FIELD OF THE INVENTION

This invention describes a rapid hydrothermal process for the production of crystalline aluminosilicates having an orthorhombic zeolite N structure within the EDI framework type.

The products of this process are novel compositions of matter with exceptional selectivity for ion exchange of certain species from solutions. These novel products demonstrate physical and chemical characteristics attributable to the method of production.

BACKGROUND OF THE INVENTION

Hydrothermal synthesis of sodic zeolites is well described in prior art such as texts by Breck (1974) and Szosak (1998). Hydrothermal synthesis of potassic zeolites is limited to early work by Barrer and colleagues (Barrer ef al., 1953; Barrer and Baynham, 1956; Barrer ef a/., 1968; Barrer and Marcilly, 1970; Barrer and Mainwaring, 1972) and recent studies by Basadela and Tara (1995), Christensen and Fjellvag (1997), Healy et al. (2000) and Belver et a/. (2002).

Prior art referred to in the background and in the attached Bibliography is fully incorporated into this specification by way of reference.

The early work by Barrer and colleagues demonstrated the formation of zeolite K-F - a tetragonal structure within the EDI framework type - predominantly at low temperatures (Ae. between 8O ⁰ C and 17O ⁰ C) over a range of KOH molarities. At higher temperatures (;.e. 200 ⁰ C to 35O ⁰ C), the dominant potassic phase is either kalsilite or kaliophyllite depending on the starting composition. Syntheses at higher temperatures favour the feldspathoids such as leucite and analcite (Barrer and Baynham, 1956; Barrer and Marcilly, 1970).

Nevertheless, Barrer and Mainwaring (1972) showed that zeolite K-F could be crystallised at temperatures as low as 8O ⁰ C under conditions of high KOH molarity while Barrer ef al. (1968) showed that kaliophyllite is formed at 8O ⁰ C with high KOH molarity. Barrer and Marcilly (1970) used a stoichiometric amount of KOH and a high excess of KCI but did not produce an orthorhombic zeolite from a kaolin starting material.

In general, reaction times for many of these early syntheses ranged from a few days up to ten days (Barrer ef al., 1968; Barrer and Marcilly, 1970). Reaction times of 16 hours to 24 hours also gave crystalline products, but at temperatures generally higher than 300 ⁰ C (Barrer and Baynham, 1956).

Data from this early period on syntheses in potassic aluminosilicate systems are contradictory and confusing as noted in a summary article by Sherman (1977). In addition, the nomenclature for zeolites has evolved over a period of decades since the early discovery of

hydrothermal synthesis routes by Barrer. The term "zeolite N" as disclosed in US 3,414,602 and US 3,306,922 was initially used to designate an ammonium or alkyl ammonium substituted cationic species. However, this nomenclature to describe alkyl ammonium or ammonium substituted species is no longer practised in order to avoid confusion (Szostak, 1998). Sherman (1977) describes the confusion at the time with nomenclature for eleven zeolites synthesised in the K ₂ O-AI ₂ O ₃ -SiO ₂ -H ₂ O system and clarifies relationships for Linde F and zeolite K-F. However, Sherman (1977) did not describe zeolite N nor any possible variants on the type structure in this work.

More recent syntheses attempting to replicate this earlier work by Barrer and colleagues, focused on the use of excess salts (e.g. KCI) to assist the formation of zeolite N (Christensen and Fjelvag, 1997). Christensen and Fjelvag (1997; 1999) reported hydrothermal synthesis of zeolite N from a static solution at 300 ⁰ C using zeolite Na-A and excess KCI as starting materials. The pH of this reaction mix is less than 11 and the reaction period is seven days.

Prior art for hydrothermal synthesis has been summarised in Figure 1 which shows phases formed in the potassic aluminosilicate system for a range of KOH molarities. This figure is based on an early attempt by Barrer ef a/. (1968) to show key relationships in this system. Figure 1 includes examples of syntheses undertaken since the publication by Barrer ef a/. (1968).

Figure 1 shows that hydrothermal synthesis of potassic aluminosilicates from static solutions will result in formation of;

(a) zeolite K-F at 8O ⁰ C < T < 200 ⁰ C at 0 < [KOH] < 10 (b) zeolite N at 200 ⁰ C < T < 300 ⁰ C at 0 < [KOH] < 5 only in the presence of excess KCI

(Barrer and Marcilly, 1970) (C) kaliophyllite at 80 ⁰ C < T < 300 ⁰ C at 1 < [KOH] < 30

(d) kalsilite at 200 ⁰ C < T < 450 ⁰ C for 0 < [KOH] < 15

(e) chabazite or near chabazite structures (zeolite K-G) at low temperatures 8O ⁰ C < T < 12O ⁰ C and low molarity 0 < [KOH] < 2

(f) other zeolites (such as JBW and L) at T < 200 ⁰ C and [KOH] < 5, where [KOH] represents molarity of KOH in the reaction mix. These examples generally occur over time periods of 2 to 10 days.

The aluminosilicate, zeolite N is the only orthorhombic structure identified in the potassic aluminosilicate system. Prior art shows that this structure is formed at high temperature (T > 200 ⁰ C) in the presence of potassium chloride over reaction periods of four days to seven days.

Barrer and Marcilly (1970) identified two other crystalline aluminosilicates of tetrahedral structure that form at temperatures above 200 ⁰ C. These structures - termed zeolite K-F(Br) and zeolite K-F(I) - are formed at 24O ⁰ C and 32O ⁰ C, respectively over periods of four days. Zeolite K-F(Br) is sometimes referred to as zeolite O (Barrer and Marcilly, 1970).

Prior art therefore teaches that at temperatures between 100 ⁰ C and 200 ⁰ C for reaction times between two days and ten days, products of hydrothermal reaction with potassic reagents are zeolite K-F (e.g. Barrer and Marcilly, 1970), kaliophyllite (Barrer and Marcilly, 1970; Barrer et al., 1968) or chabazite (Barrer ef a/., 1968).

Recently, International Publication WO 2004/087573 demonstrated that compositions as described in this reference which are a combination of a water soluble monovalent cation, a solution of hydroxyl ions, and an aluminosilicate which form a resultant mixture having a pH greater than 10 and a H ₂ OZAI ₂ O ₃ ratio in the range of 30-220 can be used to synthesise zeolite N at low temperatures (/. e. < 100 ⁰ C) under non-hydrothermal conditions in a stirred reaction at ambient pressure which was one atmosphere. This was equivalent to the reaction being carried out in an open vessel. However this meant that this process was not capable of being carried out on a commercial basis as explained hereinafter.

SUMMARY OF THE INVENTION

This invention relates to the surprising discovery of a process using caustic solutions at high molarity and any aluminosilicates such as kaolin, meta-kaolin, zeolite A and/or montmorillonite which results in the production of a crystalline aluminosilicatezeolite N structure by a stirred hydrothermal synthesis route between 100 ⁰ C and 25O ⁰ C which can be carried in a closed reacting vessel or at pressures in excess of atmosphere and thus up to 12 atmospheres if required. This meant that the reaction could be carried out much faster than the process described in International Publication WO 2004/087573 with possible reaction times of less than 2 days and more favourably between 30 minutes and 4 hours. This also meant that the process could be carried out on a commercial basis because the reaction was driven more to completion and thus provided a more purified product. The invention also relates to the direct synthesis of zeolite N aluminosilicates with different anionic compositions such as with hydroxyl, bromine, fluorine, iodine, nitrate and carbonate ions.

In one aspect of the present invention there is provided a process for making aluminosilicates of zeolite N structure including the steps of: (i) combining a water soluble monovalent alkali metal or ammonium cation with a solution of suitable anions in a basic solution and an aluminosilicate to form a resultant mixture having a pH greater than 12 and a KOH molarity greater than 1.30;

(ii) heating and stirring the resultant mixture to a temperature of between 100 ⁰ C

and 25O ⁰ C excluding a boiling point of the mixture for a time of between 1 minute and 100 hours until a crystalline product of zeolite N structure is formed as determined by X-ray diffraction or other suitable characteristic; and

(iii) separating the product from the mixture whereby said product is a solid with zeolite N structure.

Preferably the alkali metal used in step (i) comprises a potassium, sodium, lithium, rubidium or caesium ion in the solution or mixtures of these ions such as sodium and potassium. Preferably the alkali metal is potassium. The solution of suitable anions may have a pH greater than 13 and the ratio of H ₂ OZAI ₂ O ₃ in the reaction mixture may range from 1.0 to 500. The solution of suitable anions in the resultant mixture of step (i) may include halide, nitrate, carbonate or hydroxyl ion. Halide anions such as fluoride, chloride, iodide and bromide may be used. In this embodiment, the halide may have an alkali metal cation or monovalent soluble cation which may include potassium, sodium, lithium, ammonium, rubidium or caesium or mixtures thereof such as sodium and potassium. Preferably the alkali metal is potassium or mixtures of alkali metals including potassium.

In step (i) the aluminosilicate may have an Si:AI ratio in the range 1.0 to 5.0 and more preferably in the range 1.0 to 3.0.

In step (ii) the heating step is preferably carried out at temperatures in the range 100 ⁰ C to - 200 ⁰ C. Preferably, the reaction time is in the range 30 minutes to 4 hours. In step (iii) the solid product may be separated from the caustic liquor by suitable means such as, for example, by washing or filtration.

The disclosed process enables the production of many crystalline aluminosilicates of orthorhombic structure including zeolite N as example. In general, the compositions of zeolite N achievable by the synthesis process can be described by the formula: (M _1-3 , Pa)I ₂ (AIbSiO) ₁₀ O ₄ O(Xi-Ci, Yd) ₂ nH ₂ O where

M = alkali metal or ammonium (e.g. K, Na, NH ₄ ); P = alkali metal, ammonium or metal cations exchanged in lieu of alkali metal or ammonium ion, X = nitrate, carbonate or hydroxyl and Y = OH or other anion; for 0 < a < 1 , 1 < c/b ≤ oc, 0 ≤ d < 1 and 1 ≤ n < 10. In the prior art reference International Publication WO 2004/087573 reference is made to the same formula as described above with X being limited to halide. In the advent of the present invention X has now been broadened out to including nitrate, carbonate or hydroxyl.

As exemplified below, the method of the invention may give rise to potassium-only, potassium and sodium, potassium and ammonium and potassic high silica forms of zeolite N. Other forms of zeolite N produced by the disclosed invention include a potassium-only form with

hydroxyl, nitrate or carbonate ion as the anion rather than chloride. These compositional variants have common properties arising from the method of production as described below.

Other compositional variations to the forms described below are possible as will be appreciated by those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 : Plot of temperature of formation versus KOH molarity for the potassic aluminosilicate system based on data compiled from prior art.

Figure 2: Time-temperature-transformation diagram for the synthesis of zeolite N of the current invention (filled circles; Examples 2 and 3) compared with prior art synthesis of zeolite

N (filled squares).

Figure 3: Powder X-ray diffraction pattern for zeolite N synthesised by the method given in

Example 11.

Figure 4: Plot of temperature of formation versus KOH molarity for the potassic aluminosilicate system for prior art and syntheses of this invention (filled diamonds).

DETAILED DESCRIPTION OF THE INVENTION

The reaction conditions for hydrothermal synthesis of zeolite N within reaction times of less than six hours requires precise definition of key parameters such as temperature, type of reagents (i.e. KOH only, KOH with salt etc), molarity of caustic reagent, solids content (i.e. volume of aluminosilicate solid to volume of solute) and pH of reactant mixture. These parameters may have been controlled or implied by practitioners of the prior art but not always reported.

Zeolite synthesis for a particular starting mixture can be described by a conventional time- temperature transformation diagram as shown in Figure 2 for zeolite N of the present invention. Figure 2 also contains all available data from the prior art for the potassic aluminosilicate system with similar Si:AI ratios and/or similar KOH molarity to that of the present invention. The starting reagent conditions for synthesis of zeolite N represented in Figure 2 are as described in Example 2 below. Figure 2 demonstrates that zeolite N is a stable phase produced by hydrothermal synthesis up to 200 ⁰ C after reaction times between 30 minutes and greater than 20 hours contrary to disclosures in all prior art. The preferred conditions for synthesis of zeolite N are outlined by the solid line in Figure 2. Conditions for formation of zeolite N by prior art are outlined by the dotted line in Figure 2. Surprisingly, and contrary to prior art, the synthesis of zeolite N by the present invention occurs at lower temperature (i.e. < 200 ⁰ C) and in less time (i.e. < 100 hours).

Conventional wisdom teaches that higher temperature synthesis will result in more rapid

conversion of a starting mixture and thus, results in reduced reaction times to achieve the desired product.

For the starting materials described in Example 2, higher temperature synthesis (i.e. ≥ 225 ⁰ C) results in formation of kalsilite or kaliophyllite as described in Examples 13 and 14. The production of kalsilite or kaliophyllite at these temperatures is consistent with work on synthesis of potassic aluminosilicates (Barrer ef a/., 1953; Barrer and Baynham, 1956). However, neither of these works demonstrated synthesis of zeolite N.

An important factor for production of zeolite N under hydrothermal conditions is the molarity of KOH. This molarity and, to a lesser extent, the molar ratio of H ₂ O to AI ₂ O _3, strongly influence the pH of the reacting solution. Surprisingly, it has been observed that the pH of the starting reaction mixture must be greater than 12 in order to effect hydrothermal synthesis of zeolite N over the time-temperature regime described in this application.

A set of indexed reflections for Examples 1 , 2, 5, 8 and 9 are shown in Table 1. These reflections confirm the structural determination as zeolite N following data listed in the JCPDF database by Christensen and Fjellvag (1997). Variations in the intensity of key reflections in the regions 11.0° < 2Θ < 13.6 ° and 25° < 2Θ < 35° are manifestations of the different compositional variants compared to the potassium-only form identified by Christensen and Fjellvag (1997).

X-ray powder diffraction patterns for all examples identified as zeolite N in this description follow the type patterns shown in Figure 3 and the data shown in Table 1. Materials produced with these characteristic X-ray diffraction patterns are encompassed within this invention.

As noted earlier, Barrer and Marcilly (1970) describe a tetragonal form of zeolite K-F when reacted with bromide (zeolite K-F(Br), or "zeolite O") or iodide (zeolite K-F(I)) salts. Contrary to the work of Barrer and Marcilly (1970), Examples 8 and 9 demonstrate that hydrothermal synthesis with bromide or iodide salts under the conditions exemplified result in the crystalline orthorhombic aluminosilicate, zeolite N. Furthermore, reaction with a fluoride salt also produces the orthorhombic zeolite N (Example 5).

Prior art has exclusively focused on the use of chloride salts to enhance, or expedite, the formation of zeolite N (Barrer and Marcilly, 1970; Barrer et al., 1968). However, Examples 6 and 7 show that nitrate and carbonate salts are viable reactants in hydrothermal synthesis of zeolite N.

The present invention relating to the process to make zeolite N offers the following advantages:

1. high yields of zeolite N (achieves >90% yield) 2. temperature of reaction is modest (Ae. < 200 ⁰ C)

3. reaction times are very short (ranging from 30 minutes to 4 hours) and

4. volumes of solution required are low.

While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

STANDARD PROCEDURES

For zeolite N reactions at bench and pilot plant scale, a stainless steel reactor equipped with (i) a mixing blade, (ii) an internal heating coil with thermocouple and (iii) a pressurised fitted cover of the type commonly known as a PARR reactor has been employed.

Methods for characterisation of solid products include X-ray powder diffraction, surface area analysis, bulk elemental analysis and cation exchange capacity for ammonium ion. X-ray data were collected on a Bruker automated powder diffractometer using CuKa radiation (λ=1.5406) between 5° and 70° 2Θ at a scan speed of 1° 2Θ per minute using quartz as a calibration standard. The International Centre for Diffraction Data files were used to identify major phases in all samples. Cell dimensions for zeolite N samples were obtained by least-squares refinement from X-ray powder diffraction patterns. Least-squares refinements on cell dimensions require a two-theta tolerance of ±0.1° (i.e. difference between observed and calculated reflections) for convergence. Surface area measurements were obtained on a Micrometrics Tri-Star 3000 instrument using the BET algorithm for data reduction and standard procedures for adsorption and desorption of nitrogen. Bulk elemental analyses for major elements were obtained by inductively coupled plasma spectroscopy (ICP) using standard peak resolution methods.

Cation exchange capacities were determined experimentally for equilibrium exchange of ammonium ion in a 1M NH ₄ CI solution. This method for CEC determination is calibrated against a well-known clay material (Cheto montmorillonite, AZ, Clay Minerals Society Source Clays SAz-1 ; van Olphen and Fripiat, 1979) as an internal standard.

EXAMPLES AND ILLUSTRATIVE EMBODIMENT

Example 1; Production of zeolite N with KOH at T > WO ⁰ C.

66g of 98% solid potassium hydroxide (Redox Chemicals, caustic potash Capota45, QLD Australia), 66g of kaolin (Kingwhite 65, supplied by Unimin Pty Ltd, Kingaroy, QLD Australia) and 221 millilitres of water are placed in a steel hydrothermal reactor. This reaction mix is stirred and heated to 175 ⁰ C. The reactor is maintained at approximately 6 bar pressure during the reaction. The pH of this reaction mix is generally greater than 14.0 and during the course of the reaction may reduce to pH 13.0. The molarity of KOH in this reaction mixture is 5.32.

After 2.0 hours of reactant mixing at 175 ⁰ C, the reaction is stopped by reduction of the temperature to less than 5O ⁰ C via a quench bath, addition of water or both methods and the resulting slurry is separated into solid and liquid components. The solid aluminosilicate - zeolite N - is washed with water and then dried using conventional drying methods to form the final product with characteristic X-ray powder diffraction pattern as listed in Table 1.

Example 2: Production of zeolite N with KOH and KCI at T > 100 ⁰ C. 66g of 98% solid potassium hydroxide (Redox Chemicals, caustic potash Capota45, QLD Australia), 66g of 98% solid potassium chloride (Redox Chemicals, POCHLO16, QLD Australia), 66g of kaolin (Kingwhite 65, supplied by Unimin Pty Ltd, Kingaroy, QLD Australia) and 221 millilitres of water are placed in a steel hydrothermal reactor. This reaction mix is stirred and heated to 13O ⁰ C. The reactor is maintained at approximately 2bar pressure during the reaction. The pH of this reaction mix is generally greater than 14.0 and during the course of the reaction may reduce to pH 13.0. The molarity of KOH in this reaction mixture is 5.32. After 2.0 hours of reactant mixing at 13O ⁰ C, the reaction is stopped by reduction of the temperature to less than 5O ⁰ C via a quench bath, addition of water or both methods and the resulting slurry is separated into solid and liquid components. The solid aluminosilicate - zeolite N - is washed with water and then dried using conventional drying methods to form the final product with characteristic X-ray powder diffraction pattern as listed in Table 1. A reaction mixture with the same quantities of potassium hydroxide, potassium chloride and water, but using 66g of metakaolin instead of kaolin, placed in a hydrothermal reactor at 13O ⁰ C for two hours gave a product with a characteristic X-ray powder diffraction pattern for orthorhombic zeolite N.

Example 3: Variation of process for zeolite N production - time and temperature of reaction.

The reaction mixture described in Example 2 is heated and stirred at 13O ⁰ C ± 5 ⁰ C for periods between 1 hour and 20 hours in separate experiments. After cooling the reaction mix, the solid is separated and dried using conventional methods. The final product(s) with characteristic X- ray powder diffraction patterns identifying the material as zeolite N is obtained. This same reaction mixture (as described in Example 2) is heated and stirred at temperatures ranging from 13O ⁰ C to 200 ⁰ C for periods of 1 hour to 63 hours in separate experiments. After cooling, the separated solid product is an orthorhombic zeolite with characteristic powder X- ray diffraction pattern for zeolite N.

These variations on time and temperature of reaction for a specific reaction mixture which result in the formation of zeolite N are defined as data points in Figure 2 and are encompassed herein by this example.

Example 4: Variation on zeolite N process - KOH with other chloride salt. 66g of 98% solid potassium hydroxide, 15g of 98% solid sodium chloride (Cheetham Salt, Superfine grade, Australia), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. This mixture is stirred and heated to 13O ⁰ C for a period of 2 hours.

The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray diffraction pattern shows that the product is orthorhombic zeolite N.

Example 5: Variation on zeolite N process - KOH with other potassic salt. 66g of 98% solid potassium hydroxide, 51.5g of 95% solid potassium fluoride (AnalR, Selby

Scientific), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. The pH of this reaction mix is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. This mixture is stirred and heated to 13O ⁰ C for a period of 4 hours. The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray diffraction pattern shows (see Table 1) that the product is zeolite N.

Example 6: Variation on zeolite N process - KOH with other potassic salt. 66g of 98% solid potassium hydroxide, 89.5g of 95% solid potassium nitrate (AnalR, Selby Scientific), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. This mixture is stirred and heated to 175 ⁰ C for a period of 2 hours. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32.The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray diffraction pattern shows that the product is orthorhombic zeolite N.

Example 7: Variation on zeolite N process - KOH with other potassic salt.

66g of 98% solid potassium hydroxide, 61 Jg of 95% solid potassium carbonate (AnalR, Selby Scientific), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. This mixture is stirred and heated to 15O ⁰ C for a period of 2 hours. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray diffraction pattern shows that the product is orthorhombic zeolite N.

Example 8: Variation on zeolite N process - KOH with other potassic halide salt. 66g of 98% solid potassium hydroxide, 105g of 95% solid potassium bromide (AnalR, Selby Scientific), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. This mixture is stirred and heated to 13O ⁰ C for a period of 4 hours. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray

diffraction pattern (see Table 1) shows that the product is orthorhombic zeolite N.

Example 9: Variation on zeolite N process - KOH with other potassic halide salt. 66g of 98% solid potassium hydroxide, 147g of 95% solid potassium iodide (AnalR, Selby Scientific), 66g of kaolin and 221 millilitres of water are placed in a PARR reactor. This mixture is stirred and heated to 13O ⁰ C for a period of 4 hours. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. The reaction mix is cooled and the solid product separated from the mother liquor. The characteristic X-ray diffraction pattern (see Table 1) shows that the product is orthorhombic zeolite N.

Example 10: Variation on zeolite N process - range of KOH molarities. The reaction mixture described in Example 1 for which the KOH molarity is 5.32 is varied such that the KOH molarity is 2.7, 4.0 and 16.0, respectively in separate experiments. The pH of these reaction mixtures range from 13.0 to 14.0. These mixtures are stirred and heated to temperatures ranging between 13O ⁰ C and 25O ⁰ C for periods between 1 hour and 12 hours.

The reaction mix is cooled and the solid product separated from the mother liquor. X-ray diffraction patterns are used to identify the primary phase formed from these reaction mixtures and incorporated in the data presented in Figure 4. Figure 4 shows that zeolite N is formed over a range of KOH molarities at various temperatures.

Example 11: Production of zeolite N with KOH and KCI at T> 100 ⁰ C. 66g of 98% solid potassium hydroxide (Redox Chemicals, caustic potash Capota45, QLD Australia), 66g of 98% solid potassium chloride (Redox Chemicals, POCHLO16, QLD Australia), 66g of zeolite Na-A (PQ Corp) and 221 millilitres of water are placed in a steel hydrothermal reactor. The pH of this reaction mixture is greater than 13.0. The molarity of KOH in this reaction mixture is 5.32. After 16.0 hours of reactant mixing at 13O ⁰ C, the reaction is stopped by reduction of the temperature to less than 5O ⁰ C via a quench bath, addition of water or both methods and the resulting slurry is separated into solid and liquid components. The solid aluminosilicate - zeolite N - is washed with water and then dried using conventional drying methods to form the final product with characteristic X-ray powder diffraction pattern as shown in Figure 3.

Comparative Examples

Example 12: Formation of kaolin amorphous derivative with KOH at T > 10O ⁰ C.

The reaction mixture described in Example 1 is heated and stirred in a hydrothermal reactor at 13O ⁰ C fora period of 2.0 hours. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an

X-ray diffraction pattern characteristic of kaolin amorphous derivative as described in Mackinnon et al. (US Patent 6,218,329B).

Example 13: Formation of kaliophyllite with KOH and KCI at T > 100 ⁰ C. The reaction mixture described in Example 2 is heated and stirred in a hydrothermal reactor at 225 ⁰ C for a period of 2.0 hours. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kaliophyllite.

Example 14: Formation of kasilite with KOH and KCI at T > 100° C.

The reaction mixture described in Example 2 is heated and stirred in a hydrothermal reactor at 300 ⁰ C for a period of 2.0 hours. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kalsilite. Comparative data from Examples 12, 13 and 16 and additional variations on time and temperature of reaction for the same reaction mixture are included in Figure 2 and are encompassed herein by this example.

Example 15: Formation of kaliophyllite with other potassium salt. The reaction mixture described in Example 6 is heated and stirred in a hydrothermal reactor at 200 ⁰ C for a period of 2 hours. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kaliophyllite.

Example 16: Formation of kaolin amorphous derivative with KOH at T > 100 ⁰ C.

The reaction mixture described in Example 2 is heated in a hydrothermal reactor at 13O ⁰ C for a period of 2.0 hours without stirring. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kaolin amorphous derivative as described in Mackinnon et a/. (US Patent 6,218,329B).

Example 17: Formation of kaolin amorphous derivative with KOH at T > 100 ⁰ C. The reaction mixture described in Example 2 in which the aluminosilicate is metakaolin is heated and stirred in a hydrothermal reactor at 11O ⁰ C for a period of 1.0 hour. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kaolin amorphous derivative as described in Mackinnon et a/. (US Patent 6,218,329B).

Example 18: Formation ofkalsilite at 300 ⁰ C with excess KCI.

The equivalent reaction mixture described in Christensen andFjelvag (1997) comprising 2Og of zeolite Na-A (PQ Corporation), 50 g of potassium chloride ((Redox Chemicals, POCHLO16, QLD Australia) and 200 ml of water are heated and stirred in a hydrothermal reactor at 300 ⁰ C for 170 hours. The pH of this reaction mixture is less than 11.0. The molarity of KOH in this reaction mixture is 0.0. The solid aluminosilicate is separated from the mother liquor, washed with water and then dried using conventional drying methods. The product shows an X-ray diffraction pattern characteristic of kalsilite (JCPDF File No: 01-076-0635).

Table 1

Indices Example 1 Example 2 Example 5 Example 8 Example 9 k I 2Θ 20 2Θ 2Θ 2Θ

1 1 11.24 5

1 0 12.73 72 12.76 59 12.73 65 12.59 37 12.66 62

0 2 13.60 10 13.64 11 13.54 9 13.40 8 13.54 10

2 0 17.99 2

1 2 18.53 5 18.66 7 18.46 6

1 2 18.66 5

1 1 21.12 5 21.02 8

2 1 21.36 8 21.32 8 21.29 7 21.29 5 21.29 7

0 3 22.21 6

1 3 22.31 7

0 2 22.38 6 22.44 7

2 0 25.52 23 25.44 42 25.48 10 25.41 45 25.54 32

2 0 25.56 27

0 4 27.34 17 27.30 10 27.18 15 27.10 13

0 1 27.70 9

3 1 28.02 12 27.97 11 27.88 14 28.04 13

1 0 28.34 15 28.48 32 28.31 12

3 0 28.54 34 28.51 63 28.65 56

1 3 28.71 52 28.70 56

2 3 28.74 57 28.78 46

2 2 28.98 65 28.95 63 28.94 54 28.85 78 28.92 79

2 2 29.02 75

1 4 30.13 100 30.16 70 30.14 85 29.94 100 30.06 100

1 4 30.24 100 30.18 94

1 4 30.22 100

1 4 30.28 66

1 2 31.60 35 31.54 25 31.62 57 31.44 30

3 2 31.82 56 31.72 47 31.76 50 31.75 68

3 2 31.86 67 31.84 64

0 4 32.72 15 32.63 19 32.76 15

0 4 32.78 13 32.70 18

0 4 32.82 14

0 4 32.84 14

2 4 32.90 14 32.86 22 32.88 17

2 4 32.91 18

2 4 32.96 20

2 1 33.37 12 33.14 19 33.30 19

3 1 33.38 22 33.32 17

0 3 33.91 11 33.92 13 33.98 12 33.82 12 34.02 13

0 3 34.02 15 33.92 11

3 3 34.24 12 34.13 12 34.20 11 34.04 11 34.26 13

3 3 34.24 11 34.14 13

0 5 35.46 8 35.34 11 35.42 11

0 5 35.38 11

0 5 35.46 11

1 5 35.50 9 35.49 11

0 0 36.20 9 36.08 13

4 0 36.54 11 36.54 10 36.41 9 36.44 14

4 0 36.54 16

2 4 37.69 9 37.52 11 37.75 10 37.62 10 37.52 10

1 1 38.04 9 37.96 8 37.89 9

4 1 38.16 13

4 1 38.20 11

4 1 38.28 11

4 1 38.32 11

3 0 38.48 10 38.48 14

2 3 38.68 11 38.70 9 38.63 12 38.64 15

0 2 38.77 11 38.72 12 38.72 15

3 3 38.90 11 38.80 13 38.90 13 38.78 15

3 3 38.85 11

1 4 39.71 12 39.78 14

3 4 39.98 18 39.98 21 39.78 27

2 5 40.06 23 39.91 24

2 0 40.58 21

2 0 40.66 18

Bibliography

Baerlocher, Ch. and R. M. Barrer, 2. Kristallogr., 140, 10-26, 1974.

Baerlocher, Ch., and W.M. Meier, Z. Kristallogr., 135, 339-354, 1972.

Barrer, R.M. and J.W. Baynham, J. Chem. Soc, 2882-2891 , 1956.

Barrer, R.M., K. Bromley and PJ. Denny, US Patent 3,306,922, February 28 ^th , 1967.

Barrer, R.M., J. F. Cole and H. Sticher, J. Chem. Soc (A), 2475-2485, 1968.

Barrer, R.M., L. Hinds and EA White, J. Chem Soc, 1466-1475, 1953.

Barrer, R.M. and D. E. Mainwaring, J. Chem. Soc, 1254-1265, 1972.

Barrer, R.M. and C. Marcilly, J. Chem. Soc (A), 2735-2745, 1970.

Barrer, R.M. and B.M. Munday, J. Chem. Soc (A), 2914-2920, 1971.

Basaldella, E.I. and J. C. Tara, Zeolites, 15, 243-246, 1995.

Belver, C, M.A.B. Munoz and M.A. Vicente, Chem. Mater., 14, 2033-2043, 2002.

Breck, D.W. "Zeolite Molecular Sieves: structure, chemistry and use", John Wiley and Sons,

New York, 771 pp, 1974.

Breck, D.W. US Patent 3,723,308, March 27 ^th , 1973.

Christensen, A. Norlund and H. Fjellvag, Acta Chemica Scandinavica, 51, 969-973, 1997.

Christensen, A. Norlund and H. Fjellvag, Acta Chemica Scandinavica, 53, 85-89, 1999.

Cocks, P. A. and CG. Pope, Zeolites, 15, 701-707, 1995.

Healey, A.M., G. M. Johnson and MT. Weller, Microporous and Mesoporous Mater., 37, 153- 163, 2000.

Mackinnon, I.D.R., D. Page and B. Singh, US Patent 6,218.329B1, March 13 ^th , 2001.

Mackinnon, I.D.R., D. Page and B. Singh, US Patent 6,218.329B2, April 17 ^th , 2001.

Milton, R.M. US Patent 2,996,358; August 15 ^th , 1961.

Sherman, J. D. In Molecular Sieves Il (J. R. Katzer, ed.) ACS Symposium Series, 30-42, American Chemical Society, Washington DC, 1977.

Szostak, R., Molecular Sieves. Principles of Synthesis and Identification. Blackie Academic and Professional, 2 ^nd edition, 359pp. 1998.