Preparation of synthetic zeolite molecular sieves

Abstract

In the manufacture of synthetic zeolites, the formation of unwanted, contaminating zeolites is inhibited by the addition to the reactant mixture of a basic nitrogen-containing dye, and makes it possible to synthesize new zeolites AG5 and AG6 herein defined by their compositions and X-ray diffraction patterns.

Description

The present invention relates to improvements in or relating to the manufacture of synthetic zeolite molecular sieves, and in particular to the use of basic dyes containing nitrogen, to inhibit the formation of specific unwanted zeolitic phases, and as a result promote the formation of desired zeolite phases.

Surprisingly we have found that certain basic dyes (and salts and esters thereof) adsorb very strongly on specific zeolites, or only on zeolites having related framework structures. If such a basic dye (or dyes) is employed, as recommended in this invention, this property can be used to suppress the formation of unwanted zeolite products during the manufacture of more desirable products. It is believed that the basic dye or dyes adsorb on nuclei of unwanted species and inhibit nucleation and subsequent crystal growth. The net result of this discovery is that it is now possible to manufacture desired zeolite products under more advantageous operating conditions, which could not be employed in the absence of said basic dyes. Also we have found that it is possible to inhibit the formation of known zeolitic products and to promote the formation of novel zeolites AG5 and AG6. Examples of some basic dyes suitable for this invention are shown in Table 1, but this table in no way limits the scope of our invention.

The present invention provides a process for the manufacture of synthetic zeolites, wherein the normal reaction of the reactant mixture is altered by the addition thereto of an additive comprising a basic dye or mixture of dyes containing, nitrogen (or salts or esters of such dyes), the additive: Al.sub.2 0.sub.3 molar ratio being less than 0.1:1.

Such a basic dye containing nitrogen is one which promotes the formation of unwanted zeolite products. A suitable additive is a basic dye (or mixture of dyes) which adsorbs strongly on unwanted zeolite products.

TABLE 1______________________________________ADSORPTION ON ZEOLITES STRONG MEDIUMZEOLITE ADSORPTION STRONG ADSORPTION______________________________________B (near gismondite) crystal violet methyl violet nuclear fast red methylene blueR (near chabazite toluidene bluesodium) methylene blueD (near chabazite toluidene bluepotassium-sodium) methylene blueKM (potassium near malachite green magenta phillipsite) nuclear fast red crystal violet methyl violet methylene blueF methylene blue malachite greenA acriflavineX, Y, Y.sup.1 acriflavine______________________________________

In the manufacture of the faujasite-type zeolites commonly designated zeolites X, Y and Y.sup.1, and of zeolite L, the prior art routes require, especially for commercial scale manufacture, that the reactants should be mixed and aged quiescently at ambient temperature, and then heated rapidly to a crystallization temperature of, for example, 100.degree. C. Zeolite Y.sup.1 is a higher silica modification of zeolite Y; both zeolites Y and Y.sup.1 are treated as identical in the U.S. Pat. No. 3,130,007, while British Patent Specifications Nos. 909,266 and 972,831 distinguish between the Y and Y.sup.1 form, respectively. This temperature is maintained for from 48 to 120 hours, and quiescent conditions are of vital importance, ie the reactants must undergo no significant mechanical agitation, and there must be no significant thermal gradients across the reaction mixture. Such conditions are, of course, extremely difficult to maintain in large scale commercial processes.

Alternatively, for the manufacture of zeolite X, Y and Y.sup.1, the need for quiescent ageing and quiescent crystallization can be avoided by the use of active silicates, as in British Pat. No. 1,145,995, in which process ambient ageing stages are unnecessary and crystallization need not be quiescent. The limitations of the process of British Pat. No. 1,145,995 are that active silicates are essential, and that for synthetic faujasites having SiO.sub.2 /Al.sub.2 O.sub.3 ratio >4 it is necessary to use expensive colloidal silica or fume silica as the major silica source in those manufacturing ranges which are economical in raw material usage. Where the SiO.sub.2 /Al.sub.2 O.sub.3 ratio of the reaction mixture is .ltoreq.14, even with colloidal silica the reactions are unreliable and liable to give high levels of contamination with an undesirable small-port zeolite S.

In our co-pending British Patent application No. 4130/73, now British Patent Specification No. 1,450,411, (corresponding to U.S. application Ser. No: 435,507 filed 22 Jan. 1974, now abandoned) we have shown that it is possible to manufacture highly crystalline potassium or sodium/potassium faujasite under conditions which combine the advantage of easy manufacturing conditions with the use of cheaper raw materials, namely the replacement of colloidal or fume silica as the major source of silica by common water glass or other low-cost forms of silica, eg precipitated silica. A minor source of silica, necessary for the process of our said co-pending British Pat. Appln. 4130/73, is an active hydrated sodium metasilicate or active silica (as in British Pat. Nos. 1,145,995 and 1,193,254). For the purposes of our said co-pending British application No. 4130/73, an active silica(te) is defined as a source of silica, which must yield substantially pure synthetic faujasite within 17 hours at 85.degree. in a vigorously agitated reaction, and wherein the reaction mixture molar ratios are: SiO.sub.2 /Al.sub.2 O.sub.3 = 6.4, Na.sub.2 O/SiO.sub.2 = 0.35, H.sub.2 O/Na.sub.2 O = 50, SO.sub.4 /Al.sub.2 O.sub.3 = 1.5. The sulphate is introduced as aluminium sulphate, and the remainder of the alumina as sodium aluminate. The ratio of active silica(te) to silica(te) from other sources is 1:3.6. While the process of our said co-pending British application No. 4130/73 yields zeolite Y or Y.sup.1 of high purity, it has some limitations. It is essential that a minor part of the silica(te) should be in active form; also, as in the prior art processes, synthetic faujasites, when formed, may recrystallize to yield zeolite B if left in contact with the mother liquor for too long. Attempts to reduce reaction times by raising the temperature are ultimately limited by this conversion of Y or Y.sup.1 to zeolite B, because before all of the reaction mixture has been crystallized as zeolite Y or Y.sup.1, some of the product recrystallizes as zeolite B giving rise to high levels of contamination.

Similarly, in the process of our said co-pending British Patent application No. 4130/73, as in the prior art processes, attempts to reduce reaction time by seeding with pure zeolite Y or Y.sup.1 would fail, because some of the added seed is converted to zeolite B, which in turn promotes formation of more zeolite B. Examples of the effects of this over-run problem are given in Table 2.

TABLE 2__________________________________________________________________________MANUFACTURE OF ZEOLITE Y (SiO.sub.2 /Al.sub.2 O.sub.3 = 4.9) REACTION CRYSTALLIZATIONMETHOD USED TIME HOURS TEMPERATURE .degree. C PRODUCT__________________________________________________________________________As in US 40* 95 95% zeolite YPatent + zeolite S3,130,007 26* 103 70% zeolite Y + amorphous 27* 103 80% zeolite Y + 20% zeolite B 12.DELTA. 103 60% zeolite Y 30% zeolite B 10% amorphousAs in our 24-28 85 100% zeolite Ysaid Co- 161/2 95 80% zeolite Ypending + amorphousBritish 17 95 100% zeolite YApplicaton 171/2 95 80% zeolite YNo.: 4130/73 + 20% zeolite B__________________________________________________________________________ *Also aged 28 hours at 25.degree. C .DELTA.20% seed added, no preaging

We have now found that if a suitable basic dye containing nitrogen is introduced into a zeolite reaction, preferably along with the siliceous components, then synthetic faujasites with SiO.sub.2 /Al.sub.2 O.sub.3 = 2.3 to 6.3 can be prepared under highly advantageous conditions. Suitable dyes are, for example, crystal violet, methyl violet, and nuclear fast red. The advantages result (a) from the suppression of zeolite B formation, ie there are none of the over-run problems which occur in prior art routes; (b) from the fact that any hydrated sodium metasilicate can be employed as a minor source of silica, and its activity is of no significance; (c) the reaction time can be reduced substantially by either raising the temperature, or by adding zeolite seeds, or both. Typical results obtained by the process of this invention are given in Table 3, and are compared with results obtained by the process of this invention are given in Table 3, and are compared with results obtained in the absence of added organic components. The operating range for zeolite X manufacture in the temperature range 50.degree. C to 120.degree. C is as follows, on a molar basis:

wherein M.sub.2 O = Na.sub.2 O + K.sub.2 O SiO.sub.2 /Al.sub.2 O.sub.3 = 2.7 to 8 M.sub.2 o/siO.sub.2 = 0.3 to 6.0 Na.sub.2 O/M.sub.2 O = 0.7 to 1.0 sodium metasilicate hydrate / Al.sub.2 O.sub.3 = 0.3 to 6.0 H.sub.2 o/m.sub.2 o = 10 to 150 basic dye, eg crystal violet / Al.sub.2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1. The operating ranges for zeolite Y and Y.sup.1, at from 75.degree. C to 120.degree. C, are as follows: __________________________________________________________________________ Basic dyeRange SiO.sub.2 /Al.sub.2 O.sub.3 M.sub.2 O/SiO.sub.2 Na.sub.2 O/M.sub.2 O H.sub.2 O/M.sub.2 O A.sub.2 /n/Al.sub.2 O.sub.3 additive/Al.sub.2 O.sub.3__________________________________________________________________________1 4 to 6.9 0.25 to 0.4 0.7 to 1.0 40 to 120 0 to 3.0 5.times.10.sup.-.sup.4 to 0.12 6.9 to 7.9 0.25 to 0.335 " " " "3 7.9 to 10 0.25 to 0.34 " " " "4 10 to 12 0.25 to 0.40 " " " "5 12 to 14 0.25 to 0.45 " " " "6 14 to 16 0.25 to 0.50 " " " "7 16 to 40 0.25 to 1.0 " " " "__________________________________________________________________________ wherein M.sub.2 O = Na.sub.2 O + K.sub.2 O, and A = an acid radical of valence n, for example sulphate, nitrate or chloride introduced as the aluminium salt or salts. Also the ratio of hydrated sodium metasilicate to silica from other sources is preferably at least 1:8. TABLE 3 SYNTHETIC FAUJASITES__________________________________________________________________________REACTANT MOLAR RATIOS Ratio inactive hydrated metasilicate REACTIONEx. Basic dye Basic dye to other Time TempNo SiO.sub.2 /Al.sub.2 O.sub.3 M.sub.2 O/SiO.sub.2 An/2/Al.sub.2 O.sub.3 * H.sub.2 O/M.sub.2 O additive/Al.sub.2 O.sub.3 additive silica hours .degree. C Product__________________________________________________________________________1 3.85 1 1.2 47 0 None 0.125 3 95 zeolite B + zeolite C + amorphous2 3.85 1 1.2 47 5 .times. 10.sup.-.sup.3 crystal 0.125 3 95 zeolite X violet3 5 0.7 25 47 5 .times. 10.sup.-.sup.3 methyl 0 24 95 zeolite X violet4 20 1 0.4 40 0 none 0.6 24 95 zeolite S + zeolite B + amorphous5 20 1 0.4 40 5 .times. 10.sup.-.sup.3 nuclear 0.6 24 95 zeolite Y.sup.1 fast red6 6.86 1.0 0.32 63 5 .times. 10.sup.-.sup.3 crystal 0.25 24 85 zeolite Y/Y.sup.1 violet7 0 none 0.25 14 103 zeolite Y/Y.sup.18 0 none 0.25 14.5 103 80% zeolite Y/Y.sup.1 20% zeolite B9 5 .times. 10.sup.-.sup.3 methyl 0.25 14 to 103 zeolite Y/Y.sup.1 violet 2410 5 .times. 10.sup.-.sup.4 methyl 0.25 14 to 103 zeolite Y/Y.sup.1 As in Example 6 violet 1611 0 20% 0.25 7 103 50% zeolite Y zeolite 30% zeolite B Y seed + amorphous12 5 .times. 10.sup.-.sup.3 crystal 0.25 7 103 zeolite Y/Y.sup.1 violet and 20% zeolite Y seed__________________________________________________________________________ *An acid radical of valence n, preferably SO.sub.4.sup.-.sup.-, but possibly NC.sub.3.sup.- or Cl.sup.--

In the same manner, it is possible to manufacture zeolite L and the related zeolites, such as AG4 (disclosed in our co-pending British Patent Appln. No. 5492/72, now British Patent Specification No. 1,394,163 which corresponds to U.S. Application Serial No. 329,336 filed 5 May 1973, now abandoned) and a novel zeolite AG5 under advantageous conditions. Thus, in the prior art synthesis of zeolite L, there is always a tendency for the formation of unwanted zeolite KM, a small-port near-phillipsite; this can result from inadequate preageing of the reaction mixture at ambient temperature, or can result from agitation, either mechanical or resulting from thermal gradients, because quiescent crystallization is an essential feature of the manufacture and, especially on a commercial scale, true quiescent conditions are extremely difficult to maintain. Over-run problems occur in zeolite L synthesis, as with zeolites Y and Y.sup.1, the unwanted conversion products being zeolite KM or, in some cases, zeolite D.

We have found that malachite green, magenta, crystal violet, methyl violet and nuclear fast red adsorb strongly on zeolite KM, and can be used to suppress the formation of this zeolite. A further advantage found is that with the basic dye added to the reaction mixture, amibent ageing stages are unnecessary and, futhermore, agitation is preferable, ie problems relating to disturbance from mixing and by thermal agitation became non-existent. Typical results are given in Table 4. Where a basic dye additive was incorporated, crystallization under agitated conditions yielded zeolites L or AG4 or AG5, instead of the expected zeolite KM. Non-agitated reactions yielded near-chabazites along with near L-type zeolites. A further advantage over the prior art synthesis is that cheap sources of silica, eg water glass, can be employed instead of expensive colloidal or fume silica.

Zeolite AG4 is a large-port L-type disclosed in our said co-pending British Patent Application No. 5492/72, and it can be readily distinguished from zeolite L by its ability to adsorb up to about 20% of perfluorotributylamine (PFTB) at P/po = 0.6 within 4 hours, whereas zeolite L adsorbs <1% under such conditions. This demonstrates that zeolite AG4 has ports of about 11.0A, as compared with zeolite L which has ports of about 9A. The novel zeolite AG5 is a small-port near L-type zeolite which as ports of about 6.5A, as indicated by its refusal of cumene (6.9A) and adsorption of 8% cyclohexane (6A) at P/po = 0.6 for 1 hour (under these conditions zeolite AG4 and zeolite L adsorb >8% cumene).

TABLE 4__________________________________________________________________________ZEOLITES L, AG4 and AG5__________________________________________________________________________REACTION RATIOS REACTION Type of Basic dyeExample silicate SiO.sub.2 / *K.sub.2 O/ *M.sub.2 O/ *H.sub.2 O/ additive/ Time TempNo used Al.sub.2 O.sub. 3 M.sub.2 O SiO.sub.2 M.sub.2 O Al.sub.2 O.sub. 3 hours .degree. C Product__________________________________________________________________________13 Potassium 5 .times. 10.sup.-.sup.3 waterglass (crystal SiO.sub.2 /K.sub.2 O=2.24 14 1.0 0.55 100 violet) 48 95 zeolite AG514 As Example 13 14 1.0 0.55 100 None 48 95 zeolite KM15 colloidal 5 .times. 10.sup.-.sup.3 silica 20 1.0 0.65 80 (crystal 72 95 zeolite AG5 violet)16 potassium 5 .times. 10.sup.-.sup.3 waterglass (methyl SiO.sub.2 /K.sub.2 O=3.2 20 0.64 0.425 37.5 violet) 48 95 zeolite AG417 colloidal 7 0.64 0.8 70 5 .times. 10.sup.-.sup.3 24 95 zeolite AG4- silica (nuclear 5 fast red)18 potassium 28 0.58 0.452 32 5 .times. 10.sup.-.sup.3 54 95 zeolite L waterglass crystal SiO.sub.2 /K.sub. 2 O=3.2 violet19 colloidal 20 0.3 0.3 40 5 .times. 10.sup.-.sup.3 96 95 zeolite L silica (malachite green)__________________________________________________________________________ *M.sub.2 O = K.sub.2 O + Na.sub.2 O TABLE 5______________________________________X-ray diffractometer results______________________________________ZEOLITE ZEOLITEAG5 AG4 ZEOLITE L 100I/ 100I/ 100I/dA I.sub.o dA I.sub.o dA I.sub.o______________________________________16.0 100 15.85 100 15.8 1007.8 22 7.89 8 7.50 26 7.49 146.25 226.00 15.5 6.00 32 5.98 204.79 624.60 67 4.57 66 4.57 30 4.40 26 4.40 74.15 783.87 37 3.91 77 3.91 35 3.78 103.66 37 3.66 32 3.66 183.42 70 3.46 55 3.48 253.25 53 3.26 253.17 503.10 80 3.06 72 3.03 27 3.02 12 2.91 58 2.91 252.80 612.68 14 2.65 47 2.65 162.60 11 2.62 62.57 9 2.49 11 2.45 11 2.42 212.32 272.17 30 2.19 13 2.19 9______________________________________ X-ray diffraction data given in Table 5 illustrate that there are small but significant differences between zeolites L, AG4 and AG5.

The operating range for zeolite L, from 50.degree. C to 120.degree. C is for agitated reactions only, and is as follows:

SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to 28 M.sub.2 o/siO.sub.2 = 0.3 to 0.6 K.sub.2 o/m.sub.2 o = 0.26 to 1.0 H.sub.2 o/m.sub.2 o = 10 to 90 (basic dye)/Al.sub. 2 O.sub.3 = 5 .times. 10.sup.-.sup.4 to 0.1 wherein M.sub.2 O = K.sub.2 O + Na.sub.2 O

The operating range for zeolite AG4, in agitated reaction only, at 50.degree. C to 120.degree. C is

SiO.sub.2 /Al.sub.2 O.sub.3 = 7 to 20 M.sub.2 o/siO.sub.2 = 0.4 to 0.9 K.sub.2 o/m.sub.2 o = 0.5 to 0.95 H.sub.2 o/m.sub.2 o = 10 to 80 (basic dye)Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1 wherein M.sub.2 O = K.sub.2 O + Na.sub.2 O

The operating range for novel zeolite AG5, in agitated reaction only, at 50.degree. C to 120.degree. C is

SiO.sub.2 /Al.sub.2 O.sub.3 = 7 to 20 K.sub.2 o/siO.sub.2 = 0.45 to 0.65 H.sub.2 o/k.sub.2 o = 80 to 140 (basic dye)Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1

The invention therefore also provides a process for preparing the novel zeolite AG5 from a reactant composition according to the immediately preceding paragraph.

The novel zeolite AG5 has a composition in the following range, and its cations are exchangeable:

0.7 to 1.1 K.sub.2 O.Al.sub.2 O.sub.3.2.5 to 6.0SiO.sub.2.yH.sub.2 O, where y is 0 to 8.

The invention therefore also provides the novel zeolite AG5 having a composition according to the immediately preceding paragraph and an X-ray diffraction pattern substantially as shown in Table 5.

The experiments given below in Table 6 further illustrate the utility of this invention. In the field of synthesis normally yielding either zeolite F or zeolite D, the addition of both malachite green and methylene blue suppresses the formation of both zeolites, and allows formation of a novel zeolite AG6 (see Table 6). X-ray diffraction data is given in Table 7 for the novel zeolite AG6.

This novel zeolite AG6 has a composition in the following range, and its cations are exchangeable:

0.7 to 1.1 (x K.sub.2 O. (1-x) Na.sub.2 O) Al.sub.2 O.sub.3 .2.5 to 6.0 SiO.sub.2.y H.sub.2 O, wherein x is 0.2 to 0.8, and y is 0 to 8.

The invention therefore further provides the novel zeolite AG6 having a composition according to the immediately preceding paragraph and an X-ray diffraction pattern substantially as shown in Table 7.

The operating range for the manufacture of zeolite AG6, in the temperature range 50.degree. C to 120.degree. C is as follows, ambient ageing being unnecessary, and agitation being optional:

SiO.sub.2 /Al.sub.2 O.sub.3 = 1 to 10 K.sub.2 o/na.sub.2 O + K.sub.2 O = 0.4 to 0.9 M.sub.2 o/siO.sub.2 = 0.4 to 4.0 H.sub.2 o/m.sub.2 o = 10 to 50 (basic dye(Al.sub. 2 O.sub.3 = 5 .times. 10.sup.-.sup.4 to 0.1 wherein M.sub.2 O = K.sub.2 O + Na.sub.2 O

The invention therefore further provides a process for preparing the novel zeolite AG6 from a reactant composition according to the immediately preceding paragraph.

TABLE 6__________________________________________________________________________REACTION MIXTURE MOLAR RATIOS REACTIONEXAMPLE basic dye TimeNUMBER SiO.sub.2 /Al.sub.2 O.sub.3 K.sub.2 O/Na.sub.2 O+K.sub.2 O M.sub.2 O/SiO.sub.2 H.sub.2 O/M.sub.2 O additive/Al.sub.2 O.sub.3 hours Product__________________________________________________________________________20 5 0.8 2.8 13 0 24 zeolite F21 5 0.8 2.8 13 5 .times. 10.sup.-.sup.3.sup.+ 24 zeolite AG622 5 0.4 2.5 20 5 .times. 10.sup.-.sup.3.sup.+ 36 zeolite AG623 5 0.4 2.5 20 0 36 zeolite D__________________________________________________________________________ .sup.+equal (molar) quantities of malachite green and methylene blue TABLE 7______________________________________ZEOLITE 6 - X-RAY DIFFRACTION DATAdA 9.36 7.05 6.24 5.42 3.116 2.978 2.618______________________________________100I/I.sub.o 100 20 35 25 30 70 20______________________________________

Claims

1. In a process for the manufacture of synthetic zeolites, comprising crystallizing the zeolite from a reaction mixture, the improvement comprising altering the reaction mixture by the addition thereto of an additive selected from the group consisting of crystal violet, methyl violet, nuclear fast red, methylene blue, toluidene blue, malachite green, magenta, acriflavine, and mixtures, salts and esters thereof.

2. Process as claimed in claim 1, in which the silica source includes hydrated sodium metasilicate and the ratio of such silica source to other silica sources in the reactant mixture is at least 1:8.

3. Process as claimed in claim 1, for producing zeolite L, which comprises reacting, under agitated conditions and at a temperature between 50.degree. C and 120.degree. C, a reactant mixture having a molar composition in the range:

SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to 28

M.sub.2 o/siO.sub.2 = 0.3 to 0.6

K.sub.2 o/m.sub.2 o = 0.26 to 1.0

H.sub.2 o/m.sub.2 o = 10 to 90

(basic dye)/Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1

wherein M.sub.2 O = K.sub.2 0 + Na.sub.2 O

4. Process as claimed in claim 1, for producing zeolite AG4, which comprises reacting, under agitated conditions and at a temperature between 50.degree. C and 120.degree. C, a reactant mixture having a molar composition in the range:

SiO.sub.2 /Al.sub.2 O.sub.3 = 7 to 20

M.sub.2 o/siO.sub.2 = 0.4 to 0.9

K.sub.2 o/m.sub.2 o = 0.5 to 0.95

H.sub.2 o/m.sub.2 o = 10 to 80

(basic dye)/Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1

wherein M.sub.2 O = K.sub.2 O + Na.sub.2 O

5. A method of crystallizing zeolite AG5 having the composition

0.7 to 1.1 K.sub.2 O . Al.sub.2 O.sub.3 . 2.5 to 6.0 SiO.sub.2 . 0 to 8 H.sub.2 O

and the following X ray diffraction pattern:

______________________________________dA 100I/I.sub.o______________________________________16.0 1007.8 226.25 226.00 15.54.79 624.60 674.15 783.87 373.66 373.42 703.25 533.17 503.10 802.80 612.68 142.60 112.57 92.32 272.17 30______________________________________

which comprises reacting together at 50.degree.-120.degree. C a silica source and an alumina source in a potassium-containing aqueous alkaline medium in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet and nuclear fast red, the molar ratio of the constituents of the mixture being represented by

SiO.sub.2 /Al.sub.2 O.sub.3 = 7 to 20

K.sub.2 o/k.sub. 2 = 0.45 to 0.65

H.sub.2 o/k.sub. 2 o = 80 to 140

(Basic dye)/Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1

6. A method of crystallizing zeolite Y or Y.sup.1 which comprises reacting together at 75.degree.-120.degree. C. a silica source and an alumina source in an aqueous alkaline medium containing sodium ions or sodium ions and potassium ions in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet, nuclear fast red, toluidine blue and methylene blue, the molar ratio of basic dye to alumina being in the range of 5 .times. 10.sup.- .sup.4 to 0.1 and the molar composition of the mixture including SiO.sub.2 /Al.sub.2 O.sub.3 and M.sub.2 O/SiO.sub.2 which are selected in combination from

______________________________________SiO.sub.2 /Al.sub.2 O.sub.3 M.sub.2 O/SiO.sub.2______________________________________ 4 to 6.9 0.25 to 0.4;6.9 to 7.9 0.25 to 0.335;7.9 to 10 0.25 to 0.34;10 to 12 0.25 to 0.40;12 to 14 0.25 to 0.45;14 to 16 0.25 to 0.50; or15 to 40 0.25 to 1.0,______________________________________

and further including

(b)

Na.sub.2 O/M.sub. 2 O = 0.7 to 1.0

H.sub.2 o/m.sub. 2 o = 40 to 120

A.sub.2/n /Al.sub.2 O.sub.3 = 0 to 3

to produce zeolite Y or Y.sup.1,

where M.sub.2 O = Na.sub.2 O + K.sub.2 O and A is an acid radical of valence n.

7. A method of crystallizing zeolite X which comprises reacting together at 50.degree.-120.degree. C a silica source and an alumina source in an aqueous alkaline medium containing sodium ions or sodium ions and potassium ions in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet, nuclear fast red, toluidine blue and methylene blue, the molar ratio of basic dye to alumina being in the range 5 .times. 10.sup.- .sup.4 to 0.1 and the molar composition of the mixture being represented by

SiO.sub.2 /Al.sub. 2 O.sub.3 = 2.7 to 8

sodium metasilicate hydrate/Al.sub. 2 O.sub.3 = 0.3 to 6.0

M.sub.2 o/siO.sub. 2 = 0.3 to 6.0

Na.sub.2 O/M.sub. 2 O = 0.7 to 1.0

N.sub.2 o/m.sub. 2 o = 10 to 150

where M.sub.2 O = Na.sub.2 O + K.sub.2 O to produce zeolite X.

8. A method of crystallizing zeolite AG6 having the composition

0.7 to 1.1 (xK.sub.2 O.(1-x)Na.sub.2 O.sub.3 .2.5 to 6.0 SiO.sub.2 to 8 H.sub.2 O wherein x is 0.2 to 0.8, and the following X-ray diffraction pattern:

______________________________________dA 100I/I.sub.o______________________________________9.36 1007.05 206.24 355.42 253.116 302.978 702.618 20______________________________________

which comprises reacting together at 50.degree.-120.degree. C a silica source and an alumina in a potassium-containing aqueous alkaline medium in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet and nuclear fast red, the molar ratio of the constituents of the mixture being represented by

SiO.sub.2 /Al.sub.2 O.sub.3 = 1 to 10

K.sub.2 o/na.sub.2 O + K.sub.2 O = 0.4 to 0.9

M.sub.2 o/siO.sub.2 = 0.4 to 4.0

H.sub.2 o/m.sub.2 o = 10 to 50

(basic dye)/Al.sub. 2 O.sub.3 = 5 .times. 10.sup.- .sup.4 to 0.1

wherein M.sub. 2 O = K.sub.2 O + Na.sub.2 O, to produce zeolite AG6.