CRYSTALLINE HYDRATED LAYERED SODIUM AND POTASSIUM SILICATES AND METHOD OF PRODUCING SAME

Abstract: The present invention discloses a crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite material with predetermined hardness ion sequestration properties achieved by control of the process for forming the material. The process for producing the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite comprises hydrolyzing DB-1 crystalline sodium and potassium silicate glasses as a precursor material to produce the composite material known as DB-2. Hydrolysis of the DB-1 precursor material is achieved by adding typically up to 100 milliequivalents per gram of H3O<+> ions or up to 50 milliequivalents per gram of OH<-> ions. The resulting DB-2 material can sequester Ca<2+> ions, Mg<2+> ions, or both, depending on the starting materials used, processing conditions, and results desired.

Description: CRYSTALLINE HYDRATED LAYERED SODIUM AND POTASSIUM SILICATES AND METHOD OF PRODUCING SAME FIELD OF THE INVENTION This invention relates to composite materials com¬ prising a crystalline hydrated layered alkali silicate and an amorphous alkali silicate that exhibit the ability to reduce the activity of hardness ions in laundry wash water. In particular, this invention relates to crystalline hyd¬ rated layered alkali silicate/amorphous alkali silicate composite materials useful as detergent ingredients. BACKGROUND OF THE INVENTION It is known that hard water ions, specifically cal¬ cium and magnesium, adversely affect the activity of soaps and detergents. These ions deactivate detergents and can form undesirable precipitates. Thus it is desirable to remove these ions to avoid reaction with the detergent. One way to do this is to soften the water before it enters the washing machine. In many parts of the world, this is im¬ practical or impossible, and even where it can be done, in most localities it is expensive. Another approach is to remove hard water ions by reaction with another material in situ in the washer. Materials useful for removing hard water ions include alkali silicates (noncrystalline sili¬ cates, crystalline silicates, and zeolites) , particularly hydrated layered alkali silicates. Layered alkali silicates are materials chemically comprising Si0 2 organized into layers (sheets) having a nega¬ tive charge, with alkali cations for charge compensation and, in some cases, water between the layers (these mate¬ rials are known as HLS) . Hydrated layered sodium silicates have been known for a number of years, either synthetically produced or naturally occurring [McCulloch J. Am . Chem . Soc . 75, 2453 (1952)]. The Si0 2 /Na 2 0 ratios of these silicates range from 4 to 20. The first synthetic hydrated layered silicate, having a Si0 2 /Na 2 0 ratio of 4, was reported by Wills in 1953 (US Patent 2,640,756). This synthetic hy¬ drated layered silicate was claimed to be useful as an ion exchange material, specifically for calcium. However, the structure of the synthetic hydrated layered silicate pre¬ pared by Wills was not disclosed. In 1972, a naturally occurring tetrasilicate (Si0 2 /Na 2 0 = 4) was reported by Johan and Maglione [Johan and Maglione, Bull . Soc. Fr. Mineral . Cryεtallogr. 95, 371 (1972)]. The structure of this mate- rial was identified as a hydrated layered silicate, and the name "kanemite" was given to this mineral. In The Chemistry of Silica (1979) and J " . Colloid Sci . 19, 7, 648 (1964), Her concluded from the results of Johan and Maglione that the synthetic hydrated layered silicate claimed by Wills in 1953 was kanemite. Furthermore, Her reported that crystalline hydrated layered alkali silicates have the ability to ion exchange their sodium ions and protons with other metal ions or organic ions. Iler's observations are consistent with Wills' experimental findings on the calcium " ion exchange ability of kanemite materials. The synthesis of kanemite has also been reviewed by Beneke and Lagaly [Amer. Mineral . 62, 763 (1977) ] . In recent years, use of crystalline layered sodium silicates, especially crystalline sodium disilicates, as detergent builders has been suggested [see US Patents 4,585,642; 4,806,327; 4,950,310; 4,820,439; 4,664,839 and 4,959,170]. These crystalline sodium disilicates were synthesized and reported as early as 1966 [Williamson and Glasser, Physics and Chemistry of Glasses , Vol. 7, No. 4, (August 1966) ] . While the abovementioned patents claim that crystalline sodium disilicates function when incorporated into detergents, the disclosed crystalline layered silicates have not been accepted readily by the worldwide detergent industry due to their poor ability to remove hardness ions from wash water at temperatures below about 30°C. Further, there are circumstances where it may be necessary to desirable to remove only one hardness ion or the other (Ca 2+ or Mg 2+ ) . Some detergent formulations have been developed which work synergistically with one hardness ion. Accordingly, it may be undesirable to remove that ion, or it may be desirable to reduce it to a specific concentra- tion to optimize detergent performance while removing the other ion. Finally, where only one ion is present in water of a particular geographic region, only that ion (either calcium or magnesium) can be removed from the wash water. In the past, tailoring builder materials to selectively sequester hardness ions was difficult or impossible. It is an object of this invention to provide a composite material comprising a hydrated layered alkali silicate, including both sodium and potassium, and an amor¬ phous alkali silicate, including both sodium and potassium, that is more suitable as a detergent ingredient than pre¬ viously suggested materials that it would replace. A further object of this invention is to provide a detergent composition that includes a hydrated layered alkali sili¬ cate/amorphous alkali silicate composite that reduces the activity of hardness ions in the wash water without produc¬ ing the detrimental precipitates of these ions produced by some other detergent additives including sodium carbonate. It is a still further object of this invention to provide the chemistry and the processing necessary to tailor the detergent builder and ion sequestering properties of these hydrated layered alkali silicate/amorphous alkali silicate composite materials. SUMMARY OF THE INVENTION The present invention is a crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite material with predetermined hardness ion sequestration properties achieved by control of the process for forming the material, and a process for making the material. The present invention utilizes crys- talline sodium and potassium silicate glasses as a precursor material to produce the composite material known as DB-2. Although the precursor materials themselves can be utilized to sequester magnesium and calcium ions in solution, the DB-2 composite products of the present invention have superior detergent building properties compared to their individual components. The process for producing the crystalline hydrated layered sodium and potassium silicate comprises hydrolyzing the crystalline precursor materials in an alkaline or acidic media followed by drying. The hydrolysis process used is disclosed in US Patent Application Serial Number 08/258,466, which is incorporated herein by reference. This process, when applied to a crystalline sodium/potassium silicate starting material, produces a structure which is similar to a kanemite structure but contains both potassium and sodium cations between the layers (sheets) of Si0 2 . The resultant crystalline phase is referred to herein as "DB-2." It is a composite material comprising a hydrated layered alkali silicate and an amorphous alkali silicate which is produced to provide predetermined hardness ion binding properties. Although the above-referenced application discloses hydrolyzing sodium silicate glasses to produce a kanemite structure, the present invention differs in that hydrolysis of a sodium/potassium glass to produce a crystalline hydrated layered alkali silicate achieves a number of advantages. The first advantage is that a crystalline hy¬ drated layered sodium potassium silicate/amorphous sodium potassium silicate composite material having improved hard¬ ness ion binding properties as compared to pure crystalline hydrated layered sodium silicate/amorphous sodium silicate composite is achieved by controlling the process for forming the material. Additionally, the use of potassium in con¬ junction with sodium glass affords the opportunity to eliminate the spray drying process required in converting pure sodium silicate glasses through their delta-phase crystalline forms, which is required to achieve good hardness ion binding properties in the finished material. The spray drying process is energy intensive and expensive. Eliminating spray drying makes the present process much more desirable economically. DESCRIPTION OF THE DRAWING Figure 1 is a schematic representation of the hydro¬ lysis process used to produce the hydrated layered sodium silicates of U.S. Patent Application 08/258,466 and the hy¬ drolysis process of the present invention used to produce sodium/potassium silicates. DETAILED DESCRIPTION OF THE INVENTION The composite materials of the present invention have superior properties as compared with prior art de¬ tergent builder/sequestering materials. These composite materials remain free flowing powders under ambient or high humidity conditions. Under similar humidity conditions, prior art detergent builders such as crystalline disilicates become a dilatent mass. In addition, the hydrated layered silicate composite materials of this invention are more effective in reducing the activity of hardness ions in laundry wash water than previously reported kanemite or crystalline disilicate materials. This is observed in a pH range of 8 to 10, the operating pH range of most detergents currently in use. The detergent building properties of the hydrated layered silicate/amorphous silicate composite ate- rials of the present invention can be adjusted to maximize performance in varying wash conditions. The inventors believe such adaptability has not heretofore been known. The exact silica to alkali ratio of the hydrated layered silicate included in the composite of the present invention depends on the history of the material and the extent of any hydrolysis that has taken place. The X-ray diffraction pattern of the composite material indicates that it includes hydrated layered silicate with the same crystal¬ line structure as the mineral kanemite. Kanemite has a distinctive X-ray diffraction pattern summarized in Table 1. The data in Table 1 are summarized from Joint Committee on Powder Diffraction Standards (JCPDS) File 25-1309. The mineral kanemite has been reported to have a Si0 2 /Na 2 0 ratio of 4. However, pure kanemite produced in accordance with the teachings of Beneke and Lagaly (see above) was shown to have a Si0 2 /Na 2 0 ratio of only 3.36. This material gave an X-ray diffraction pattern indicating pure kanemite, which shows that the Si0 2 /Na 2 0 ratio of pure kanemite may be variable. TABLE 1 X-RAY DIFFRACTION PATTERN OF KANEMITE d-spacing (A) I/I 0 10.300 100 5.130 50 4.010 100 3.640 50 3.440 90 3.160 70 3.090 70 2.480 80 2.386 60 2.073 40 1.995 50 1.929 40 1.464 40 1.191 40 The composition of kanemite with a Si0 2 /Na 2 0 ratio of 4 is 56.08% Si0 2 , 14.49% Na 2 0, and 29.43% water on a weight basis. When heated to 150°C, the weight lost due to water removal is approximately 16.82%. An additional 8.41% weight reduction occurs when water is driven off at temperatures between 150°C and 280°C. The remaining 4.2% water can be driven off at temperatures above 280°C. These dehydrated forms of kanemite also have distinctive X-ray diffraction patterns which can be found in JCPDS File 27-709 (NaHSi 2 0 5 - H 2 0) and File 27-708 (NaHSi 2 0 5 ) , which are incorporated herein by reference. Synthetic kanemite (which will be referred to herein simply as "kanemite" since it possesses the same X-ray dif¬ fraction pattern as natural kanemite) can be prepared by various methods including the hydrolysis of various species of crystalline sodium disilicates or the base exchange of disilicic acids. Kanemite can also be recovered as the crystallization product of sodium silicate solutions that have been stored for long periods of time at ambient condi¬ tions or for shorter periods of time at elevated temperature. Seeding of the sodium silicate solutions is advantageous if kanemite production is desirable. Synthesis of the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium sili¬ cate composite materials of the present invention can be accomplished by hydrolyzing precursor DB-1 materials. The precursor materials can be made by any one of several pro¬ cesses as disclosed in US Patent Application Serial Number 08/270,489 which is incorporated herein by reference. The first process which can be utilized to produce the precursor material involves the production of an amor- p ous Na/K silicate glass in a furnace using conventional sodium silicate production means. The term Na/K silicate glass as used herein refers to a silicate glass (i.e., an amorphous material) containing both sodium and potassium ions. This amorphous glass is then milled and optionally mixed with water. The mixture is calcined to produce the precursor starting material of the present invention which is a DB-1 phase crystalline composite material. the cal¬ cination is generally performed at temperatures between 500°C and 800°C, although calcination temperatures outside this range may be effective with specific formulations. Temperatures outside this range generally yield either an amorphous alkali silicate or undesirable crystalline alkali silicates. The calcined material can then be milled to the appropriate particle size before further processing. A second process for producing the DB-1 precursor material begins with the production of a sodium silicate glass by conventional means. This glass is then milled and mixed with water and a suitable potassium compound such as potassium hydroxide. This mixture is calcined to produce the DB-1 precursor. In a third process for producing these precursor starting materials, amorphous Na/K silicate glass is dis¬ solved in soft water and then spray dried to produce a hydrate Na/K silicate, followed by calcination to produce the DB-1 phase precursor material of the present invention. In each of the above processes, the product can be recycled into the calciner to seed the formation of the desired crystalline product. The synthesis of the hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composites of the present invention can be produced by performing a controlled hydrolysis of a DB-1 crystalline silicate and can be accomplished by the following process. Starting with the DB-1 precursor materials, a slurry is made using double deionized water which is utilized to ensure that the resultant material is free of hardness ions. The slurry is then hydrolyzed using either hydronium or hydroxyl ions which can be accomplished b>y introducing various amounts of hydrochloric or other suitable acid or potassium or sodium hydroxide or other suitable base, respectively. Typically, hydrochloric acid is used in amounts which yield up to and including 100 milliequivalents (meq) hydronium ions per gram of DB-1 material, while potassium hydroxide is used in amounts which yield up to and including 50 meg of hydroxyl ions per gram DB-1 material. More preferably, hydrochloric acid is used in amounts which yield up to 10 meq hydronium ions per gram of DB-1 material. The mate¬ rials of the present invention are produced by either filtering or spray drying the hydrolyzed DB-1 slurry. The advantages of spray drying over some other separation method (such as crystallization and filtering) performed upon the hydrolyzed slurry is that the total recovery of solids from the slurry is greater and a composite product results which has superior ion binding performance compared to hydrated layered sodium silicate/amorphous sodium silicate composites produced by the same process with a different separation technique. The resulting hydrolyzed material is a hydrated crystalline layered sodium and potassium silicate/amorphous sodium and potassium silicate composite material, referred to herein as DB-2, and typically yielding the following X-ray diffraction pattern: TABLE 2 X-RAY DIFFRACTION PATTERN OF DB-2 d-spacing (A) 10.30 5.13 4.02 3.63 3.16 3.09 2.47 2.42 2.09 Based upon the X-ray diffraction pattern results in Table 2, it is believed that the DB-2 material of the pres¬ ent invention contains both sodium and potassium within a kanemite crystalline phase. It is to be understood, how¬ ever, that this crystalline phase is not to be taken as a limitation of the present invention in that a different crystalline phase may be present. In US Patent Application Serial Number 08/258,466, a hydrolysis process was disclosed for producing a crystal¬ line hydrated layered sodium silicate/amorphous sodium silicate composite material having a synthetic kanemite phase. This process required spray drying the sodium silicate precursor materials in order to produce the proper synthetic kanemite phase. In utilizing potassium in con¬ junction with sodium in the precursor material in the present invention, however, the spray-drying step which is required in the preparation of pure delta-phase sodium disilicate precursor materials for hydrolysis can be elim¬ inated while still achieving the desired kanemite phase in the final product. That is, a kanemite crystalline struc- ture results form hydrolysis of DB-1 phase sodium potassium precursor materials which can be produced without the spray drying step necessary to produce the delta-phase sodium silicate precursor required for hydrolysis to produce kane¬ mite in a pure sodium system. Thus hydrolysis of the sodium and potassium precursor materials as disclosed in the pres¬ ent application provides a more economical process since a spray-drying step can be eliminated when producing the pre¬ cursor materials while providing a resulting material with enhanced hardness ion binding properties. The concentration of ions (hydronium or hydroxyl) in the hydrolyzing media will dictate the final detergent builder properties, including the Si0 2 /alkali ratio of the composite material. The hydrolyzed composite material can either be dried by filtering the slurry and drying the filter cake at temperatures up to 100°C or by spray drying at temperatures up to 120°C. The hydrolyzed product is then pulverized by ball milling to produce the resultant hydrated layered amorphous alkali silicate composite containing a kanemite phase. The resulting composite material provides excellent builder behavior for detergents. For example, the composite material does not cakewhen exposed to atmospheric conditions. The material remains a free-flowing powder when exposed to 80% relative humidity for a period of at least three months. Ordinary crystalline disilicates become a dilatent mass within a few weeks at such humidity. The buffering capacity of the composite material is excellent. Buffering takes place in an attractive pH range for effective laundering, i.e., a pH range of about 8 to 10. The composite material of the present invention has a high ion binding capacity and will reduce the activity of both hardness water ions (Ca 2+ and Mg 2+ ) in wash water if desired. This is superior to presently used detergent builders such as Zeolite NaA and delta-phase disilicate. Zeolite NaA primarily exchanges calcium, and delta-phase disilicate requires much higher pH ranges, generally 10 to 12, to provide effective hardness ion binding capacity. Further, delta-phase disilicate may dissolve at these high pH conditions to produce undesirable precipitates of calcium and magnesium silicates or hydroxides. The DB-2 hydrated layered sodium and potassium sili- cate/amorphous sodium and potassium silicate detergent builder of the present invention can be formulated into detergent formulations with most commonly used ingredients to form stable compositions. Anionic, nonionic and zwiter- ionic surfactants can be used in detergent formulations. Co-builders such as crystalline aluminosilicates (including clays and zeolites) , organic sequestrants and condensed polyphosphates are also compatible with the material of the present invention, as are other conventional detergent ingredients. More particularly, the zeolites utilized can include those such as Zeolite NaA having a Si0 2 /Al 2 0 3 ratio of 2.0 to 2.2, Zeolite P having a Si0 2 /Al 2 0 3 ratio of 2.0 to 7.0 (including maximum aluminum NaP phase having a Si0 2 /Al 2 0 3 ratio of 2.0 to 2.3 to yield the maximum aluminum possible in the P phase) , Zeolite NaX having a Si0 2 /Al 2 0 3 ratio of 2.3 to 5.0, and Zeolite K/NaX having a Si0 2 /Al 2 0 3 ratio of 2.0 to 2.3. Spray drying, agglomeration and dry blending methods can be utilized to form stable and efficient detergents con¬ taining the products of the present invention. Further properties and advantages of the hydrated layered sodium and potassium silicates/amorphous sodium and potassium silicate composite compositions of the present invention are illustrated in the following examples. The examples are divided into three categories to illustrate the hydrolyzed materials of the present invention as follows: (1) examples 1-9 enumerate the production of the DB-1 phase precursor materials which are to be hydrolyzed; (2) examples 10-45 are comparative examples of hydrated layered sodium silicate/amorphous sodium silicate composites disclosed and produced by the hydrolysis process as disclosed in US Patent Application Serial Number 08/258,466; and (3) examples 46-121 are the hydrolyzed product of the present invention (i.e., crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite materials) . EXAMPLES The proportions are in parts by weight (pbw) , percent weight (%) , parts per million (ppm) , moles or equi¬ valents unless otherwise indicated. The notation "DI 2 -water" refers to double distilled water. The calcium and magnesium ion exchange rates and capacities were determined for various products and are reported as the calcium exchange rate (CER) , calcium ex¬ change capacity (CEC) , magnesium exchange rate (MgER) , and magnesium exchange capacity (MgEC) . The results shown in the tables are expressed as milligrams (mg) of CaC0 3 per gram (g) of anhydrous product for both calcium and magnesium. For brevity, the calcium and magnesium exchange capacities of the products of this invention, as described in the disclosure and recited in the claims, can also be (and frequently are) expressed in units of milliequivalents of Ca (or Mg) per gram of anhydrous product. The calcium and magnesium performance (CER, CEC, MgER and MgEC) were determined as follows. The product (0.5 g on an anhydrous basis) was reacted with 250 milli- liters (ml) of a solution containing either calcium or magnesium ions. The concentration of these solutions was 1000 ppm expressed as CaC0 3 . The stirred reaction mixture was buffered at a pH of 10 with 2 to 3 ml of a solution of NH 4 C1 and NH 4 OH. The temperature was held at 25°C (unless otherwise noted) during the exchange reaction. An aliquot (15 ml) was removed after 2 minutes to determine the calcium and magnesium exchange rates (CER and MgER) by pulling the suspension through a 1.0 micron filter into a syringe. A second aliquot was removed at 15 minutes to determine the calcium and magnesium exchange capacities (CEC and MgEC) . The filtrates from the calcium exchange reaction were analyzed for calcium in solution as follows. A 5 ml aliquot of filtrate was combined with 5 ml of 1 molar NaOH and about 100 mg of hydroxy naphthol blue indicator. A titration to a definite blue end point was carried out with 0.005 molar ethylene diaminotetracetic acid (EDTA), and the volume of EDTA used was recorded. A blank titration using 5 ml of the 1000 ppm CaC0 3 solution was carried out using the same method and the volume of EDTA was recorded. Filtrates from the magnesium exchange reaction were analyzed in the same manner except that 5 ml of an NH 4 0H/NH 4 C1 buffer and about 100 mg of Erichrome Black T (3-hydroxy-4-[ (l-hydroxy-2-naphthalenyl) azo]-7-nitro-l-naphthalenesulfonic acid monosodium salt, available from Sigma Chemical Co., St. Louis, Missouri) were used. The rates and capacities for calcium and magnesium ions removed by the product were calculated as mg of CaC0 3 /g of anhydrous product as follows: milligrams CaC0 3 _ (B-V) • M- FW- 50 gram anhydrous product [ (100-LOI) /100] • W where: B = volume of EDTA for blank titration (ml) V = volume of EDTA for sample titration (ml) M = molarity of EDTA solution FW = formula weight of CaC0 3 (100.1 g/mole) LOI = loss on ignition of product at 800°C (%) W = weight of product (g) Phase identification of the examples was determined using standard X-ray diffraction techniques. A 5-50 two- theta scan was used. To assess the effect of the hydrolysis process upon the sodium and potassium concentrations in the final layered silicates, 8 samples were analyzed. The results, found in Table 16, show that sodium and potassium was present in the crystalline phase of the final composite material and that there was little variation in the final sodium and potassium concentrations which resulted from the starting materials. The analysis was based on a hot acidic extraction of the sodium and potassium from powdered samples followed by atomic adsorption (AA) determination of the extract. Specifically, 1 gram portions of the samples were refluxed in 40 ml of 2N HCL for 1 hour. After filtering, the residue was refluxed again in fresh acid. After filtering again, the residue was washed 3 times with hot water. The fil¬ trates were combined, diluted to 200 g, and analyzed for sodium and potassium on a Perkin-Elmer Model 603 AA manufactured by the Perkin-Elmer Corporation, Pottstown, Pennsylvania. EXAMPLES 1-3 : PREPARATION OF SODIUM DISILICATE PRECURSORS TO BE HYDROLYZED TO PRODUCT HYDRATED LAYERED SODIUM SILI¬ CATE/AMORPHOUS SODIUM SILICATE COMPOSITES TO BE USED FOR COMPARISON TO THE MATERIALS OF OUR INVENTION . EXAMPLE 1: Delta-phase; Si 2 0/Na 2 0 = 2 Hydrated layered sodium silicate/amorphous sodium silicate composite materials can be produced from crystal¬ line Na- disilicates according to the following process. An amorphous sodium silicate glass, having a composition of Si0 2 /Na 2 0 in a mole ratio of 2, is prepared by the fusion of a sodium carbonate and silica between 1100°C and 1300°C fol¬ lowed by rapid cooling of the molten sodium glass. The cool amorphous sodium glass is dissolved in DI 2 -water to produce liquid silicate. The liquid silicate is spray dried to produce a sodium hydrous polysilicate having approximately 18 to 22 percent by weight water. The sodium hydrous poly- silicate is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium silicate phase present in the product as identified by X-ray diffraction was determined to be delta-phase disilicate. EXAMPLE 2: Delta-phase; Si0 2 /Na 2 0 = 2.4 Preparation of hydrated layered sodium silicate/ amorphous sodium silicate composite materials to be used as a comparison to the materials of our invention begin by synthesizing a crystalline disilicate which is produced according to the following process. The first step in the synthesis of a crystalline disilicate is the preparation of an amorphous sodium silicate glass, having a composition of Si0 2 /Na 2 0 in a mole ratio of 2.4, by the fusion of a sodium carbonate and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium glass. The cool amor- phous sodium glass is dissolved in DI 2 -water to produce liquid silicate. The liquid silicate is spray dried to produce a sodium hydrous polysilicate having approximately 18 to 22 percent by weight water. The sodium hydrous poly¬ silicate is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium silicate phase present in the product as identified by X-ray diffraction was determined to be delta disilicate. EXAMPLE 3: Delta-phase; Si0 2 /Na 2 0 = 3.22 Preparation of hydrated layered sodium silicate/ amorphous sodium silicate composite materials to be used as a comparison to the materials of our invention begin by synthesizing a crystalline disilicate which is produced according to the following process. The first step in the synthesis of a crystalline disilicate is the preparation of an amorphous sodium silicate glass, having a composition of Si0 2 /Na 2 0 in a mole ratio of 3.22, by the fusion of a sodium carbonate and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium glass. The cool amor¬ phous sodium glass is dissolved in DI 2 -water to produce liquid silicate. The liquid silicate is spray dried to produce a sodium hydrous polysilicate having approximately 18 to 22 percent by weight water. The sodium hydrous poly- silicate is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium silicate phase present in the product as identified by X-ray diffraction was determined to be delta disilicate. EXAMPLES 4-9 : PREPARATION OF CRYSTALLINE Na-K SILICATE PRECURSORS (DB-1 PHASE) TO BE HYDROLYZED TO PRODUCE HYDRATED LAYERED Na-K SILICATE /AMORPHOUS Na-K SILICATE COMPOSITES OF THE PRESENT INVENTION EXAMPLE 4: DB-1 phase produced from Na/K glass; SiO 2 /(0.9Na 2 O + 0.1K 2 O) = 1.7 Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 /(0.9Na 2 O + 0.1K 2 O) in a mole ratio of 1.7, by the fusion of a sodium carbonate, potassium carbonate, and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium/potassium glass. The cool amorphous sodium/potassium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium/potassium glass and 2 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crys¬ talline DB-1 phase silicate, as disclosed in US Patent Application Serial Number 08/270,489. EXAMPLE 5: DB-1 phase produced from Na/K glass; SiO 2 /(0.9Na 2 O + 0.1K 2 O) = 2 Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 / (0.9Na 2 O + 0.1K 2 O) in a mole ratio of 2, by the fusion of a sodium carbonate, potassium carbonate, and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium/potassium glass. The cool amorphous sodium/potassium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium/potassium glass and 2 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crys- talline DB-1 phase silicate. EXAMPLE 6: DB-1 phase produced from Na/K glass; SiO 2 /(0.8Na 2 O + 0.1K 2 O) = 2 Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 / (0.8Na 2 O + 0.1K 2 0) in a mole ratio of 2, by the fusion of a sodium carbonate, potassium carbonate, and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium/potassium glass. The cool amorphous sodium/potassium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium/potassium glass and 2 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crys¬ talline DB-1 phase silicate. EXAMPLE 7: DB-1 phase produced from Na/K glass; Si0 2 /(0.9Na 2 0 + 0.1K 2 0) = 2.4 Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 /(0.9Na 2 O + 0.1K 2 O) in a mole ratio of 2.4, by the fusion of a sodium carbonate, potassium carbonate, and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium/potassium glass. The cool amorphous sodium/potassium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium/potassium glass and 2 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crys¬ talline DB-1 phase silicate. EXAMPLE 8: DB-1 phase produced from Na/K glass; SiO 2 /(0.9Na 2 O + 0.1K 2 O) = 3.22 Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 / (0.9Na 2 O + 0.1K 2 O) in a mole ratio of 3.22, by the fusion of a sodium carbonate, potas- sium carbonate, and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium/potassium glass. The cool amorphous sodium/potassium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium/potassium glass and 2 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crystalline DB-1 phase silicate. EXAMPLE 9: DB-1 phase produced from Na glass and KOH; Ground glass/KOH/DI 2 -water Preparation of the materials of our invention begins by synthesizing a crystalline DB-1 phase silicate which is produced according to the following process. The first step in the synthesis of a crystalline DB-1 phase silicate is the preparation of an amorphous sodium/potassium silicate glass, having a composition of Si0 2 /Na 2 0 in a mole ratio of 2, by the fusion of a sodium carbonate and silica between 1100°C and 1300°C followed by rapid cooling of the molten sodium glass. The cool amorphous sodium glass is ball milled whereby particles of less than 200 microns are produced. A mixture of 8 pbw of ground sodium glass, 11 pbw of 10 molar KOH solution, and 9 pbw of DI 2 -water is heated to 700°C at a heating rate of 5°C/minute and held at this temperature for 3 hours followed by ball milling of the cooled crystalline product whereby particles of less than 50 microns are produced. The crystalline sodium/potassium silicate phase present in the product as identified by X-ray diffraction was determined to be crystalline DB-1 phase silicate. COMPARATIVE EXAMPLES 10-45: PREPARATION OF HYDRATED LAYERED Na-SILICATE /AMORPHOUS Na-SILICATE COMPOSITE MATERIALS FOR COMPARISON TO THE SODIUM /POTASSIUM MATERIALS OF OUR INVENTION COMPARATIVE EXAMPLES 10-18: Sodium hydrated layered silicate (HSL) composite material; Si0 2 /Na 2 0 = 2; ions utilized for hydrolysis H 3 0 A hydrated layered sodium silicate/amorphous sodium silicate composite material was prepared according to the following process. Twenty grams of product from Example 1 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl) , as described in Table 3, for 2 minutes followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. As explained, the product is milled both before and after hydrolyzation. Although ball milling is specified, any appropriate type of milling may be used. Preferably, such milling will reduce the average particle size of the product to less than 200 microns before hydrolyzation and to less than 75 microns after hydrolyzation. This will produce material with sufficient surface area to allow diffusion of the hydrolyzing agent during hydrolysis, and to provide a small enough particle to allow for rapid removal of hardness ions upon introduction into wash water. If the particles are too large before hydrolysis, only the outer particle layers may be hydrolyzed resulting in reduced effectiveness. Similarly, if the particles are too large after hydrolysis, the rate of removal of hardness ions will be controlled by the rate of diffusion into the particle. Generally, the larger the particle, the slower the diffusion of hardness ions will be into the exchanging material. Elemental analysis indicated that the Si0 2 /Na 2 0 ratio of the products synthesized depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen from Table 3. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 3. Table 3: Hydrated Layered Silicates Synthesized by Hydrolysis of Delta Phase Product with a SiO 2 /Na 2 O of 2.0 from Example 1 Example Amount of meq H 3 O + / gram SiO 2 /Na 2 O LOI CER CEC MgER MgEC No. product from anhydrous % Example 1 product from Example 1 (grams) (acid used was 2N HCl) 10 20 0 2.20 13.98 228 259 253 335 βrfθ 11 20 0.24 2.35 15.72 249 272 273 345 12 20 0.60 2.45 22.60 238 291 331 370 13 20 1.20 2.42 22.60 225 274 192 293 14 20 2.40 2.74 31.07 241 294 225 324 15 20 3.00 2.93 27.16 150 275 122 184 16 20 3.60 3.13 27.70 166 284 110 164 17 20 4.20 3.00 26.00 183 286 112 192 18 20 4.80 3.25 23.68 197 282 30 95 COMPARATIVE EXAMPLES 19-29: Sodium HLS composite material; Si0 2 /Na 2 0 = 2.4; ions utilized for hydrolysis H 3 0 + A hydrated layered sodium silicate/amorphous sodium silicate composite material was prepared according to the following process. Twenty grams of product from Example 2 was slurried in 300 ml of DI 2 -water containing various amounts of HCl, as described in Table 4, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /Na 2 0 ratio of the products synthesized depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen from Table 4. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 4. Table 4 Hydrated Layered Silicates Synthesized by the Hydrolysis of Delta Phase Product with a SiO 2 /Na 2 O of 2.4 from Example 2 β EXAMPLES 30-39 : Sodium HLS composite material; Si0 2 /Na 2 0 = 3.22; ions H 3 0 + A hydrated layered sodium silicate/amorphous sodium silicate composite material was prepared according to the following process. Twenty grams of product from Example 3 was slurried in 300 ml of DI 2 -water containing various amounts of HCl, as described in Table 5, for 2 minutes fol¬ lowed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /Na 2 0 ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen from Table 5. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 5. Table 5 Hydrated Layered Silicates Synthesized by Hydrolysis of Delta Phase Product with a SiO 2 /Na 2 O of 3,22 from Example 3 Example Amount of meq H 3 O + / gram SiO 2 /Na 2 O LOI CER CEC MgER MgEC No. product from anhydrous % Example 3 product from Example 3 (grams) (acid used was 2N HCl) 30 20 0 4.40 19.35 249 284 15 49 31 20 0.20 4.52 19.60 235 279 24 24 ftf 32 20 0.40 4.66 19.13 224 282 24 35 t cn 33 20 0.60 5.08 21.84 224 258 24 44 34 20 0.80 5.02 21.67 230 275 24 39 35 20 1.00 5.16 20.01 211 269 20 20 Bf» 36 20 1.50 5.37 18.75 204 276 5 20 37 20 2.00 5.68 19.69 215 254 15 20 38 20 3.00 5.73 18.21 187 231 10 49 39 20 4.00 7.19 20.19 132 185 15 34 COMPARATIVE EXAMPLES 40-43: Sodium HLS composite material; Si0 2 /Na 2 0 = 2; ions utilized for hydrolysis OH~ A hydrated layered sodium silicate/amorphous sodium silicate composite material was prepared according to the following process. Twenty grams of product from Example 1 was slurried in 300 ml of DI 2 -water containing various amounts of sodium hydroxide (NaOH) pellets, as described in Table 6, for 2 minutes followed by filtering and drying at ambient conditions. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /Na 2 0 ratio of the products synthesized depended on the concentration of hydroxyl ions used during the hydrolysis step. Hardness ion binding performance was observed to vary with the Si0 2 /Na 2 0 ratio of the hydrated layered sodium silicate/amorphous sodium silicate composite product, as observed in Table 6. Table 6 Hydrated Layered Silicates Synthesized by the Hydrolysis of Delta Phase Product with a SiO 2 /Na 2 O of 2.0 from Example 1 Example Amount of meq OH ' /gram SiO 2 /Na 2 O LOI CER CEC MgER MgEC No. product from anhydrous product % Example 1 from Example 1 (grams) (base used was NaOH pellets) 00 40 20 0 3.24 26.72 265 325 251 303 41 20 2.0 3.22 26.80 277 337 265 311 42 20 20.0 2.91 24.86 240 294 243 298 43 20 50.0 2.51 20.06 225 283 219 261 COMPARATIVE EXAMPLES 44 AND 45: Sodium HLS composite material of the present invention; varying Si0 2 /Na 2 0 ratio; ions utilized for hydrolysis H 3 0 + ; spray dried A hydrated layered sodium silicate/amorphous sodium silicate composite material was prepared according to the process of the present invention as follows. Two hundred grams of material from each of Examples 44 and 45 were slur¬ ried in 1000 ml of DI 2 -water containing various amounts of HCl, as described in Table 7, for 15 minutes. Each slurry was then introduced into a spray tower through either a wheel atomizer or a nozzle atomizer using an inlet tempera¬ ture of 150°C to 300°C, an outlet temperature of 50°C to 100°C, and a feed rate of 10 to 75 cc/min, depending on the particular product processed. Product from the main chamber and cyclone chamber were combined. X-ray diffraction re¬ vealed that a kanemite phase was present in all cases. Hardness ion binding performance and the Si0 2 /Na 2 0 ratio of the sodium HLS composite products are found in Table 7. It should be noted that the Si0 2 /Na 2 0 ratios of the resulting products did not change from the original Si0 2 /Na 2 0 ratios since the material was spray dried. This is in contrast to previous examples where the products were syn¬ thesized and filtered, resulting in the removal of some soluble material in the supernatant liquid during the fil¬ tering step. It can be concluded from this series of examples and Example 10, that the hardness ion binding performance is dependent on the processing of the hydrolyzed product. Specifically, comparing Example 44 to Example 10, the Si0 2 /Na 2 0 ratios of the resulting products are very similar, but the properties of the materials differ. The magnesium ion binding capacity of the spray dried materials (Example 44) is much higher than the magnesium ion binding capacity of the synthesized and filtered materials (Example 10) . However, the calcium ion binding capacity of the spray dried materials (Example 44) is comparative to the calcium ion binding capacity of the synthesized and filtered materials (Example 10) . Thus the processing of the material dictates the properties of the resulting product. Table 7 Hardness Ion Performance of Hydrated Layered Sodium Silicate/Amorphous Sodium Silicate Spray Dried Composite Products Example Feedstock from meq H 3 O + /gram SiO 2 /Na 2 O LOI CER CEC MgER MgEC No. Example... anhydrous product % (acid used was 2N HCl) 44 1 1.5 2.00 24.39 305 315 347 397 45 3 0.5 3.22 9.13 225 280 242 283 EXAMPLES 46-121: PREPARATION OF HYDRATED LAYERED Na,K- SILICATE/AMORPHOUS Na, K- SILICATE COMPOSITES (DB-2 PHASE)— MATERIALS OF THE PRESENT INVENTION A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of product from Example 5 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl), as described in Table 8, for 2 minutes followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen in Table 8. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product, which was a function of the H 3 0 + concentration, as observed in Table 8. Table 8 Hydrated Layered Na-K Silicates/Amoφhous Na-K Silicate Composites Synthesized by Hydrolysis of Crystalline DB-1 Silicates with a Si ^O^ Na 2 O + 0.1 K 2 O) = 2.0 from Example 5 Example Amount of meq H 3 O + / gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product from Ratio % Example 5 Example 5 (grams) (acid used was 2N HCl) 46 20 0 2.85 26.62 250 290 285 351 47 20 0.2 2.91 26.33 240 300 295 350 48 20 0.4 2.93 27.03 250 305 270 330 49 20 0.6 2.97 26.70 240 290 245 320 NJ 50 20 0.8 2.98 27.24 245 287 230 295 C-Ξ 51 20 1.0 3.07 26.80 235 275 225 316 52 20 1.5 3.19 27.82 240 275 220 292 53 20 2.0 3.38 27.65 237 279 222 286 54 20 3.0 3.53 27.74 201 268 150 240 55 20 4.0 3.74 27.40 181 275 127 191 56 20 5.0 4.16 26.77 140 219 104 158 57 20 7.5 7.76 21.97 125 160 62 117 58 20 10.0 43.09 17.79 55 60 13 23 EXAMPLES 59-71 : DB-2 phase composite material; Si0 2 /(0.8Na 2 O + 0.1K 2 O) = 2; ions utilized for hydrolysis H 3 0 + A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 6 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl), as described in Table 9, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen in Table 9. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 9. Table 9 Hydrated Layered Na-K Silicates/Amoφhous Na-K Silicate Composites Synthesized by Hydrolysis of Crystalline DB-1 Silicates with a SiO 2 /(0.8 Na 2 O + 0.2 K 2 O) = 2.0 from Example 6 Example Amount of meq H 3 O + /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product from Ratio % Example 6 Example 6 (grams) (acid used was 2N HCl) 59 20 0 2.80 29.21 225 270 265 340 60 20 0.2 2.89 28.95 229 279 204 299 61 20 0.4 2.88 28.90 195 270 160 256 o 62 20 0.6 2.91 28.70 185 265 100 195 63 20 0.8 2.97 29.50 185 275 70 115 64 20 1.0 2.99 29.40 180 280 70 140 65 20 1.5 3.07 29.00 145 265 105 150 66 20 2.0 3.22 29.04 150 275 70 140 67 20 3.0 3.50 29.34 160 280 65 130 68 20 4.0 3.71 28.31 170 255 55 115 69 20 5.0 4.13 27.55 145 230 60 115 70 20 7.5 7.02 22.33 120 165 50 105 71 20 10.0 31.03 17.91 20 20 15 20 EXAMPLES 72-84 : DB-2 phase composite material; Si0 2 /(0.9Na 2 0 + 0.1K 2 O) = 2.4 ions utilized for hydrolysis H 3 0 + A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 7 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl) , as described in Table 10, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen in Table 10. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 10. Table 10 Hydrated Layered Na-K Silicates/Amorphous Na-K Silicate Composites Synthesized by Hydrolysis of Crystalline DB-1 Silicates with a SiO 2 /(0.9 Na 2 O + 0.1 K 2 O) = 2.4 from Example 7 Example Amount of meq H 3 O + /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product from Ratio % Example 7 Example 7 (grams) (acid used was 2N HCl) 72 20 0 2.90 25.04 260 286 215 250 73 20 0.2 2.94 24.39 262 306 230 280 74 20 0.4 2.99 23.69 250 290 240 295 Λ OJ ON 75 20 0.6 3.02 22.29 245 285 190 275 76 20 0.8 3.06 22.57 230 288 170 250 X9 77 20 1.0 3.09 21.61 215 275 119 237 78 20 1.5 3.22 21.70 221 282 100 229 79 20 2.0 3.39 21.08 204 274 96 215 80 20 3.0 3.84 20.75 209 269 81 202 81 20 4.0 4.62 19.78 195 275 85 165 82 20 5.0 5.41 19.35 162 241 67 110 83 20 7.5 13.25 15.45 129 155 53 70 84 20 10.0 14.14 15.52 50 65 45 60 EXAMPLES 85-97 : DB-2 phase composite material; Si0 2 /(0.9Na 2 0 + 0.1K 2 O) = 3.22; ions utilized for hydrolysis H 3 0 + A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 8 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl) , as described in Table 11, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen in Table 11. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 11. Table 11 Hydrated Layered Na-K Silicates/Amorphous Na-K Silicates Composites Synthesized by Hydrolysis of Crystalline DB-1 Silicates with a SiO 2 /(0.9 Na 2 O + 0.1 K 2 O) = 3.22 from Example 8 Example Amount of meq H 3 O + /gram SiOj/Alkali LOI CER CEC MgER MgEC No. product from anhydrous product from Ratio % Example 8 Example 8 (grams) (acid used was 2N HCl) 85 20 0 4.33 20.23 250 289 75 115 86 20 0.2 4.35 21.46 241 287 70 150 87 20 0.4 4.48 19.72 249 291 60 140 CO «Λ oo 88 20 0.6 4.62 20.64 239 279 50 121 89 20 0.8 4.75 20.51 242 283 48 109 90 20 1.0 5.0 19.27 231 276 55 95 91 20 1.5 5.42 18.38 225 268 50 85 i_s» 92 20 2.0 6.06 19.48 216 262 45 75 93 20 3.0 6.12 19.33 201 270 40 65 94 20 4.0 6.29 20.59 187 221 35 55 95 20 5.0 8.51 19.23 78 159 30 48 96 20 7.5 42.41 10.91 55 77 25 35 97 20 10.0 77.09 8.73 21 35 20 30 EXAMPLES 98-101 : DB-2 phase composite material; Si0 2 /(0.9Na 2 O + 0.1K 2 O) = 2 ions utilized for hydrolysis OH ~ A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 5 was slurried in 300 ml of DI 2 -water containing various amounts of sodium hydroxide (NaOH) pellets, as described in Table 12, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydroxyl ions used during the hydrolysis step, as may be seen in Table 12. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the OH " concentration) , as observed in Table 12. Table 12 Hydrated Layered Na-K Silicate/ Amorphous Na-K Silicates Composites Synthesized by the Hydrolysis of Crystalline DB-1 Silicates with a Siθ 2 /(0.9 Na 2 O + 0.1 K 2 O) 2.0 from Example 5 Example Amount of meq OH ' /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product Ratio % Example 5 from Example 5 (grams) (base used was NaOH pellets) CO 4-» 98 20 0 2.85 26.62 250 290 285 351 O 99 20 2.0 2.78 24.24 240 289 274 335 100 20 20.0 2.54 25.01 225 282 269 311 101 20 50.0 2.46 24.79 216 277 245 288 EXAMPLES 102-105 : DB-2 phase composite material; Si0 2 /(0.9Na 2 O + 0.1K 2 O) = 2; ions utilized for hydrolysis OH " A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 5 was slurried in 300 ml of DI 2 -water containing various amounts of sodium hydroxide (NaOH) pellets, as described in Table 13, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydroxyl ions used during the hydrolysis step, as may be seen in Table 13. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the OH " concentration) , as observed in Table 13. Table 13 Hydrated Layered Na-K Silicate/Amorphous Na-K Silicates Composites Synthesized by the Hydrolysis of Crystalline DB-1 Silicates with a Si J(0.9 Na 2 O + 0.1 K 2 O) 2.0 from Example 5 Example Amount of meq OH ' /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product Ratio % Example 5 from Example 5 (grams) (base used was KOH pellets) CΛ to 102 20 0 2.85 26.62 250 290 285 351 103 20 2.0 2.85 27.51 242 287 275 332 104 20 20.0 2.58 28.38 220 283 273 311 105 20 50.0 2.11 28.83 195 268 231 250 ■ » EXAMPLES 106-118 : DB-2 phase composite material; ground glass/KOH/DI 2 -water; ions utilized for hydrolysis H 3 0 + A DB-2 phase composite material was prepared accord- ing to the process of our invention as follows. Twenty grams of material from Example 9 was slurried in 300 ml of DI 2 -water containing various amounts of hydrochloric acid (HCl), as described in Table 14, for 2 minutes, followed by filtering and drying at ambient conditions. The product was pulverized by ball milling. X-ray diffraction revealed that a kanemite phase was present. Elemental analysis indicated that the Si0 2 /alkali ratio of the products depended on the concentration of hydronium ions used during the hydrolysis step, as may be seen in Table 14. Hardness ion binding performance was observed to vary with the Si0 2 /alkali ratio of the resulting product (which was a function of the H 3 0 + concentration) , as observed in Table 14. Table 14 Hydrated Layered Na-K Silicates/Amoφhous Na-K Silicate Composites Synthesized by Hydrolysis of Crystalline DB-1 Silicates with a SiO 2 /( Na 2 O + K 2 O) = from Example 9 Example Amount of meq H 3 O + /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. product from anhydrous product from Ratio % Example 9 Example 9 (grams) (acid used was 2N HCl) 106 20 0 2.95 24.25 235 290 288 338 107 20 0.2 3.03 23.01 220 285 268 323 108 20 0.4 3.07 22.47 230 291 237 297 109 20 0.6 3.09 19.77 225 285 242 292 110 20 0.8 3.22 23.69 206 277 230 280 111 20 1.0 3.39 22.29 210 265 189 245 112 20 1.5 3.84 21.61 190 271 172 242 113 20 2.0 3.91 21.70 201 246 158 235 114 20 3.0 4.24 20.75 179 235 145 237 115 20 4.0 4.62 19.35 161 202 120 205 116 20 5.0 5.41 19.78 138 189 62 138 117 20 7.5 13.32 15.45 114 175 57 112 118 20 10.0 54.14 15.52 25 45 10 25 EXAMPLES 119-121 : DB-2 phase composite material of the present invention; varying Siθ 2 /alkali ratio; ions utilized for hydrolysis H 3 0 + ; spray dried DB-2 phase composite materials were prepared accord¬ ing to the process of the present invention as follows. Two hundred grams of material from each of Examples 4, 5 and 8 were slurried in 1000 ml of DI 2 -water containing various amounts of HCl, as described in Table 15, for 15 minutes. Each slurry was then introduced into a spray tower through either a wheel atomizer or a nozzle atomizer using an inlet temperature of 150°C to 300°C, an outlet temperature of 50°C to 100°C, and a feed rate of 10 to 75 cc/min, depending on the particular product processed. Product from the main chamber and cyclone chamber were combined. X-ray diffrac¬ tion revealed that a kanemite phase was present in all cases. Hardness ion binding performance and the Si0 2 /alkali ratio of the sodium/potassium HLS composite products are found in Table 15. It should be noted that the Si0 2 /alkali ratios of the resulting products did not change from the original Si0 2 /alkali ratios since the material was spray dried. This is in contrast to previous examples where the products were synthesized and filtered, resulting in the removal of some soluble material in the supernatant liquid during the filtering step. It can be concluded from these examples and the abovementioned Examples 44 and 45, that the hardness ion binding performance is also dependent on the processing of the hydrolyzed product. Specifically, comparing Examples 120 and 121 to Examples 44 and 45, respectively, it can be seen that the hardness ion binding performance is very similar at near identical Si0 2 /alkali ratios. However, comparing hydrated layered alkali silicates/amorphous alkali silicate composites produced by spray drying to hydrated layered alkali silicates/amorphous alkali silicate compo¬ sites produced by slurrying and filtering, reveals that spray drying produces a product composition which is identi¬ cal to the precursor composition and a product that has superior hardness ion binding performance. Thus, the pro¬ cessing of the material dictates the properties of the resulting product. Table 15 Hardness Ion Performance of Hydrated Layered Na-K Silicate/Amorphous Na-K Silicate Spray Dried Composite Products Example Feedstock from meq H 3 O + /gram SiO 2 /Alkali LOI CER CEC MgER MgEC No. Example... anhydrous product Ratio % (acid used was 2N HCl) 119 4 1.5 1.7 13.94 320 343 408 433 Λ» 120 5 0.5 2.0 14.07 270 295 350 380 121 8 3.0 3.22 14.13 225 275 215 265 EXAMPLES 122-124: COMPARISON OF MATERIALS OF PRESENT INVENTION TO PRIOR ART EXAMPLE 122: Comparison of DB-2 phase composites to hydrated layered Na- co posites produced from their crystalline precursors; Si0 2 /alkali = 2; H 3 0 + ions Comparing Example 48 to Example 15 (both having a similar Si0 2 /alkali ratio) reveals that the CER and CEC improved by 67% and 11%, respectively, and the MgER and MgEC improved by 121% and 79%, respectively, as seen in Table 16. The increase in hardness ion binding performance may be due to the present of potassium in the composite. For equivalent calcium ion binding performance, one must compare Examples 47 and 12; however, it should be noted that the Si0 2 /alkali ratios of these two composites are different. This indicates that the composition and pro¬ cessing of the crystalline silicate precursor are important factors in producing the composite of our invention. Table 16 Comparison of Hardness Ion Binding Performance at 25°C of Hydrated Layered Sodium/Potassium Silicate Products (from Examples 47 and 48) to Hydrated Layered Sodium Silicate Products (from Examples 12 and 15) Example Si0 2 /Alkali CER CEC MgER MgEC No. Ratio 12 2.74 241 294 225 324 15 2.93 150 275 122 184 47 2.91 240 300 295 350 48 2.93 250 305 270 330 EXAMPLE 123: Comparison of DB-2 phase composites to hydrated layered Na- co posites produced from their crystalline precursors having Si0 2 /alkali = 2.4 and 3.22; H 3 0 + ions At similar Si0 2 /alkali ratios, the DB-2 products of this invention exhibit comparable calcium binding perform¬ ances to the Na- HLS system, but higher magnesium binding performances. This can be seen when comparing Example 19 to Example 80 and Example 32 to Example 88 (see Table 17) . This may also be attributable to the potassium in the DB-2 material. Table 17 Comparison of Hardness Ion Binding Performance at 25°C of Hydrated Layered Sodium/Potassium Silicates Products (from Example 80 and 88) to Hydrated Layered Sodium Silicate Products (from Examples 19 and 32) Example Siθ 2 /Alkali CER CEC MgER MgEC No. Ratio 19 3.94 206 277 63 163 32 4.66 224 282 24 35 80 3.84 209 269 81 202 88 4.62 239 279 50 121 48 SUBSMΪE SHEET R EXAMPLE 124: Comparison of DB-2 phase composites to hydrated layered Na- co posites produced from their crystalline precursors having Si0 2 /alkali = 2; ions OH " Comparing Example 100 to Example 43 (both having a similar Si0 2 /alkali ratio and produced using NaOH as the hydrolyzing agent to synthesize the composites) revealed that the calcium ion binding performances are comparable, whereas the MgER and MgEC increased by 23% and 19%, res¬ pectively, as seen in Table 18. When KOH was used as the hydrolyzing agent, Example 104, the hardness ion binding performance was similar to a composite produced using NaOh as the hydrolyzing agent, Example 100. Overall, the pre¬ sence of potassium in the DB-2 composite enhances the magnesium hardness binding performance as well as the cal¬ cium hardness ion binding performance. It is to be understood that both the foregoing gen¬ eral description and detailed description are exemplary, but are not restrictive, of the invention. Table 18 Comparison of Hardness Ion Binding Performance at 25°C of Hydrated Layered Sodium/Potassium Silicate Products (from Examples 100 and 104) to Hydrated Layered Sodium Silicate Products (from Example 43) Example Si0 2 /Alkali CER CEC MgER MgEC No. Ratio 43 2.51 225 283 219 261 100 2.54 225 282 269 311 104 2.58 220 283 273 311 49

Claims: CLAIMS We claim: 1. A process for the production of a composite product including a crystalline hydrated layered sodium and potassium silicate and an amorphous sodium and potassium silicate comprising: a. producing a material including a crystalline disilicate by heating a sodium silicate for a predetermined time, at a predetermined temperature; b. hydrolyzing said material with a hydrolyzing agent sel¬ ected to provide hydrolyzing ions selected from H 3 0 + and OH ~ to produce a composite product; and c. separating said composite product from said hydrolyzing agent. 2. The process of claim 1 wherein said hydrolyzing agent is used in an amount calculated to provide up to 75 milliequivalents of hydrolyzing ions per gram of material. 3. The process of claim 1 wherein the step of prod¬ ucing a material including a crystalline alkali disilicate by heating an alkali silicate for a predetermined time, at a predetermined temperature comprises: a. combining an alkali silicate glass and water to form a mixture; and b. heating said glass and water mixture. 4. The process of claim 1 wherein the step of prod¬ ucing a material including a crystalline alkali disilicate by heating an alkali silicate for a predetermined time, at a predetermined temperature comprises: a. combining a sodium silicate glass and a potassium source to form a mixture; and b. heating said mixture. 5. The process of claim 4 wherein said potassium source is potassium hydroxide. 6. The process of claim 1 including the further step of spray drying said hydrolyzed material. 50 7. A crystalline hydrated layered alkali silicate/ amorphous alkali silicate composite including DB-2 crystal¬ line phase potassium/sodium crystalline material, wherein the crystalline structure of said material is the crystal- line structure of kanemite. 8. The crystalline hydrated layered alkali sili¬ cate/amorphous silicate composite of claim 7 wherein said alkali includes up to 20 mole percent potassium, and at least 80 mole percent sodium. 9. The process of claim 1 wherein said alkali sili¬ cate includes up to 20 mole percent potassium, and at least 80 mole percent sodium. 10. The process of claim 1 wherein the ratio of silicate to alkali in said sodium and potassium silicate is between 1.7 and 3.22. 11. The crystalline hydrated layered alkali sili¬ cate/amorphous alkali silicate composite product produced by the process of claim 1. 12. The crystalline hydrated layered alkali sili- cate/amorphous alkali silicate composite product produced by the process of claim 4. 13. The crystalline hydrated layered alkali sili¬ cate/amorphous alkali silicate composite product produced by the process of claim 6. 14. A detergent builder comprising a composite of crystalline hydrated layered sodium and potassium silicate and amorphous sodium and potassium silicate. 15. A detergent builder comprising the crystalline hydrated layered sodium and potassium silicate and amorphous sodium and potassium silicate composite produced by the pro¬ cess of claim 1. 16. A cleaning composition comprising effective amounts of surfactants and a builder comprising a composite of crystalline hydrated layered sodium and potassium sili- cate and amorphous sodium and potassium silicate. 51 LE26 17. The composite product of claim 11 wherein said composite product has a silica to alkali ratio between 2.75 and 4.25 and a hardness ion binding capacity of up to 6.1 milliequivalents Ca 2+ per gram of anhydrous product and up to 7 milliequivalents Mg 2+ per gram of anhydrous product. 18. The composite product of claim 11 wherein said composite product has a silica to alkali ratio between 2.9 and 5.5 and a hardness ion binding capacity of up to 6.2 milliequivalents Ca 2+ per gram of anhydrous product and up to 5.9 milliequivalents Mg 2+ per gram of anhydrous product. 19. The composite product of claim 11 wherein said composite product has a silica to alkali ratio between 4.25 and 8.75 and a hardness ion binding capacity of up to 5.9 milliequivalents Ca 2+ per gram of anhydrous product and up to 3 milliequivalents Mg 2+ per gram of anhydrous product. 20. The composite product of claim 11 wherein said composite product has a silica to alkali ratio between 2.1 and 2.9 and a hardness ion binding capacity of up to 5.9 milliequivalents Ca 2+ per gram of anhydrous product and up to 7.1 milliequivalents Mg 2+ per gram of anhydrous product. 21. The composite product of claim 12 wherein said composite product has a silica to alkali ratio between 2.9 and 13.5 and a hardness ion binding capacity of up to 5.9 milliequivalents Ca 2+ per gram of anhydrous product and up to 6.8 milliequivalents Mg 2+ per gram of anhydrous product. 22. The composite product of claim 11 wherein said composite product has a silica to alkali ratio between 1.7 and 3.22 and a hardness ion binding capacity of up to 7.0 milliequivalents Ca 2+ per gram of anhydrous product and up to 8.7 milliequivalents Mg 2+ per gram of anhydrous product. 23. The cleaning composition of claim 16 wherein said composite has a Si0 2 /Na 2 0 ratio between 1.7 and 14.25 and a hardness ion binding capacity of up to 7.0 milliequi¬ valents Ca 2+ per gram of anhydrous product and up to 8.7 milliequivalents Mg 2+ per gram of anhydrous product. 24. The cleaning composition of claim 23 wherein said composition further comprises a co-builder effective in reducing the activity of calcium in solution. 25. The cleaning composition of claim 24 wherein said co-builder is a crystalline aluminosilicate. 26. The cleaning composition of claim 25 wherein said composition includes 5 to 75 weight percent total builder and co-builder which comprises 5 to 95 weight per¬ cent of said builder and 95 to 5 weight percent of said co-builder. 27. A cleaning composition comprising effective amounts of surfactants and the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite product produced by the process of claim 1. 28. A cleaning composition comprising effective amounts of surfactants and the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite product produced by the process of claim 3. 29. A cleaning composition comprising effective amounts of surfactants and the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium silicate composite product produced by the process of claim 4. 30. A cleaning composition comprising effective amounts of surfactants, builder, and co-builder including 5 to 75 weight percent total- builder and co-builder which comprises 5 to 95 weight percent of said builder and 95 to 5 weight percent of said co-builder, and wherein said builder comprises the crystalline hydrated layered sodium and potassium silicate/amorphous sodium and potassium sili¬ cate composite of claim 1. 31. The cleaning composition of claim 16 wherein said composition includes 5 to 75 weight percent total builder and co-builder which comprises 5 to 95 weight percent of said builder and 95 to 5 weight percent of said co-builder. 32. The cleaning composition of claim 31 wherein said co-builder is a zeolite. 33. The cleaning composition of claim 32 wherein said zeolite is selected from the group consisting of Zeol¬ ite NaA, Zeolite P, Zeolite NaX and Zeolite K/NaX. 34. A crystalline hydrated layered alkali silicate/ amorphous alkali silicate composite including DB-2 crystal- line phase potassium/sodium crystalline material with an X-ray diffractionpattern having d-spacings of 10.30A, 5.13A, 4.02A, 3.63A, 3.43A, 3.16A, 3.09A, 2.47A, 2.42A and 2.09A. 54

Inventors: BORGSTEDT ERIC VON REHREN, DENKEWICZ RAYMOND P JR, DENKEWICZ, RAYMOND, P., JR., VON REHREN BORGSTEDT, ERIC
Applicants: PQ CORP, PQ CORPORATION
Application year: 1995
Main classification: C01B33
IPC codes: C01B33, C11D3