C. 8. A method as claimed in claim 7, wherein said temperature is in the range of from 450°C to 550°C. 13 14 9. A method for producing crystalline calcium hexaborate tetrahydrate, substantially as herein described, particularly with reference to the foregoing examples and the accompanying drawings. An improved method is provided for producing crystalline calcium hexaborate tetrahydrate, synthetic nobleite, by the reaction of boric acid and lime in an aqueous slurry. Reaction conditions include boric acid to water molar ratios of greater than 0.25:1, lime to boric acid molar ratios in the range of 0.05-0.15:1 and temperatures in the range of 85°-105°C. A novel crystalline product is produced having a unique crystal habit resulting in improved physical properties. Dehydration of this product produced a novel amorphous, anhydrous product having similar crystal habit and physical properties.

Full Text

This invention in general relates to a method for producing crystalline calcium hexaborate tetrahydrate and more particularly to an improved method for producing crystalline calcium hexaborate tetrahydrate, a synthetic form of the mineral nobleite, by the reaction of boric acid and lime in an aqueous slurry.
BACKGROUND OF THE INVENTION
Calcium borates have many industrial applications. They are used as a source of boron in fiberglass manufacture when the desired glass composition requires that sodium addition be limited, such as for textile fiberglass. They are also useful as fire retardant agents in such materials as plastics and rubber polymers, cellulosics, resins and oils, etc. Further, they are useful in the manufacture of steel and ceramics.
Many different calcium borate compositions are known, both natural and synthetic; they are most commonly formed as hydrated compounds. Naturally occurring calcium borates which are commonly used commercially include colemanite, which has the chemical composition 2CaO.3B2O3.5H2O, and ulexite, a mixed sodium-calcium borate of the composition Na20.2CaO.5B2O3.16H2O. Disadvantages of these naturally occurring calcium borate minerals include the presence of mineral impurities,the need for fine grinding when very fine particle sizes are needed, such as to achieve fine dispersions in polymeric resins for fire retardant applications, and in the case of ulexite, the presence of sodium and substantial water content. The borate contents of colemanite and ulexite are about 51% B2O3 and 43% B2O3, respectively.
1A

Known synthetic calcium borates include the tetrahydrate and hexahydrate forms of calcium metaborate, CaO.B2O3.4H2O and CaO.B2O3.6H2O, which contain about 35% and 30% B2O3, respectively. Although these synthetic compositions have the potential of being of higher purity, since they lack the mineral impurities found in naturally occurring colemanite and ulexite, they are relatively low in borate content by comparison. Synthetic gowerite, consisting of calcium hexaborate pentahydrate (CaO.3B2O3.5H2O), contains about 59% B2O3/ which is substantially higher in borate content than the calcium metaborate compositions. However, gowerite tends to.
1B

crystallize in a coarse, granular form, thus requiring grinding to achieve the fine particle sizes needed for many applications.
Calcium hexaborate tetrahydrate, which has the formula CaO 3B2O34H2O, has the same ratio of boron to calcium as synthetic gowerite, but contains less water. At 62% B2O3 it has a higher borate content than gowerite, the calcium metaborates and (he minerals colemanite and ulexite. It is known to occur in nature as the mineral nobleite, although it is not found in commercially exploitable quantities.
Various methods for producing synthetic forms of the minerals nobleite and gowerite are known. For example synthetic nobleite can be produced by the hydrothermal treatment of meyerhofferite (2CaO 3B2O37H2O) in boric acid solution for 8 days at 85°C. See U.S. Patent No. 3,337,292.
Ditte, Acad. Sci. Paris Copies rendus, 77, 783-785 (1873), described the formation of lime borates by reaction of Iceland spar (calcite) with a saturated boric acid solution. The resultant salt was described as small needles of "a hydrated lime borate" .which contains "3BoO2, CaO and 4HO, which can be written as (2BoO2 CaO HO)(BoO2, 3HO)." Subsequently, Erd, McAllister and Vlisidis, American Mineralogist, 46 , 560-571 (1961), suggested the Ditte product was nobleite. Erd et al also synthesized nobleite by stirring CaO and boric acid in water for 30 hours at 48°C. and then holding the product at 68°C for 10 days.
Kemp, The Chemistry of Borates, Part I, page 70 (1956), reported that an aqueous solution of boric acid kept at 40°C for 3 weeks deposits a mixture of CaO-3B2O3 4H2O and 2CaO-3B2O39H2O. Kemp also reported that CaO.3B2O38H2O decomposes to form CaO.3B2O3.4H2O. According to Supplement to Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Volume V. Part A: Boron-Oxygen Compounds, pages 550-551 (1980), CaO-3B2O3.4H2O occurs as a solid phase in the systems Na2O-CaO-B2O3-H2O and CaO-NaCl-B2O3-H2O at 25°C and pH 5.5-6.5. Hydrothermal treatment of meyerhofferite in boric acid solution at 85-250°C produced crystals of both the tetrahydrate and pentahydrate together with gineritc (2CaO-7B2O3-8H2O).
Mellor further reported that nobleite is a stable phase in the CaO-B2O3-H2O system at 25°C and at 45°C and is also formed from an aqueous mixture of lime (CaO
2

and boric acid at 60°C. Also, Mellor reports on page 551 that CaO.3B2O3.5H2O (gowerite) is formed from lime and boric acid in aqueous media at 100°C.
Lehmann et al, Zeitshrift fur Anorqanische und Allgemeine Chemie, Volume 346, pages 12-20, (1966), teach that the formation of gowerite from CaO, H3BO3 and water is favored by a relatively high temperature (100°C), and higher CaO concentration, whereas nobleite formation is predominantly formed in more dilute solutions with lower CaO content and at lower temperature (60°C}.
In contrast to the teachings of the art, it has been discovered that the reaction of boric acid and lime in an aqueous mixture at high temperature will produce nobleite instead of gowerite provided that the reactants, and boric acid in particular, are present at sufficiently high concentration in the reaction slurry, and the molar ratio of lime to boric acid ( CaO:H3BO3) added is within specific limits.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides, a method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. The method of this
3

invention results in a rapid reaction rate, high product yield and favorable product characteristics such as fine particle size distribution, rapid filtration and good flow and bulk handling properties. Further, there is provided a novel crystalline calcium hexaborate tetrahydrate composition having a distinctive crystal habit.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate produced at low temperature (approximately 22°C). Figure 2 is a photomicrograph of calcium hexaborate tetrahydrate produced at high temperature (approximately 95°C) by the improved method of this invention.
3A

DETAILED DESCRIPTION OF THE INVENTION
The method of this invention comprises reacting high concentrations of boric acid and lime in water at high temperature, such as in the range of 85° to 105°C, to form crystalline calcium hexaborate tetrahydrate. The preferred reaction temperatures are near the boiling point of the slurry, and preferably in the range of from 95° to 101°C.
The concentration of the reactants is important to the production of calcium hexaborate tetrahydrate according to the process of this invention. In particular, a high ratio of boric acid to water in the reaction mixture will produce nobleite rather than gowerite at the high temperature conditions of this invention. Boric acid, which is highly soluble in water at high temperatures, should be added in quantities which are substantially greater than the solubility limit, in order to produce nobleite at these temperatures. The molar ratio of boric acid to water (H3BO3:H2O) in the starting mixture should be greater than 0.25:1, such as in the range of from 0.25 to 0.5:1 and preferably in the range of from 0.3 to 0.45:1. This is substantially higher than the solubility limit of boric acid at temperatures of 80° to 100°C which ranges from 0.07 to 0.11 moles of H3BO3 per mole of water.
The molar ratio of lime to boric acid (CaO:H3BO3) in the starting mixture is in the range of from 0.05 to 0.15:1, and preferably 0.1 to 0.13:1. As used herein, lime includes calcium oxide such as burnt lime and quick lime, calcium hydroxide such
4

as hydrated lime, slaked lime and lime hydrate, and calcium carbonate, including calcite and limestone.
It appears to be beneficial to have a high concentration of undissolved solids in the reaction mixture such as would provide at least 25% by weight undissolved solids in the final product slurry and preferably at least 30% by weight. If the solids concentration is too low, this may lead to the formation of gowerite instead of the desired nobleite.
The method of this invention may be used in producing calcium hexaborate tetrahydrate in a batch, continuous or semi-continuous process. In a batch process, the boric acid and lime may be combined in water and heated at the required temperature range to initiate the reaction. Alternatively, a mother liquor recycled from previous runs or freshly prepared mother liquor may be used as the reaction media. In a continuous or semi-continuous process, the desired product is continuously removed from the reaction vessel and the remaining mother liquor is recycled by adding additional boric acid and lime and heating the reactants at the reaction temperatures.
The reaction is essentially complete within one hour, although small improvements in the product B2O3 analysis may be attained by heating the reaction mixture for up to about 4 hours. When calcium oxide or calcium hydroxide are used as reactants, the reaction occurs as a noticeable exotherm within about 15 to 25 minutes, during which time the majority of the starting materials are converted to the desired product.
5

Preferably, the reaction mixture is agitated, such as by stirring, during the reaction period. After the reaction is completed, the nobleite product is separated from the hot mother liquor such as by filtration or centrifugation or other suitable mean of solid-liquid separation. The wet solids may be washed, such as with water, to remove any entrained mother liquor, and subsequently dried to provide a crystalline calcium hexaborate tetrahydrate.
If a product with higher B2O3 content is desired, the calcium borate tetrahydrate can be dehydrated by heating at a temperature of at least 325°C, preferably in the range of 450°C to 550°C to produce a novel amorphous, anhydrous calcium hexaborate, CaO.3B2O3, which contains about 79% B2O3.
The production of nobleite by the method of this invention has a number of advantages over the previously known methods. The reaction time is substantially reduced from as long as several weeks at low temperatures, to as short as less than an hour at the temperatures of this invention. Also, the high concentration of reactants provides a higher yield of product per unit volume of the reaction mixture. Substantially pure nobleite can be produced under the preferred conditions of this invention, while under the conditions outside of this region, nobleite is partially or totally replaced by the formation of gowerite during the reaction.
It has been further discovered that the product of the method of this invention has a unique crystal habit not found in nobleite formed at low concentrations and temeratures.Nobleite, as
found in nature and as synthesized at room temperature, is
5A

distinguished by a platy morphology. Although it is monoclinic, the platelets have a pseudohexagonal form. The platelets are commonly found in aggregates that arc stacked or arranged sub parallel to the 100 plane. The large thin crystals have been found in sizes up to a centimeter in length and have a hexagonal aspect, while the smaller crystals are more rhombic shaped and may form drusy coatings. See also Erd, McAllister and Vlisidis, American Mineralogist-46 , 560-571 (1961). Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate crystals formed at room temperature, obtained by scanning electron microscopy at a magnification of 5500x.
Although the crystalline form of the calcium hexaborate tetrahydrate produced by the process of this invention is also composed of platelets, the crystal habit or arrangement of these platelets is very distinctive and unique. Individual thin platelets, are arranged in nearly spherical radial clusters. Figure 2 is a photomicrograph of the crystalline product of this invention obtained by scanning electron microscopy at a magnification of 3000x and shows the unique crystal habit of the product produced according to the method of this invention.
Particle size analysis of the crystalline product of this invention indicates a relatively small mean particle size distribution, typically of about 90% less than 75 micrometers in diameter. This small mean particle diameter is advantageous for many applications where a fine dispersion of the solids is required, such as for fire retardant applications in polymeric resins. Yet it is easy to filter, facilitating the separation of the solid product from the mother liquor, which then can be recycled back into the process. Further, the spherical shape of the crystal habit results in excellent handling and flow properties of the dried solids despite the extremely fine particle size distribution. It was also found that the crystalline product docs not have a significant tendency toward caking.
The product dehydrates in three distinct stages, losing water at about 91°, 177° and 312°C. It was found to melt at a temperature of about 927°C. The anhydrous calcium borate product produced by dehydration of the product is less hygroscopic than most dehydrated metal borate compounds.
EXAMPLES

The following examples illustrate the novel methods and compositions of this invention.
EXAMPLE 1
Boric acid (1,448 grams) and 31.7 grams of calcium hydroxide (Ca(OH)2) were combined in 5.00 liters of deionized water in a stirred flask to make up a batch of synthetic mother liquor. This mixture was stirred and heated to 95°C and two batches, each of 2,089 grams of boric acid and 417 grams of calcium hydroxide, were added over a period of about six minutes to give a final reaction slurry (33% undissolved solids) containing a lime to boric acid (CaO:H3BO3) molar ratio of 0.13:1 and a boric acid to water (H3BO3H2O) molar ratio of 0.33:1. There was a slight drop in temperature after the addition of each batch, followed by a final exotherm which raised the temperature to boiling (1010C). The resultant reaction mixture was stirred at about 95° to 100°C for 3 hours and samples of the solid product and liquor were taken for analysis after each hour. The results are shown in Table 1. The reaction slurry was diluted with warm water and filtered to give a filter cake of product which was washed with cold water to remove adhering liquor. The resultant crystalline product was dried and determined to be substantially pure nobleite by X-ray diffraction analysis, titration and thermogravimetric analysis (TGA).
Figure 2 is a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 3000x.

7

TABLE 1

Reaction Time
Weight % B2O3 in solids
Weight % CaO in solids
Molar Ratio CaO/B2O3 in solids
Weight % B2O3 in liquor
Weight %CaO in liquor
1 Hour
61.69
15.90
0.320
10.82
0.29
2 Hours
61.84
15.94
0.320
9.08
0.24
3 Hours
62.11
15.96
0.319
8.90
0.24
Theoretical
62.00
16.62
0.333

The crystalline nobleite product had a very fine particle size distribution with more than 90% by weight passing a 200 mesh (74 micrometer) lest sieve and 70% by weight passing a 325 mesh (45 micrometer) test sieve. The particle size distribution is shown in Table 2.
TABLE 2

U.S. Mesh
Opening Size (micrometers)
Weight % Retained
Cum. Weight
% Passing
80
180
0.93
99.07
100
150
0.19
98.88
140
105
1.10
97.78
200
75
3.82
93.96
325
45
22.84
71.12
EXAMPLES 2-13
Synthetic mother liquors were prepared by combining boric acid, lime (in the form of calcium hydroxide) and deionized water in a stirred flask. These mixtures were heated to a temperature of 95°C and additional boric acid and lime were added to the reaction mixtures in up to four batches. The reaction mixtures were stirred at 95°C for 3 to 4 hours following the final addition of boric acid and lime. At the end of the reaction time the slurry was filtered and washed to recover the solid product. The
8
molar ratios of reactants, namely boric acid:water (BA/Water) and lime:boric acid (CaO/BA), are shown in Table 3 below along with the product B2O3 analyses and mineralogical results. The mineralogy of the crystalline product was generally determined by X-ray diffraction and microscopy. The nobleite/gowerite ratio was estimated for some of the products from X-ray diffraction data.
TABLE 3

Example No.
Mole Ratios of Reactants

Product Analyses

BA/Water
CaO/BA
%B2O3
Mineralopv
2
0.43
0-09
63.3
Nobleilc
3
0.33
0.13
62
Nobleitc
4
0.30
0.14
62.2
Nablcitc + Gowcritc (92/8)'
5
0.30
0.14
61.4
Nobleite
6
0.23
0.11
62.1
Nobleitc + Gowerite (94/6)
7
0.20
0.15
59.1
Nobicite + Gowcritc
8
0.17
0.09
59.1
G owe rite
9
0.12
0.12
59.4
Nobleilc + Gowcrite
10
0.12
0 12
58.9
Goweritc
11
0.10
0.14
58.2
Gowcritc
12
0.06
0.09
58.3
Gowcritc
13
0.04
0.16
41.3
Sibirskite
As shown in the Examples of Table 3, substantially pure nobleitc, having a high B2O3 analysis, is produced when the boric acid/water molar ratio is above about 0.25 and the lime/boric acid molar ratio is less than about 0.15. When the boric acid/water ratio is reduced and/or the lime/boric acid ratio is increased, the boric oxide content of the product decreases and the nobleite product is replaced by gowerite.
9
EXAMPLES 14-17
The following reactions were carried out using calcium carbonate as the source of lime. Example 14 was carried out by a procedure similar to Example I above, wherein a synthetic mother liquor was made by mixing boric acid, calcium carbonate and deionized water in a stirred flask and after heating to 95°C additional boric acid and calcium carbonate were added.
In examples 15-17 deioniz.ed water and calcium carbonate were combined and, after heating to 95°C, boric acid v/as added. Substantial foaming of the reaction mixtures was observed as a result of CO2 gas released by the reaction of the boric acid and calcium carbonate. This resulted in a drop in temperature from 95°C.to about 63-66°C. The reaction mixtures were reheated to 95°C within 15 to 20 minutes.
The reaction mixtures were stirred continuously and the temperatures controlled at about 95°C for about 3 to 3.5 hours after the final reagent additions. At the end of the reaction period the slurries were filtered and the solids washed to remove entrained solution. The mole ratios of the reactants and the chemical and mineralogical analyses of the solid products are summarized in Table 4.
TABLE 4
Example No. Mole Ratio of Reactants Product Analyses
BA/water CaO/BA %B2O3 Mineralogy
14 0 33 0.13 62 2 Nobleite
15 0.33 0.16 60 5 Nobleite
16 0.33 0.13 62.3 Nobleite
17 0.24 0.21 55.6 Nobleite+Calcite
10

EXAMPLE 18
(Comparative)
Boric acid (40 grams) and 8 grams of hydrated lime were added to 200 grams of water to give a reaction mixture containing a boric acid to water molar ratio of 0.06:1 and a lime to boric acid molar ratio of 0.17:1. The mixture was stirred initially and then allowed to sit at room temperature (approximately 22°C) over a seven day period. The resulting solid product was recovered and determined to be nobleite by X-ray diffraction analysis. Figure 1, a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 5500x, shows the product as consisting of stacked aggregates of hexagonal platelets.
The above example shows that while synthetic nobleite can be formed at low
ratios of boric acid to water at low temperatures, long reaction times are required.
Further, the crystal habit of the resultant product is more like that described for natural
nobleite than the spherical radial clusters obtained by the process of the present
invention as illustrated in Example 1.
EXAMPLE 19
A 5.9 kilogram sample of synthetic nobleite containing product from Examples 1, 3 and 5 was distributed into several stainless steel pans and heated in an oven at 500°C for about 17 hours. The residual water content of the dehydrated product was determined to be less than 0.5% by weight by thermogravimetric analysis. This product was observed to have the same free-flowing properties characteristic of the nobleite product prior to dehydration. This is attributed to the particle form or habit which was confirmed by scanning electron microscopy to resemble the crystal habit of the hydrate prior to dehydration except that there are generally some openings of the radial platelets making up the spherical radial clusters. Despite this characteristic particle form or habit which is residual from the crystalline form existing prior to dehydration. X-ray diffraction analysis indicated that the dehydrated product is essentially amorphous.
11

Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.
12

WE CLAIM:
1. A method for producing crystalline calcium
hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry.
2. A method as claimed in claim 1, wherein said molar
ratio of boric acid to water is in the range of from 0.3 to
0.45:1.
3. A method as claimed in claim 1, wherein said molar
ratio of lime to boric acid is in the range of from 0.1 to 0.13:1.
4. A method as claimed in claim 1, wherein said
temperature is in the range of from 95° to 101°C.
5. A method as claimed in claim 1, wherein source of said
lime is calcium carbonate.
6. A method as claimed in claim 1, wherein said lime is
hydrated lime.
7. A method as claimed in claim 1, wherein said
crystalline calcium hexaborate tetrahydrate is dehydrated by
heating at a temperature above 325°C.
8. A method as claimed in claim 7, wherein said
temperature is in the range of from 450°C to 550°C.
13

14
9. A method for producing crystalline calcium hexaborate tetrahydrate, substantially as herein described, particularly with reference to the foregoing examples and the accompanying drawings.

This invention in general relates to a method for producing crystalline calcium hexaborate tetrahydrate and more particularly to an improved method for producing crystalline calcium hexaborate tetrahydrate, a synthetic form of the mineral nobleite, by the reaction of boric acid and lime in an aqueous slurry.
BACKGROUND OF THE INVENTION
Calcium borates have many industrial applications. They are used as a source of boron in fiberglass manufacture when the desired glass composition requires that sodium addition be limited, such as for textile fiberglass. They are also useful as fire retardant agents in such materials as plastics and rubber polymers, cellulosics, resins and oils, etc. Further, they are useful in the manufacture of steel and ceramics.
Many different calcium borate compositions are known, both natural and synthetic; they are most commonly formed as hydrated compounds. Naturally occurring calcium borates which are commonly used commercially include colemanite, which has the chemical composition 2CaO.3B2O3.5H2O, and ulexite, a mixed sodium-calcium borate of the composition Na20.2CaO.5B2O3.16H2O. Disadvantages of these naturally occurring calcium borate minerals include the presence of mineral impurities,the need for fine grinding when very fine particle sizes are needed, such as to achieve fine dispersions in polymeric resins for fire retardant applications, and in the case of ulexite, the presence of sodium and substantial water content. The borate contents of colemanite and ulexite are about 51% B2O3 and 43% B2O3, respectively.
1A

Known synthetic calcium borates include the tetrahydrate and hexahydrate forms of calcium metaborate, CaO.B2O3.4H2O and CaO.B2O3.6H2O, which contain about 35% and 30% B2O3, respectively. Although these synthetic compositions have the potential of being of higher purity, since they lack the mineral impurities found in naturally occurring colemanite and ulexite, they are relatively low in borate content by comparison. Synthetic gowerite, consisting of calcium hexaborate pentahydrate (CaO.3B2O3.5H2O), contains about 59% B2O3/ which is substantially higher in borate content than the calcium metaborate compositions. However, gowerite tends to.
1B

crystallize in a coarse, granular form, thus requiring grinding to achieve the fine particle sizes needed for many applications.
Calcium hexaborate tetrahydrate, which has the formula CaO 3B2O34H2O, has the same ratio of boron to calcium as synthetic gowerite, but contains less water. At 62% B2O3 it has a higher borate content than gowerite, the calcium metaborates and (he minerals colemanite and ulexite. It is known to occur in nature as the mineral nobleite, although it is not found in commercially exploitable quantities.
Various methods for producing synthetic forms of the minerals nobleite and gowerite are known. For example synthetic nobleite can be produced by the hydrothermal treatment of meyerhofferite (2CaO 3B2O37H2O) in boric acid solution for 8 days at 85°C. See U.S. Patent No. 3,337,292.
Ditte, Acad. Sci. Paris Copies rendus, 77, 783-785 (1873), described the formation of lime borates by reaction of Iceland spar (calcite) with a saturated boric acid solution. The resultant salt was described as small needles of "a hydrated lime borate" .which contains "3BoO2, CaO and 4HO, which can be written as (2BoO2 CaO HO)(BoO2, 3HO)." Subsequently, Erd, McAllister and Vlisidis, American Mineralogist, 46 , 560-571 (1961), suggested the Ditte product was nobleite. Erd et al also synthesized nobleite by stirring CaO and boric acid in water for 30 hours at 48°C. and then holding the product at 68°C for 10 days.
Kemp, The Chemistry of Borates, Part I, page 70 (1956), reported that an aqueous solution of boric acid kept at 40°C for 3 weeks deposits a mixture of CaO-3B2O3 4H2O and 2CaO-3B2O39H2O. Kemp also reported that CaO.3B2O38H2O decomposes to form CaO.3B2O3.4H2O. According to Supplement to Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Volume V. Part A: Boron-Oxygen Compounds, pages 550-551 (1980), CaO-3B2O3.4H2O occurs as a solid phase in the systems Na2O-CaO-B2O3-H2O and CaO-NaCl-B2O3-H2O at 25°C and pH 5.5-6.5. Hydrothermal treatment of meyerhofferite in boric acid solution at 85-250°C produced crystals of both the tetrahydrate and pentahydrate together with gineritc (2CaO-7B2O3-8H2O).
Mellor further reported that nobleite is a stable phase in the CaO-B2O3-H2O system at 25°C and at 45°C and is also formed from an aqueous mixture of lime (CaO
2

and boric acid at 60°C. Also, Mellor reports on page 551 that CaO.3B2O3.5H2O (gowerite) is formed from lime and boric acid in aqueous media at 100°C.
Lehmann et al, Zeitshrift fur Anorqanische und Allgemeine Chemie, Volume 346, pages 12-20, (1966), teach that the formation of gowerite from CaO, H3BO3 and water is favored by a relatively high temperature (100°C), and higher CaO concentration, whereas nobleite formation is predominantly formed in more dilute solutions with lower CaO content and at lower temperature (60°C}.
In contrast to the teachings of the art, it has been discovered that the reaction of boric acid and lime in an aqueous mixture at high temperature will produce nobleite instead of gowerite provided that the reactants, and boric acid in particular, are present at sufficiently high concentration in the reaction slurry, and the molar ratio of lime to boric acid ( CaO:H3BO3) added is within specific limits.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides, a method for producing crystalline calcium hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry. The method of this
3

invention results in a rapid reaction rate, high product yield and favorable product characteristics such as fine particle size distribution, rapid filtration and good flow and bulk handling properties. Further, there is provided a novel crystalline calcium hexaborate tetrahydrate composition having a distinctive crystal habit.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate produced at low temperature (approximately 22°C). Figure 2 is a photomicrograph of calcium hexaborate tetrahydrate produced at high temperature (approximately 95°C) by the improved method of this invention.
3A

DETAILED DESCRIPTION OF THE INVENTION
The method of this invention comprises reacting high concentrations of boric acid and lime in water at high temperature, such as in the range of 85° to 105°C, to form crystalline calcium hexaborate tetrahydrate. The preferred reaction temperatures are near the boiling point of the slurry, and preferably in the range of from 95° to 101°C.
The concentration of the reactants is important to the production of calcium hexaborate tetrahydrate according to the process of this invention. In particular, a high ratio of boric acid to water in the reaction mixture will produce nobleite rather than gowerite at the high temperature conditions of this invention. Boric acid, which is highly soluble in water at high temperatures, should be added in quantities which are substantially greater than the solubility limit, in order to produce nobleite at these temperatures. The molar ratio of boric acid to water (H3BO3:H2O) in the starting mixture should be greater than 0.25:1, such as in the range of from 0.25 to 0.5:1 and preferably in the range of from 0.3 to 0.45:1. This is substantially higher than the solubility limit of boric acid at temperatures of 80° to 100°C which ranges from 0.07 to 0.11 moles of H3BO3 per mole of water.
The molar ratio of lime to boric acid (CaO:H3BO3) in the starting mixture is in the range of from 0.05 to 0.15:1, and preferably 0.1 to 0.13:1. As used herein, lime includes calcium oxide such as burnt lime and quick lime, calcium hydroxide such
4

as hydrated lime, slaked lime and lime hydrate, and calcium carbonate, including calcite and limestone.
It appears to be beneficial to have a high concentration of undissolved solids in the reaction mixture such as would provide at least 25% by weight undissolved solids in the final product slurry and preferably at least 30% by weight. If the solids concentration is too low, this may lead to the formation of gowerite instead of the desired nobleite.
The method of this invention may be used in producing calcium hexaborate tetrahydrate in a batch, continuous or semi-continuous process. In a batch process, the boric acid and lime may be combined in water and heated at the required temperature range to initiate the reaction. Alternatively, a mother liquor recycled from previous runs or freshly prepared mother liquor may be used as the reaction media. In a continuous or semi-continuous process, the desired product is continuously removed from the reaction vessel and the remaining mother liquor is recycled by adding additional boric acid and lime and heating the reactants at the reaction temperatures.
The reaction is essentially complete within one hour, although small improvements in the product B2O3 analysis may be attained by heating the reaction mixture for up to about 4 hours. When calcium oxide or calcium hydroxide are used as reactants, the reaction occurs as a noticeable exotherm within about 15 to 25 minutes, during which time the majority of the starting materials are converted to the desired product.
5

Preferably, the reaction mixture is agitated, such as by stirring, during the reaction period. After the reaction is completed, the nobleite product is separated from the hot mother liquor such as by filtration or centrifugation or other suitable mean of solid-liquid separation. The wet solids may be washed, such as with water, to remove any entrained mother liquor, and subsequently dried to provide a crystalline calcium hexaborate tetrahydrate.
If a product with higher B2O3 content is desired, the calcium borate tetrahydrate can be dehydrated by heating at a temperature of at least 325°C, preferably in the range of 450°C to 550°C to produce a novel amorphous, anhydrous calcium hexaborate, CaO.3B2O3, which contains about 79% B2O3.
The production of nobleite by the method of this invention has a number of advantages over the previously known methods. The reaction time is substantially reduced from as long as several weeks at low temperatures, to as short as less than an hour at the temperatures of this invention. Also, the high concentration of reactants provides a higher yield of product per unit volume of the reaction mixture. Substantially pure nobleite can be produced under the preferred conditions of this invention, while under the conditions outside of this region, nobleite is partially or totally replaced by the formation of gowerite during the reaction.
It has been further discovered that the product of the method of this invention has a unique crystal habit not found in nobleite formed at low concentrations and temeratures.Nobleite, as
found in nature and as synthesized at room temperature, is
5A

distinguished by a platy morphology. Although it is monoclinic, the platelets have a pseudohexagonal form. The platelets are commonly found in aggregates that arc stacked or arranged sub parallel to the 100 plane. The large thin crystals have been found in sizes up to a centimeter in length and have a hexagonal aspect, while the smaller crystals are more rhombic shaped and may form drusy coatings. See also Erd, McAllister and Vlisidis, American Mineralogist-46 , 560-571 (1961). Figure 1 is a photomicrograph of calcium hexaborate tetrahydrate crystals formed at room temperature, obtained by scanning electron microscopy at a magnification of 5500x.
Although the crystalline form of the calcium hexaborate tetrahydrate produced by the process of this invention is also composed of platelets, the crystal habit or arrangement of these platelets is very distinctive and unique. Individual thin platelets, are arranged in nearly spherical radial clusters. Figure 2 is a photomicrograph of the crystalline product of this invention obtained by scanning electron microscopy at a magnification of 3000x and shows the unique crystal habit of the product produced according to the method of this invention.
Particle size analysis of the crystalline product of this invention indicates a relatively small mean particle size distribution, typically of about 90% less than 75 micrometers in diameter. This small mean particle diameter is advantageous for many applications where a fine dispersion of the solids is required, such as for fire retardant applications in polymeric resins. Yet it is easy to filter, facilitating the separation of the solid product from the mother liquor, which then can be recycled back into the process. Further, the spherical shape of the crystal habit results in excellent handling and flow properties of the dried solids despite the extremely fine particle size distribution. It was also found that the crystalline product docs not have a significant tendency toward caking.
The product dehydrates in three distinct stages, losing water at about 91°, 177° and 312°C. It was found to melt at a temperature of about 927°C. The anhydrous calcium borate product produced by dehydration of the product is less hygroscopic than most dehydrated metal borate compounds.
EXAMPLES

The following examples illustrate the novel methods and compositions of this invention.
EXAMPLE 1
Boric acid (1,448 grams) and 31.7 grams of calcium hydroxide (Ca(OH)2) were combined in 5.00 liters of deionized water in a stirred flask to make up a batch of synthetic mother liquor. This mixture was stirred and heated to 95°C and two batches, each of 2,089 grams of boric acid and 417 grams of calcium hydroxide, were added over a period of about six minutes to give a final reaction slurry (33% undissolved solids) containing a lime to boric acid (CaO:H3BO3) molar ratio of 0.13:1 and a boric acid to water (H3BO3H2O) molar ratio of 0.33:1. There was a slight drop in temperature after the addition of each batch, followed by a final exotherm which raised the temperature to boiling (1010C). The resultant reaction mixture was stirred at about 95° to 100°C for 3 hours and samples of the solid product and liquor were taken for analysis after each hour. The results are shown in Table 1. The reaction slurry was diluted with warm water and filtered to give a filter cake of product which was washed with cold water to remove adhering liquor. The resultant crystalline product was dried and determined to be substantially pure nobleite by X-ray diffraction analysis, titration and thermogravimetric analysis (TGA).
Figure 2 is a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 3000x.

7

TABLE 1

Reaction Time
Weight % B2O3 in solids
Weight % CaO in solids
Molar Ratio CaO/B2O3 in solids
Weight % B2O3 in liquor
Weight %CaO in liquor
1 Hour
61.69
15.90
0.320
10.82
0.29
2 Hours
61.84
15.94
0.320
9.08
0.24
3 Hours
62.11
15.96
0.319
8.90
0.24
Theoretical
62.00
16.62
0.333

The crystalline nobleite product had a very fine particle size distribution with more than 90% by weight passing a 200 mesh (74 micrometer) lest sieve and 70% by weight passing a 325 mesh (45 micrometer) test sieve. The particle size distribution is shown in Table 2.
TABLE 2

U.S. Mesh
Opening Size (micrometers)
Weight % Retained
Cum. Weight
% Passing
80
180
0.93
99.07
100
150
0.19
98.88
140
105
1.10
97.78
200
75
3.82
93.96
325
45
22.84
71.12
EXAMPLES 2-13
Synthetic mother liquors were prepared by combining boric acid, lime (in the form of calcium hydroxide) and deionized water in a stirred flask. These mixtures were heated to a temperature of 95°C and additional boric acid and lime were added to the reaction mixtures in up to four batches. The reaction mixtures were stirred at 95°C for 3 to 4 hours following the final addition of boric acid and lime. At the end of the reaction time the slurry was filtered and washed to recover the solid product. The
8
molar ratios of reactants, namely boric acid:water (BA/Water) and lime:boric acid (CaO/BA), are shown in Table 3 below along with the product B2O3 analyses and mineralogical results. The mineralogy of the crystalline product was generally determined by X-ray diffraction and microscopy. The nobleite/gowerite ratio was estimated for some of the products from X-ray diffraction data.
TABLE 3

Example No.
Mole Ratios of Reactants

Product Analyses

BA/Water
CaO/BA
%B2O3
Mineralopv
2
0.43
0-09
63.3
Nobleilc
3
0.33
0.13
62
Nobleitc
4
0.30
0.14
62.2
Nablcitc + Gowcritc (92/8)'
5
0.30
0.14
61.4
Nobleite
6
0.23
0.11
62.1
Nobleitc + Gowerite (94/6)
7
0.20
0.15
59.1
Nobicite + Gowcritc
8
0.17
0.09
59.1
G owe rite
9
0.12
0.12
59.4
Nobleilc + Gowcrite
10
0.12
0 12
58.9
Goweritc
11
0.10
0.14
58.2
Gowcritc
12
0.06
0.09
58.3
Gowcritc
13
0.04
0.16
41.3
Sibirskite
As shown in the Examples of Table 3, substantially pure nobleitc, having a high B2O3 analysis, is produced when the boric acid/water molar ratio is above about 0.25 and the lime/boric acid molar ratio is less than about 0.15. When the boric acid/water ratio is reduced and/or the lime/boric acid ratio is increased, the boric oxide content of the product decreases and the nobleite product is replaced by gowerite.
9
EXAMPLES 14-17
The following reactions were carried out using calcium carbonate as the source of lime. Example 14 was carried out by a procedure similar to Example I above, wherein a synthetic mother liquor was made by mixing boric acid, calcium carbonate and deionized water in a stirred flask and after heating to 95°C additional boric acid and calcium carbonate were added.
In examples 15-17 deioniz.ed water and calcium carbonate were combined and, after heating to 95°C, boric acid v/as added. Substantial foaming of the reaction mixtures was observed as a result of CO2 gas released by the reaction of the boric acid and calcium carbonate. This resulted in a drop in temperature from 95°C.to about 63-66°C. The reaction mixtures were reheated to 95°C within 15 to 20 minutes.
The reaction mixtures were stirred continuously and the temperatures controlled at about 95°C for about 3 to 3.5 hours after the final reagent additions. At the end of the reaction period the slurries were filtered and the solids washed to remove entrained solution. The mole ratios of the reactants and the chemical and mineralogical analyses of the solid products are summarized in Table 4.
TABLE 4
Example No. Mole Ratio of Reactants Product Analyses
BA/water CaO/BA %B2O3 Mineralogy
14 0 33 0.13 62 2 Nobleite
15 0.33 0.16 60 5 Nobleite
16 0.33 0.13 62.3 Nobleite
17 0.24 0.21 55.6 Nobleite+Calcite
10

EXAMPLE 18
(Comparative)
Boric acid (40 grams) and 8 grams of hydrated lime were added to 200 grams of water to give a reaction mixture containing a boric acid to water molar ratio of 0.06:1 and a lime to boric acid molar ratio of 0.17:1. The mixture was stirred initially and then allowed to sit at room temperature (approximately 22°C) over a seven day period. The resulting solid product was recovered and determined to be nobleite by X-ray diffraction analysis. Figure 1, a photomicrograph of the crystalline product obtained by scanning electron microscopy at a magnification of 5500x, shows the product as consisting of stacked aggregates of hexagonal platelets.
The above example shows that while synthetic nobleite can be formed at low
ratios of boric acid to water at low temperatures, long reaction times are required.
Further, the crystal habit of the resultant product is more like that described for natural
nobleite than the spherical radial clusters obtained by the process of the present
invention as illustrated in Example 1.
EXAMPLE 19
A 5.9 kilogram sample of synthetic nobleite containing product from Examples 1, 3 and 5 was distributed into several stainless steel pans and heated in an oven at 500°C for about 17 hours. The residual water content of the dehydrated product was determined to be less than 0.5% by weight by thermogravimetric analysis. This product was observed to have the same free-flowing properties characteristic of the nobleite product prior to dehydration. This is attributed to the particle form or habit which was confirmed by scanning electron microscopy to resemble the crystal habit of the hydrate prior to dehydration except that there are generally some openings of the radial platelets making up the spherical radial clusters. Despite this characteristic particle form or habit which is residual from the crystalline form existing prior to dehydration. X-ray diffraction analysis indicated that the dehydrated product is essentially amorphous.
11

Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.
12

WE CLAIM:
1. A method for producing crystalline calcium
hexaborate tetrahydrate which comprises reacting boric acid and lime in an aqueous slurry, at a temperature in the range of from 85° to 105°C, wherein the molar ratio of boric acid to water is in the range from 0.25 to 0.5:1 and the molar ratio of lime to boric acid is in the range of 0.05 to 0.15:1 and optionally, separating said crystalline calcium hexaborate tetrahydrate from said slurry.
2. A method as claimed in claim 1, wherein said molar
ratio of boric acid to water is in the range of from 0.3 to
0.45:1.
3. A method as claimed in claim 1, wherein said molar
ratio of lime to boric acid is in the range of from 0.1 to 0.13:1.
4. A method as claimed in claim 1, wherein said
temperature is in the range of from 95° to 101°C.
5. A method as claimed in claim 1, wherein source of said
lime is calcium carbonate.
6. A method as claimed in claim 1, wherein said lime is
hydrated lime.
7. A method as claimed in claim 1, wherein said
crystalline calcium hexaborate tetrahydrate is dehydrated by
heating at a temperature above 325°C.
8. A method as claimed in claim 7, wherein said
temperature is in the range of from 450°C to 550°C.
13

14
9. A method for producing crystalline calcium hexaborate tetrahydrate, substantially as herein described, particularly with reference to the foregoing examples and the accompanying drawings.

An improved method is provided for producing crystalline calcium hexaborate tetrahydrate, synthetic nobleite, by the reaction of boric acid and lime in an aqueous slurry. Reaction conditions include boric acid to water molar ratios of greater than 0.25:1, lime to boric acid molar ratios in the range of 0.05-0.15:1 and temperatures in the range of 85°-105°C. A novel crystalline product is produced having a unique crystal habit resulting in improved physical properties. Dehydration of this product produced a novel amorphous, anhydrous product having similar crystal habit and physical properties.

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Patent Number

190088

Indian Patent Application Number

60/CAL/1997

PG Journal Number

30/2009

Publication Date

24-Jul-2009

Grant Date

13-Jan-1997

Date of Filing

13-Jan-1997

Name of Patentee

U. S. BORAX INC.

Applicant Address

26877, TOURNEY ROAD, VALENCIA, CALIFORNIA

Inventors:

#	Inventor's Name	Inventor's Address
1	DAVID MICHAEL SCHUBERT	11252, NEBRASKA AVENUE, LOS ANGELES, CALIFORNIA 90025

PCT International Classification Number

C01B 35/12

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA