WO1995003248A1

WO1995003248A1 - Process for preparing ammonium zeolites of low alkali metal content

Info

Publication number: WO1995003248A1
Application number: PCT/US1994/008181
Authority: WO
Inventors: David A. Cooper
Original assignee: Pq Corporation
Priority date: 1993-07-22
Filing date: 1994-07-20
Publication date: 1995-02-02
Also published as: US5435987A; CZ101995A3; ATE170826T1; SK46095A3; AU690137B2; KR100424384B1; KR950703407A; FI951358A; EP0665816A1; AU7473794A; EP0665816A4; EP0665816B1; ES2121606T3; DE69413199T2; FI951358A0; CA2145201C; DE69413199D1; DK0665816T3; CA2145201A1; RU2119452C1

Abstract

Ammonium zeolites of extremely low alkali metal content are prepared by a process of potassium ion exchange followed by ammonium ion exchange. Zeolite X or zeolite Y that contain a significant amount of sodium are contacted with a potassium salt solution under conditions that provide a substantial exchange of potassium for sodium. The potassium enriched zeolite is then contacted with an ammonium salt solution so that the ammonium ion replaces the sodium and potassium ions. The resulting ammonium zeolite X or Y contains considerably less than 1 % alkali metal calculated as Na2O.

Description

PROCESS FOR PREPARING AMMONIUM ZEOLITES OP LOW ALKALI METAL CONTENT

BACKGROUND OF THE INVENTION This invention relates to the ion exchange of zeolites and provides a process for preparing ammonium zeolites of extremely low alkali metal content. In particular, the process involves ion exchange of a zeolite usually containing a significant amount of sodium to a potassium enriched form of the zeolite. Contact with an ammonium salt solution then provides the ammonium form zeolite with low alkali metal content.

Most zeolites (crystalline aluminosilicates) con¬ tain significant amounts of alkali metals, usually sodium. Many applications of said zeolites require the removal of nearly all the sodium and its replacement with ammonium ions. Many zeolite modifications such as stabilization also require removal of nearly all the sodium. Some zeolites including the faujasites have structures that impede the exchange of ammonium ion for sodium, especially when more than 70 to 80% of the sodium they contain is to be exchanged. Prior art methods include exhaustive ion exchange processes with solutions of high concentrations of ammonium salts. See Example IX of US Patent 3,449,020. An alternative process involves the steam calcination of an ammonium zeolite Y that still contains 2.5 to 5% Na₂0 followed by an additional exchange with an ammonium salt solution. See U.S. Patent 3,929,672 among others. This process is not always desirable, as some of the properties of the zeolite are changed and the hydrogen form of the zeolite is formed upon steam calcination. Not all zeolites of the faujasite structure are stable in the hydrogen form. U.S. Patent 4,058,484 discloses a method for providing an ammonium zeolite which involves ion exchange with at least 20 equivalents of ammonium ions for each equivalent of sodium in the zeolite. The temperatures required for the exchange are very high, being in excess of 300°F. It is an object of this invention to provide ammonium zeolite X or ammonium zeolite Y by a method that does not involve temperatures above boiling, the use of ammonium salt solutions of high concentrations, and/or high ammonium ion to zeolite contact ratios.

SUMMARY OF THE INVENTION I have found that ammonium zeolites of faujasite structure such as zeolite X, Y, ZSM-20, ZSM-3 and CSZ-1 with very low alkali metal content can be prepared by a process that includes an initial potassium ion exchange followed by an ammonium ion exchange. The starting zeolite X or Y which can contain sodium (about 11% Na₂0 or more) is contacted with a potassium salt solution at a temperature less than boiling. The contact is such that a significant portion of the zeolitic sodium is replaced by potassium. This exchange need not be exhaustive, as only 80 to 90% of the sodium needs to be exchanged. The nearly complete ion exchange of the zeolitic potassium and sodium for ammonium is now attained relatively easily. The extremely low level of alkali metal in the ammonium zeolite is attained at temperatures less than boiling and without numerous exchange steps. Ion exchange solutions of very high concentrations of ammonium salt and high ammonium ion to zeolite contact ratios are not required. In contrast to the prior art methods that require high temperatures, high contact ratios of NH₄ ⁺/zeolite, highly concentrated ammonium salt solutions, numerous contacts, and steam calcinations to remove the most difficult-to-exchange sodium ions, my process's initial potassium exchange surprisingly renders all of the alkali metal ions (sodium and potassium) easily exchanged for ammonium ions, as will be shown in the examples.

THE INVENTION The zeolites treated by the process of my invention are faujasite-type materials, the most common of which are designated as zeolite X or Y. Such materials are prepared by the hydrothermal treatment of sources of Si0₂, A1₂0₃ and Na₂0 as described in numerous U.S. Patents including 2,882,244 and 3,130,007. The zeolites produced by the processes disclosed in these patents are represented by the following formula:

0.9 ±0.2 Na₂0:Al₂0₃:X Si0₂:Y H₂0 wherein X can be about 2 to 6, and Y can be 0 to 9 and have a faujasite structure. The amount of sodium these mate- rials contain depends upon the Si0₂/Al₂0₃ ratio. A zeolite Y with a Si0₂/Al₂0₃ ratio of 6 contains about 11% Na₂0. Faujasites of lower Si0₂/Al₂0₃ ratio contain more Na₂0. These materials are articles of commerce and are available as powders and agglomerates. The zeolite is contacted with a potassium salt solution using conditions that produce zeolites wherein at least about 80% of the sodium for zeolite X and at least about 90% of the sodium for zeolite Y is replaced with potassium. The contacting solution can contain one or more potassium salts of strong acids. These can include among others KC1, K₂S0₄, KN0₃. The concentration can be 1 to 10 normal. The contact time can be 0.5 to 5 hours. The temperature is below boiling, but is usually above room temperature. The number of contacts can be varied, but not more than 5 are needed. Usually 1, 2 or 3 contacts are all that are required. After contact or between contacts the zeolite is filtered and washed.

The potassium exchanged zeolite contains sufficient potassium to facilitate the nearly complete exchange of ammonium ion for the sodium and potassium in the zeolite. For zeolite X which has 2.0 to 2.5 moles of Si0₂ for each mole of A1₂0₃ about 84% of the sodium must be exchanged for potassium. For zeolite Y, which has about 3 to 6 moles of Si0₂ for each mole of A1₂0₃, about 90% of the sodium must be exchanged for potassium. To obtain the potassium content required, the starting zeolite should be contacted with up to 10 moles of potassium ion for each mole of sodium to be exchanged. The potassium level can be more than the minimum required to facilitate the ammonium exchange but no additional process advantages are realized.

The predominately potassium substituted zeolite X or Y is now contacted with a solution of one or more ammonium salts. The salts of strong mineral or organic acids are all useful, and examples include NH₄C1, (NH₄)₂S0₄ and NH₄N0₃. The concentration of the solution can be 1 to 10 normal and is usually considerably less than about 10 normal. The contact time can vary considerably but is usually 0.5 to 24 hours. The temperature of the exchange is 100°C or less. Several contacts can be used, but we prefer 2 or 3 contacts. For example, using zeolite Y a 3 stage counter-current contact of a total of 7 moles of NH₄ ⁺ ion for each mole of M⁺ would provide a 97% replacement of M⁺, where M = [Na⁺ + K⁺] .

An alternative method of carrying out the process of my invention involves the contact of a zeolite such as zeolite X, zeolite Y, zeolite ZSM-20, or zeolite CSZ-1 to a solution containing both ammonium and potassium salts under conditions to produce the desired replacement of sodium by either potassium or ammonium ions. Then the ammonium, potassium exchanged zeolite is contacted with a solution containing an ammonium salt. This alternative method results in saving potassium salt values.

The products of this ion exchange process are faujasite-type zeolites wherein the properties of the zeolites are not changed very much except that the alkali metal- content is well below about 0.8% calculated as Na₂0, and usually well below about 0.5%. I prefer materials that contain less than 0.15% alkali metal calculated as Na₂0. These products can be used in various sorption and catalyst applications. They are also useful as starting materials for stabilization and dealumination processes. EXAMPLES

The following examples illustrate certain embodi¬ ments of my invention. These examples are not provided to establish the scope of the invention, which is described in the disclosure and recited in the claims. The proportions are in parts by weight (pbw) , percent by weight (wt%) , moles or equivalents. In the tables summarizing the results, Na₂0/Al₂0₃ represents the equivalents of Na for each equivalent of Al in the zeolite, K₂0/A1₂0₃ represents the equivalents of K for each equivalent of Al, Na₂0 + K₂0 represents the equivalents of Na + K for each equivalent of Al and M or M₂0 represents Na + K or Na₂0 + K₂0 respectively. Examples 1 through 8 were carried out with a start¬ ing zeolite Y with 5.5 moles of Si0₂ for each mole of A1₂0₃. This material (a commercial product) will be designated NaY or NaY zeolite. The intermediate products of the potassium exchanges are designated KY or KY zeolite even though they still contain some sodium. The product of the ammonium exchange is designated NH₄Y or NH₄Y zeolite. Examples 9 through 17 were carried out with a low silica form of zeolite X (Si0₂/Al₂0₃ = 2) which is repre¬ sented herein as LSX. This material was synthesized by the method described by Kuhl, Zeolites 1987 Vol. 7, "Crystal¬ lization of Low Silica Faujasite (Si0₂/Al₂0₃ = 2)." This synthesis is carried out using a mixed alkali of sodium and potassium. This product was my starting material and is designated "NaK LSX" or "NaK LSX zeolite." The inter¬ mediate products of the potassium exchange are designated "K LSX" or "K LSX zeolite", even though they still contain some sodium. The product of the ammonium exchange is designated ^»NH₄ LSX" or "NH₄ LSX zeolite."

Example l (Comparative example)

NaY zeolite (Si0₂/Al₂0₃ = 5.5) was contacted with various quantities of 3N NH₄N0₃ solution for 24 hours at 180°F. The ion exchange contact ratios and residual Na₂0 levels are shown in Table 1. The zeolite was washed with 15 pbw hot deionized (DI) H₂0 after each ion exchange contact.

TABLE 1

Meq N__₄ ⁺ gm 0 8.4 12.5 37.5 125 375 1250 zeolite

Wt% Na₂0 13.99 6.07 5.42 4.38 3.23 1.96 1.42 ( anhydrous )

Na_zO ( final ) / 1.0 0.43 0.38 0.31 0.23 0.14 0.10 Na₂0 Initial

These results show that very high ammonia to zeolite contact ratios carried out according to the prior art provide products that still have substantial alkali metal content.

Example 2 (Preparing KY Zeolite)

KY zeolite was prepared by contacting NaY zeolite (Si0₂/Al₂0₃ = 5.5) with 5 pbw of KC1 per pbw of NaY zeolite at 150°F for 2 hours using 2N KC1 solution. After the K⁺ exchange the zeolite was washed with 5 pbw hot DI H₂0. The ion exchange contact was repeated twice. The properties after the third contact are shown in Table 2.

These results indicate that potassium ion exchanges readily for sodium ion in NaY.

Example 3 (Converting KY Zeolite to NH₄Y Zeolite)

KY zeolite prepared as described in Example 2 was contacted with various quantities of 3N NH₄C1 solution for 24 hours at 100°C. The ion exchange contact ratios and residual Na₂0 and K₂0 levels are shown in Table 3.

TABLE 3

Meq NH₄ ⁺/gm 0 8 40 100 400 1667

Wt% Na₂0 ( anhydrous ) 0.59 0.03 0.01 0.01 0.01 0.01

Wt% K₂0 (anhydrous) 17.03 10.37 4.19 1.73 0.58 0.19

K₂θ/Al₂0₃ 0.95 0.56 0.22 0.09 0.03 0.01

Na₂0/Al₂0₃ 0.05 0.00 0.00 0.00 0.00 0.00 l^O ( Final ) /M₂0 (Initial) 1.0 0.61 0.25 0.11 0.03 0.01 These results, when compared with the results in Table 1, show how the process of my invention allows the removal of nearly all the alkali metal in zeolite Y. Sodium is com¬ pletely removed.

Example 4 (Comparative Example) NaY zeolite (13.3% Na₂0) was repeatedly contacted with NH₄N0₃ solution. Between each ion exchange contact the zeolite was washed with 15 pbw DI H₂0. The contact condi¬ tions and characterization results are shown in Table 4.

TABLE 4

Contact 1 2 3 4 5

Meq NH₄ ⁺/gm — 44 44 44 62.5 62.5

Contact Temperature ( °F) — 180 180 180 180 180

Contact Time (hr) — 3 3 5 5 5

Wt% Na₂0 13.3 4.03 1.24 1.09 0.57 0.17

Na₂0/Al₂0₃ 1.0 0.30 0.09 0.08 0.04 0.01 These results show how difficult it is to remove nearly all of the sodium from NaY using prior art conventional ion exchange methods.

Example 5 (Converting KY Zeolite to NH₄ Y Zeolite)

KY prepared as described in Example 2 was contacted with NH₄C1 solution three times at 180°F for 2 hours each contact. The zeolite was washed with 15 pbw DI H₂0 in each interval between contacts. The contact conditions and residual Na₂0 and K₂0 levels are shown in Table 5.

These results also show the advantages of my process in the number of ion exchange contacts and the amount of ammonium salt required to achieve the desired low levels of Na and K remaining in the zeolite is reduced.

Examples 6 and 6a (Preparing KY Zeolite outside Invention Limits)

KY zeolites with higher levels of residual Na₂0 were prepared by contacting NaY zeolite with 2N KCl solution.

The contact conditions and residual Na₂0 and K₂0 levels are shown in Table 6. TABLE 6

Example Example Example 2 6 6a

Meq K⁺/gm NaY zeolite — 20 40

Contact Temperature ( °F) — - 180 180

Contact Time (hr) — 2 2

Wt% Na₂0 (anhydrous) 0.59 2.20 1. 19 t% K₂0 (anhydrous) 17. 03 14.80 16. 18

K₂0/A1₂0₃ 0.95 0.82 0. 90

Na₂0/Al₂0₃ 0. 05 0. 18 0. 10

Example 7 (Converting KY Zeolite to NH₄Y Zeolite Outside Invention Limits)

KY from Example 6 (K₂0/A1₂0₃ = 0.82) was contacted with various quantities of NH₄C1 solution for 24 hours at

100°C. The ion exchange contact conditions and residual

Na₂0 and K₂0 levels are shown in Table 7.

TABLE 7

Meq NH₄ ⁺/gm KY 0 40 100 400 1746 t% Na₂0 (anhy) 2 .20 1.81 1.46 0.99 0.53 t% K₂0 (anhy) 14.80 3.78 2.32 0. 69 0. 11

Na₂0/Al₂0₃ 0.18 0.19 0.16 0.11 0.05

K₂0/A1₂0₃ 0.82 0.26 0. 17 0. 05 0. 01

Na₂0+K₂0/Al₂0₃ 1. 00 0.45 0. 33 0. 16 0. 06

These results show that a KY zeolite that still retains 0.18 Na₂0/Al₂0₃ does not provide the advantages of my process. These results should be compared with those in Table 3. Example 8 (Converting KY Zeolite to NH₄Y Zeolite)

KY from Example 6a (K0/A1₂0₃ = 0.90) was contacted with various quantities of NH₄C1 solution for 24 hours at 100°C. The ion-exchange contact conditions and residual Na₂0 and K₂0 levels are shown in Table 8.

These results, combined with those of Examples 1 and 8, show that more than 82% of the available ion exchange sites must be in the potassium form to provide the advantages of my process.

Example 9 (Comparative Example)

NaK LSX was contacted with various quantities of NH₄N0₃ solution for 6 hours at 195°F. The ion-exchange contact ratios and residual Na₂0 and K₂0 levels are shown in Table 9.

These results indicate that severe conditions are required to prepare NH₄ LSX of very low alkali metal content by conventional prior art ion exchange processes.

Example 10 (Preparing K LSX)

K LSX was prepared by contacting NaK LSX (Na₂0/Al₂0₃ = 0.75) with 3 pbw of KCl per pbw of NaK LSX zeolite at 160°F for 2 hours using 3N KCl. After the K⁺ exchange, the zeolite was washed with 5 pbw hot DI H₂0. The ion exchange contact was repeated three times. The properties after the fourth contact are shown in Table 10.

Example 11 (Converting K LSX to NH₄ LSX)

K LSX zeolite prepared as described in Example 10 was contacted with various quantities of NH₄N0₃ solution for 6 hours at 160°F. The ion exchange contact ratios and residual Na₂0 and K₂0 levels are shown in Table 11.

After NH₄ ⁺ ion exchange, the residual K₂0 + Na₂0/Al₂0₃ ratio is much lower when starting with K LSX than when starting with NaK LSX.

Example 12 (Comparative Example)

NaK LSX was contacted repeatedly with NH₄C1 solution. The zeolite was washed with 15 pbw DI H₂0 after each contact. After four contacts the NH₄NaK LSX was analyzed for residual Na₂0 and K₂0. A summary of the contact conditions and residual Na₂0 and K₂0 is shown in Table 12.

These results further illustrate that even very exhaustive prior art ion exchange processes do not provide NH₄ LSX of very low alkali metal content.

Example 13 (Converting K LSX to NH₄ LSX) K LSX, prepared as described in Example 10, was contacted with NH₄C1 solution three times at 160°F for 2 hours each contact. The zeolite was washed with 15 pbw DI H₂0 between each contact. The contact conditions and residual K₂0 level after the third contact are shown in Table 13.

These results illustrate the advantages of my invention, especially when compared to the results of Example 12 sum¬ marized in Table 12.

Examples 14 and 14a (Preparing K LSX Outside Invention Limits)

K LSX with varying levels of residual Na₂0 were prepared by contacting NaK LSX (Na₂0/Al₂0₃ = 0.75) with

3N KCl solution. The contact conditions and residual Na₂0 and K₂0 levels are shown in Table 14.

TABLE 14

Example Example 14 14a

Meq NH₄ ⁺/gm NaKLSX 0 13 53

Temperature ( ° F ) — 180 180

Contact Time (hr) — 2 2 t% Na₂0 (anhydrous) 15.9 12.53 3. 19 t% κ₂0 (anhydrous) 8. 1 12 . 67 25.40

Na₂0/Al₂0₃ 0.75 0.40 0. 16

K₂0/A1₂0₃ 0.25 0. 60 0.84

Na₂0 + K₂0/A1₂0₃ 1.00 1.00 1.00

Example 15 (Converting K LSX to NH₄ LSX Outside Invention Limits)

K LSX (K₂0/A1₂0₃ = 0.84) prepared as described in

Example 14a was contacted with various quantities of

4N NH₄C1 solution for 24 hours at 180°F. The ion-exchange conditions and residual Na₂0 and K₂0 levels are shown in Table 15.

TABLE 15

Meq NH₄ ⁺/gm KNa LSX 0 40 160 400 800

Wt% Na₂0 (anhydrous) 3.19 1.32 0.66 0.22 0.06 t% K₂0 (anhydrous) 25.40 5.01 3.34 1.33 0.53

Na₂0/Al₂0₃ 0.16 0.06 0.03 0.01 —

K₂0/A1₂0₃ 0.84 0.15 0.10 0.04 0.02

Na₂0 + K₂0/A1₂0₃ 1.00 0.21 0.13 0.05 0.02

These results indicate that the advantages of my process are realized when the K LSX still retains 0.16 Na₂0/Al₂0₃. Compare these results with Example 11 and Table 11.

Example 16 (Converting K LSX to NH₄ LSX Outside Invention Limits) K LSX (K₂0/A1₂0₃ = 0.60) prepared as described in

Example 14 was contacted with various quantities of 4N NH₄C1 solution for 24 hours at 180°F. Ion-exchange conditions and residual Na₂0 and K₂0 levels are shown in Table 16.

TABLE 16

Meq NH₄ ⁺1 (gm KNa LSX) 0 40 160 400 800

Wt% Na₂0 (anhydrous) 12.53 6.18 4.63 4.40 0.44

Wt% K₂0 (anhydrous) 12.67 1.67 1.00 0.67 0.65

Na₂0/Al₂0₃ 0.40 0.28 0.21 0.20 0.02

K₂0/A1₂0₃ 0.60 0.05 0.03 0.02 0.02

Na₂0 + K₂0/A1₂0₃ 1.00 0.33 0.24 0.22 0.04

These results indicate that the advantages of my process are not fully realized when the K LSX still retains suffi¬ cient sodium to provide 0.60 Na₂0/Al₂0₃.

Claims

CLAIMSI claim:

1. A process for preparing an ammonium zeolite of the faujasite structure selected from the group consisting of zeolite X, zeolite Y, zeolite ZSM-20, zeolite ZSM-3 and zeolite CSZ-l, of extremely low alkali metal content comprising the steps of: a. contacting said zeolite that contains sodium with a solution of a potassium salt under ion-exchange conditions that provide exchange of the sodium for potassium to provide a residual sodium content of 0.1 equivalent of Na₂0 or less for each equivalent of A1₂0₃; b. filtering and washing the resulting potassium exchanged zeolite; c. contacting said potassium exchanged zeolite with a solution of an ammonium salt under ion-exchange conditions such that ammonium ions replace sodium and potassium ions in the zeolite to produce an ammonium Y zeolite that contains less than 0.1 equivalent of Na₂0 + K₂0 per equivalent of Al₂0₃; and d. filtering and washing the resulting zeolite product.

2. A process for preparing ammonium zeolite Y of extremely low alkali metal content, comprising the steps of: a. contacting zeolite Y that contains sodium with a solu¬ tion of a potassium salt under ion-exchange conditions that provide exchange of the sodium for potassium to provide a residual sodium content of 0.18 equivalent of Na₂0 or less for each equivalent of A1₂0₃; b. filtering and washing the resulting potassium exchanged zeolite; c. contacting said potassium exchanged zeolite with a solution of an ammonium salt under ion-exchange conditions such that ammonium ions replace sodium and potassium ions in the zeolite to produce an ammonium Y zeolite that contains less than 0.1 equivalent of Na₂0 + K₂0 per equivalent of A1₂0₃; and d. filtering and washing the resulting zeolite Y product.

3. A process for preparing ammonium zeolite X of extremely low alkali metal content, comprising the steps of: a. contacting zeolite X that contains sodium with a solu¬ tion of a potassium salt under ion-exchange conditions that provide exchange of the sodium for potassium to provide a residual sodium content of 0.16 equivalents of Na₂0 or less for each equivalent of A1₂0₃; b. filtering and washing the resulting potassium exchanged zeolite; c. contacting said potassium exchanged zeolite with a solution of an ammonium salt under ion-exchange conditions such that ammonium ions replace sodium and potassium ions in the zeolite to produce an ammonium Y zeolite that contains less than 0.1 equivalent of Na₂0 + K₂0 per equivalent of A1₂0₃; and d. filtering and washing the resulting zeolite X product.

4. A process for preparing an ammonium zeolite of the faujasite structure selected from the group consisting of zeolite X, zeolite y, zeolite ZSM-20, zeolite ZSM-3 and zeolite CSZ-l of extremely low alkali metal content comprising the steps of: a. contacting said zeolite that contains sodium with a solution that contains a potassium salt and an ammonium salt under ion-exchange conditions that provide ex¬ change of the sodium for potassium or ammonium to result in a residual sodium content of 0.1 equivalents of Na₂0 or less for each equivalent of A1₂0₃; b. filtering and washing the resulting potassium, ammonium exchanged zeolite; c. contacting said potassium, ammonium exchanged zeolite with a solution of an ammonium salt under ion-exchange conditions such that ammonium ions replace sodium and potassium ions in the zeolite to produce an ammonium Y zeolite that contains less than 0.1 equivalent of Na₂0 + K₂0 per equivalent of A1₂0₃; and d. filtering and washing the resulting zeolite product.