ZEOLITES

Abstract: A synthetic zeolite material, designated zeolite Nu-4, hav­ ing a molar composition expressed by the formula: 0.1 to 7.5 M 1 / 2O:0.2 to 2.5 Y₂O₃:100 XO₂:0 to 50 H₂O wherein M¹ is a monovalent cation or 1/n of a cation of valency n, X is silicon or germanium, Y is aluminium, iron, chromium, vanadium, mo­ lybdenum, arsenic, antimony, manganese, gallium, or boron, and H₂O is water of hydration additional to water notionally present when M¹ is H and having a defined X-ray pattern is pre­ pared from defined aqueous mixtures containing the oxide XO₂, the oxide Y₂O₃ and a polyalkylene polyamine. The zeolite is a useful catalyst for xylenes isomerisation and the like.

Description: ZEOLITES The present invention relates to a zeolite material, hereinafter referred to as zeolite Nu-4, to a method of making it and to processes using it as a catalyst. According to the present invention, we provide a synthetic zeolite material, designated zeolite Nu-4, having a molar composition expressed by the formula: 0.1 to 7.5 M2 : 0.2 to 2.5 Y203 : 100 XO2 : 0 to 50 H20 wherein M1 is a monovalent cation or 1/n of a cation of valency n, X is silicon or germanium, Y is aluminium, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium, or boron, and H20 is water of hydration additional to water notionally present when M1 is H, and having an X-ray pattern substantially as set out in Table 1 (as determined by standard technique using copper Ka radiation). Table 1 shows X-ray data for zeolite Nu-4 as prepared. The X-ray pattern is little affected by the type of cation present or by calcination or hydration. TABLE 1 EMI2.1 <tb> <SEP> Zeolite <SEP> Nu-4 <SEP> Zeolite <SEP> Nu-4 <tb> <SEP> Example <SEP> 3 <SEP> (as <SEP> mode) <SEP> Example <SEP> 4 <SEP> (calcined <SEP> H <SEP> forms) <tb> <SEP> dA <SEP> 100 <SEP> I/I0 <SEP> dA <SEP> 100 <SEP> I/I0 <tb> <SEP> 11.3 <SEP> 16 <SEP> - <SEP> <tb> <SEP> 11.1 <SEP> 20 <SEP> 11.07 <SEP> 33 <tb> <SEP> 10.08 <SEP> 15 <SEP> 10.07 <SEP> 36 <tb> <SEP> 9.90 <SEP> S <SEP> 9.96 <SEP> 10 <tb> <SEP> 9.77 <SEP> 4 <SEP> 9.79 <SEP> 10 <tb> <SEP> - <SEP> - <SEP> 9.38 <SEP> 1 <tb> <SEP> 9.05 <SEP> 1 <SEP> 9.02 <SEP> 1.5 <tb> <SEP> - <SEP> - <SEP> 8.08 <SEP> 1 <tb> <SEP> 7.50 <SEP> 2 <SEP> 7.45 <SEP> 4 <tb> <SEP> 7.09 <SEP> 1 <SEP> 7.09 <SEP> 2 <tb> <SEP> 6.76 <SEP> 2 <SEP> 6.72 <SEP> 4 <tb> <SEP> 5.44 <SEP> 5 <SEP> 6.38 <SEP> 5 <tb> <SEP> 6.07 <SEP> 4 <SEP> 6.08 <SEP> 5 <tb> <SEP> 6.05 <SEP> 5 <SEP> 5.02 <SEP> 7 <tb> <SEP> 5.97 <SEP> 1 <SEP> <SEP> 5.99 <SEP> 7 <SEP> <tb> <SEP> 5.75 <SEP> 5 <SEP> 5.13 <SEP> 9 <tb> <SEP> 5.65 <SEP> 4 <SEP> 5.97 <SEP> 3 <tb> <SEP> 3.63 <SEP> 3 <SEP> - <SEP> <tb> <SEP> 5.41 <SEP> 2 <SEP> 5.36 <SEP> 2 <tb> <SEP> 5.19 <SEP> 2 <SEP> 5.15 <SEP> 4 <tb> <SEP> 5.07 <SEP> 2 <SEP> 5.04 <SEP> 3 <tb> <SEP> 5.01 <SEP> 4 <SEP> 5.005 <SEP> 5 <tb> <SEP> 4.919 <SEP> 1 <SEP> 4.899 <SEP> 1 <tb> <SEP> - <SEP> - <SEP> 4.725 <SEP> 1 <tb> 4.629 <SEP> 9 <SEP> <SEP> 4.61n <SEP> <SEP> 9 <tb> <SEP> 1 <SEP> 4.915 <tb> <SEP> 4.495 <SEP> 2 <SEP> 0.490 <SEP> 1 <tb> <SEP> 4.4n5 <SEP> 2 <SEP> 4.470 <SEP> 2 <tb> <SEP> 4.386 <SEP> 13 <SEP> 4.380 <SEP> 14 <tb> <SEP> 4.291 <SEP> 10 <SEP> 4.280 <SEP> 13 <tb> <SEP> 4.124 <SEP> 13 <SEP> 4.103 <SEP> 3 <tb> <SEP> 4.104 <SEP> 4 <SEP> - <SEP> <tb> <SEP> 4.039 <SEP> 6 <SEP> 4.022 <SEP> 7 <tb> <SEP> 3.950 <SEP> 1 <SEP> 3.950 <SEP> 2 <tb> <SEP> 3.380 <SEP> 100 <SEP> - <SEP> <tb> <SEP> 3.850 <SEP> 69 <SEP> 2.869 <SEP> 100 <tb> <SEP> - <SEP> - <SEP> 3.836 <SEP> 73 <tb> <SEP> 3.743 <SEP> 51 <SEP> 3.764 <SEP> 35 <tb> <SEP> 3.730 <SEP> 50 <SEP> 3.735 <SEP> 54 <tb> <SEP> 3.678 <SEP> 21 <SEP> 3.662 <SEP> 29 <tb> <SEP> 3.649 <SEP> 22 <SEP> 3.604 <SEP> 4 <tb> <SEP> 3.629 <SEP> 5 <SEP> - <SEP> - <SEP> <tb> <SEP> - <SEP> - <SEP> 3.900 <SEP> 5 <tb> <SEP> 3.466 <SEP> 12 <SEP> 3.469 <SEP> 10 <tb> <SEP> 3.364 <SEP> 6 <SEP> 3.368 <SEP> 7 <tb> <SEP> 3.332 <SEP> 5 <SEP> . <SEP> 3.342 <SEP> 10 <tb> <SEP> 3.329 <SEP> 4 <SEP> <tb> <SEP> 3.273 <SEP> 4 <SEP> 3.265 <SEP> 3 <tb> <SEP> 1.267 <SEP> 4 <SEP> - <SEP> <tb> <SEP> 3.260 <SEP> 4 <SEP> 3.260 <SEP> 12 <tb> Within the above definition of chemical composition, zeolite Nu-4 appears to be most readily formed in a state of high purity when the number of-moles of Y203 is in the range 0.5 to 2. This definition includes both freshly prepared zeolite Nu-4 ("freshly prepared" means the product of synthesis and washing, with optional drying, as hereinafter described) and also forms of it resulting from dehydration, and/or- calcination, and/or ion exchange. In freshly prepared zeolite Nu-4, M1 may include an alkali metal cation, especially sodium, possibly with ammonium and/or hydrogen and usually, or when prepared from nitrogen compounds, includes nitrogen-containing organic cations as described below or cationic degradation products thereof, or precursors thereof. These nitrogencontaining cations are hereinafter referred to as Q. Whilst potassium or rubidium can be present as alkali metal ions, there is a tendency to form zeolite Nu-10 (described in our co-pending. United Kingdom Patent Application No. 8115410) as a significant impurity. The freshly-prepared zeolite Nu-4 may -contain nitrogen-containing compounds, typically in the range 0.4 to 6 moles per mole of XO2. Since Nu-4 is a zeolite, the nitrogen-containing base must be physically trapped within the crystal lattice. It can-be removed by thermal or oxidative degradation or by displacement by suitable small molecules. This physically trapped basic material does not constitute part of the composition for the purposes of the definition. Thus a zeolite Nu-4 as made typically has the following molar composition: 0.1 to 7.5 M20 : 0.4 to 6 Q : 0.2 to 2.5 Y203 : 100 X02 o to 50 H 0 wherein M is an alkali metal or ammonium, or hydrogen. The H2 0 content of freshly prepared zeolite Nu-4 depends on the conditions.in which it has been dried after synthesis. In calcined forms of zeolite Nu-4, M1 may be alkali metal and possibly hydrogen but includes less or no nitrogerr containing organic compounds, since these are burnt ou, in the presence of air leaving hydrogen as the other balancing cation, or otherwise displaced prior to calcination. Among the ion-exchanged fo=s of zeolite Nu-4, the ammonium (NH4+) is of importance since it-can be readily converted to the hydrogen form by calcination. The hydrogen form can also beprepard'directly by exchange with an acid. The hydrogen-form and forms containing metals introduced by ion exchange are described further below. We believe that zeolite Nu-4 is a new member of the ZSM5/ll series of zeolites, which has the lowest symmetry possible for members of this series. ZSMll has the highest i.e. has tetragonal symmetry. ZSM5 usually exhibits orthorhombic symmetry, but recently (E L Wu et al J Phys. Chem. 83, 2777 (1979)) it has been claimed that ZSMS under special circumstances, can exhibit pseudo monoclinic symmetry. Specific treatments, e.g. NE4+ exchange, calcination, sorption, can cause displacive transformation from orthorhombic to pseudo monoclinic symmetry. These transformations are completely reversible and in ZSM5 depend only upon the ions or sorbate present within the ZSM5 lattice. We have found that zeolite Nu-4 as made, or in all its ion exchanged, calcined, hydrated, dehydrated or sorbing forms, always exhibits true monoclinic symmetry. This is best demonstrated by reference to Nature 275, 120 (1978), where it is noted that the major clue to differences in structure, between the closely related zeolites ZSM5 and ZSMll, came from differences in X-ray diffraction data. In the diffraction data for ZSM5 (orthorhombic) there is a significant splitting of certain ZSMll (tetragonal) type peaks into doublets and there are variations in peak heights. This behaviour confirms that ZSM5 has a lower order of symmetry than ZSMll, but is nevertheless closely related. In going from tetragonal ZSM5 to pseudo-monoclinic ZSM5 there is further marginal peak splitting. However in the case of zeolite Nu-4 there is very substantial splitting of peaks as compared with tetragonal or even pseudo-monoclinic ZSM5. This splitting includes many new doublets and even triplets, and also marked variations in 14re intensities. Table 2 compares zeolite Nu-4. with pseudomonoclinic and tetragonal ZSM5 and also ZSMll. Crystals of zeolite Nu-4 are always characteristically large and prismatic with typical dimensions in the range 3 to 100 mp. Twinning is a very common feature. Further confirmation of differences between zeolite Nu-4 and ZSM5 comes from sorption behaviour. Table 3 gives sorption results which indicate that HNu-4 has a more constrained tunnel network than HZSM5 since both m-xylene and cyclohexane are sorbed such more slowly than in ZSM5. This sorption data suggests that zeolite Nu-4 may be useful in separating C8 aromatic fractions. Zeolite Nu-4 has molecular sieve properties analogous to those of known zeolites. Thus zeolite Nu-4 may be characterised by its adsorption capacity for mole cules of various sizes. Typical results are shown in Table 3. Slight sorption of cyclohexane and rapid sorption of p-xylene suggest an entry port size of about 6.0 A in diameter. The results given in Table 3 also show that m-xylene is sorbed more slowly than p-xylenes, thereby indicating that zeolite Nu-4 may be used:to separate xylene isomers. By comparison with ZSM5 prepared from tetraalkylammonium or hexamethylenediamine, r zeolite Nu-4 should be more effective in separating xylene isomers. The invention provides also a method of making zeolite Nu-4 which comprises reacting an aqueous mixture comprising at least one oxide X02, at least one oxide Y 203 and at least one polyalkylene polyamine having the formula: TABLE 2 EMI6.1 <tb> <SEP> 28M5 <SEP> + <SEP> 28M5 <SEP> + <SEP> 25Mil <SEP> a <tb> <SEP> Zeolite <SEP> No-4 <SEP> NH4 <SEP> exchanged <SEP> as <SEP> made <SEP> as <SEP> made <tb> <SEP> of <SEP> Example <SEP> 3 <SEP> 1@addomonoclinic <SEP> <SEP> crthorhombic <SEP> tetraqonal <tb> <SEP> dA <SEP> 100 <SEP> I/I0 <SEP> dA <SEP> 100I/I0 <SEP> dA <SEP> 100I/I0 <SEP> dA <SEP> 100I/I0 <tb> <SEP> 11.2 <SEP> D <SEP> 16 <SEP> 11.2 <SEP> 100 <SEP> 11.2 <SEP> 45 <SEP> 11.9 <SEP> 27 <tb> 11.1 <SEP> 20 <SEP> 10.0 <SEP> 70 <SEP> 10.0 <SEP> 30 <SEP> 10.07 <SEP> 23 <tb> <SEP> 10.06 <SEP> 15 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 9.90 <SEP> T <SEP> 8 <SEP> 9.71 <SEP> 12 <SEP> 9.71 <SEP> 20 <SEP> - <SEP> <tb> <SEP> 5.72 <SEP> 8 <SEP> 9.02 <SEP> 1 <SEP> 9.02 <SEP> 2 <SEP> - <SEP> <tb> <SEP> 9.05 <SEP> 1 <SEP> 8.19 <SEP> 1 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 7.50 <SEP> 2 <SEP> 7.38 <SEP> 2 <SEP> 7.36 <SEP> 15 <SEP> 7.5 <SEP> 2 <tb> <SEP> - <SEP> - <SEP> 7.20 <SEP> 1 <SEP> 7.20 <SEP> 1 <SEP> 7.25 <SEP> 1 <tb> <SEP> 7.09 <SEP> 1 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 7.11 <SEP> 1 <tb> <SEP> 6.78 <SEP> 2 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 6.73 <SEP> 3 <tb> <SEP> - <SEP> - <SEP> 6.56 <SEP> 15 <SEP> 4.36 <SEP> 10 <SEP> - <SEP> <tb> <SEP> 6.44 <SEP> 5 <SEP> 6.37 <SEP> 15 <SEP> 6.37 <SEP> 10 <SEP> 6.42 <SEP> 2 <tb> <SEP> - <SEP> - <SEP> 6.21 <SEP> 21 <SEP> 6.21 <SEP> 14 <SEP> 6.33 <SEP> 2 <tb> <SEP> 6.07D <SEP> 5 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 605 <SEP> 5 <SEP> 6.03 <SEP> 17 <SEP> 6.03 <SEP> ) <SEP> 12 <SEP> 6.09 <SEP> 3 <tb> <SEP> 5.97 <SEP> 1 <SEP> - <SEP> - <SEP> 5.99D <SEP> 12 <SEP> 6.02D <SEP> 3 <tb> <SEP> 5.75 <SEP> 8 <SEP> 5.72 <SEP> 12 <SEP> 5.72 <SEP> 5 <SEP> 5.75 <SEP> 2 <tb> <SEP> 5.65 <SEP> ) <SEP> 6 <SEP> 5.60 <SEP> 12 <SEP> 5.60 <SEP> 28 <SEP> 5.61 <SEP> 5 <tb> <SEP> 5.63 <SEP> ) <SEP> 2 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 5.41 <SEP> 2 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 5.19 <SEP> 2 <SEP> 5.22 <SEP> <SEP> 2 <SEP> 5.22 <SEP> 5 <SEP> 5.1X <SEP> <tb> <SEP> 5.07 <SEP> ) <SEP> x <SEP> <SEP> 5.09 <SEP> 3 <SEP> 5.09 <SEP> 5 <SEP> 5.03 <SEP> 3 <tb> <SEP> 5.01 <SEP> ) <SEP> 4 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> - <SEP> - <SEP> 4.96 <SEP> 8 <SEP> 4.95 <SEP> 2 <SEP> - <SEP> <tb> <SEP> 4.915 <SEP> 1 <SEP> 4.93 <SEP> ) <SEP> # <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 4.629 <SEP> 9 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> - <SEP> - <SEP> 4.592 <SEP> 1 <SEP> - <SEP> - <SEP> 4.62 <SEP> 4 <tb> <SEP> 4.558 <SEP> 1 <SEP> 4.55 <SEP> ) <SEP> 5 <SEP> 4.55 <SEP> 4 <SEP> 4.48 <SEP> 1 <tb> <SEP> 4.495T <SEP> 2 <SEP> 4.40D <SEP> 5 <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 4.475 <SEP> 2 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 4.386 <SEP> 13 <SEP> 4.375 <SEP> 8 <SEP> 4.375 <SEP> 8 <SEP> 4.37 <SEP> 9 <tb> <SEP> 4.291 <SEP> 10 <SEP> 4.250 <SEP> 2 <SEP> 4.250 <SEP> 1 <SEP> <SEP> 4.2S <SEP> 2 <SEP> <tb> <SEP> 4.124) <SEP> 13 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 4.204T <SEP> 4 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 4.029 <SEP> 6 <SEP> 4.047 <SEP> 2 <SEP> 4.047 <SEP> 1 <SEP> 4.08 <SEP> 4 <tb> <SEP> 3.550 <SEP> 1 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 3.880D <SEP> 100 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 3.850 <SEP> 69 <SEP> 3.867D <SEP> 56 <SEP> 1.867 <SEP> 100 <SEP> 3.86 <SEP> 100 <tb> <SEP> - <SEP> - <SEP> 3.830 <SEP> 50 <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 3.743) <SEP> 51 <SEP> 3.74 <SEP> 50 <SEP> 3.77 <SEP> ) <SEP> 30 <SEP> - <SEP> <tb> <SEP> 3.730D <SEP> 50 <SEP> - <SEP> - <SEP> 3.74D <SEP> 50 <SEP> - <SEP> <tb> <SEP> 3,678 <SEP> 27 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> <tb> <SEP> 3.649T <SEP> 22 <SEP> 3.660 <SEP> 20 <SEP> 3.660 <SEP> 35 <SEP> 3.68 <SEP> 5 <tb> <SEP> 1.629 <SEP> 5 <SEP> 2.640 <SEP> 19 <SEP> - <SEP> - <SEP> - <SEP> D = Doublet + From 3 Phys Chem 83, (71) # 2777 (1979) T = Triplet a form US Patent 3,709,979 TABLE 3 - SORPTION ON HNu-4 (Example 4) AND HZSMS AT 25 C EMI7.1 <SEP> % <SEP> Sorption <SEP> w/w <tb> <SEP> Cyclo <SEP> n-hexane <SEP> p-xylene <SEP> m-xylene <SEP> hexane <tb> <SEP> p/p0 <SEP> = <SEP> 0.33 <SEP> p/p0 <SEP> = <SEP> 0.5 <SEP> p/p0=0.5 <SEP> p/p0 <SEP> = <SEP> 0.4 <tb> Zeolite <SEP> Form <SEP> A <SEP> B <SEP> C <SEP> D <SEP> A <SEP> B <SEP> C <SEP> D <SEP> A <SEP> B <SEP> C <SEP> D <SEP> C <SEP> D <tb> HZSMS <SEP> pseusomonoclinic <SEP> 9.3 <SEP> - <SEP> 9.6 <SEP> 10.5 <SEP> 8.5 <SEP> - <SEP> 9.5 <SEP> 100 <SEP> 6.2 <SEP> - <SEP> 9.1 <SEP> 9.8 <SEP> 2.0 <SEP> 3.0 <tb> HNu-4 <SEP> monoclinic <SEP> 10.5 <SEP> 11 <SEP> 11.2 <SEP> 12.0 <SEP> 8.5 <SEP> 9.7 <SEP> 9.8 <SEP> 10.3 <SEP> 1.9 <SEP> 4.2 <SEP> 6.8 <SEP> 10.0 <SEP> 0.5 <SEP> 2.5 <tb> A,B,C,D are 10 minutes, 1, 2 and 24 hours respectivaly. EMI8.1 wherein each RÚ and Rê, independently, represents hydrogen or a C1-C6 alkyl group, x is an integer from 2 to 6 and y is an integer from 0 to 10, provided that when y is 0 and RÚ and Rê are both alkyl groups, x is 2 to 5 and that when Y is 0 and R and Rê are not both alkyl groups, x is 4 or 5, an amine degradation pro duct thereof, 'or-a precursor thereof. The reaction mixture can have the following molar ratios: X02/Y203 = 40 to 1000 Q/X 2 = 0.01 to 4.0 MlOH/XO2 = O to 2.0 H2o/X02 = 10 to 200 M2Z/X02 = O to 4.0 However, zeolite Nu-10 of our copending UR Patent Application No. 8115410 can be synthesised from a similar range of mo.lar ratios.. Therefore, to ensure that zeolite Nu-4 is obtained free of zeolite Nu-10 it is necessary to employ either low H20/X02 ratios or high MÚOH/XO2 ratios or both. The preferred ranges for preparing zeolite Nu-4 are as follows: Range 1 = 40 to 70 XO2/Y2O3 Q/XO2 = 0.1 to 4.0 H2O/XO2 = 15 to 45 M10H/x02 = 0 to 1.0 M2Z/X02 = O to 2.0 Range 2(a) X02/Y203 = 70 to 120 Q/X02 = 0.1 to 4.0 M2Z/X02 = O to 2.0 if H20/X02 = 20 to 30 then MloH/XO2 = 0.04 to 1.0 2(b): if H20/X02 = 30 to 40 then MÚOH/XO2 = 0.1 to 1.0 2(c): : if H20/X02 = 40 to 60 then MÚOH/XO2 = 0.18 to 1.0 Range 3 X02/Y203 = 120 to 300 Q/X 2 = 0.05 to 4.0 M2Z/X02 = O to 2.0 H20/X02 = 20 to 60 M1OH/X02 = 0.08 to 1.0 Range 4 XO2/Y2O3 = 300 to 500 Q/X02 = 0.02 to 4.0 M2Z/X02 = O to 2.0 H2O/XO2 = 10 to 70 M OH/X02 = O to 1.0 Zeolite Nu-4 can be prepared in the temperature range 50 to 2500 C. The preferred range is 90 to 1800C and crystallisation is carried out until substantially pure crystalline Nu-4 is obtained. Agitated reactions are preferred. X is silicon or germanium, Y is aluminium, iron, chromium, vanadium molybdenum, arsenic, antimony, manganese, gallium or boron, M1 is an alkali metal optionally with ammonium and/or hydrogen, M2 is an alkali metal or ammonium or hydrogen and can be the same as M1 and Q is the aforesaid polyalkylene polyamine, amine degradation product thereof or a precursor thereof, or a related compound. Z is a strong acid radical present as a salt of Mê and may be added as a free acid to reduce the free M1OH level to a desired value. M2Z addition, while not essential, can accelerate crystallisation of zeolite Nu-4 and can also effect the size of crystals obtained. It should be noted that addition of M2 Z can promote the formation of a-quartz and a-crystobalite, this can usually be avoided by reducing reaction times and/or temperature to minimise the chances of overrun. If MêZ remains intercalated within the zeolite Nu-4 framework, then it can have substantial effects on the sorption and catalytic properties. M1 and/or Q can be present as hydroxides or salts of inorganic or organic acids provided the MlOHJXO2 requirement is fulfilled. The preferred polyalkylene polyamines are triethylene tetramine, tetraethylene pentamine, and unsymmetrical disubstituted diamines such as N, N-diethyl ethylenePdiamine. The preferred alkali metal z1 is sodium and for M21 sodium or hydrogen is preferred. The preferred o < ìds X 2 is silica (Sic2) and the preferred oxide Y203 i5 alumina (Al203). ,The silica source-can be any of those ccmmonly considered for use in synthesising zeolites, for example powdered solid silica, silicic acid, colloidal silica or dissolved silica. Pmong the powdered silicas usable are precipitated silicas, especially those made by precipitation from an alkali metal silicate solution, such as the type known as "KS 300" made by AKZO, and similar products, aerosil silicas, fume silicas and silica gels suitably in grades for use in reinforcing pigments for rubber or silicone rubber. Colloidal silicas of various particle sizes may be used, for example 10-15 or 40-50 microns, as sold under the Registered Trade Marks "LUDOX", "NALCOAG" and "SYTON". The usable dissolved silicas include commercially available waterglass silicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of Si02 per mol of alkali metal oxide, "active" alkali metal silicates as defined in UK Patent 1193254, and silicates made by dissolving silica in alkali metal hydroxide or quaternary ammonium hydroxide or a mixture thereof. The alumina source is most conveniently sodium aluminate, but can be or include aluminium, an aluminium salt,. for example the chloride, nitrate pr sulphate, an aluminium alkoxide or alumina itself, which should preferably be in a. hydrated or hydratable form such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina or the alpha or beta trihydrate. The reaction mixture is reacted usually under autogenous pressure, optionally with added gas, e.g. nitrogen at a temperature between 85 and 2500C until crystals of zeolite Nu-4 form, which can be from 1 hour to many months depending on the reactant composition and the operating temperature. Agitation is optional, but is preferable since it reduces the reaction time. At the end of the reaction, the solid phase is collected on a filter and¯washed and is then- ready for further steps such as drying, dehydration and ion-exchange. If the product of the reaction contains alkali metal ions, these have to be at least partly removed in order to prepare the hydrogen form of Nu-4 and this can be done by ion exchange with an acid, especially a strong mineral acid such as hydrochloric acid or by way of the ammonium compound, made by ion exchange with a solution of an ammonium salt such as ammonium chloride. Such ion exchange can be carried out by slurrying once or several times with the solution. In general, the cation(s) of zeolite Nu-4 can be replaced by any cation(s) of metals, and particularly those in Groups IA, IB, IIA, IIB, III (including rare earths) VIII (including ncble metals) and by lead, tin and bismuth. (The Periodic Table is as in "Abridgements of Specifications" published by the UK Patent Office). Exchange is carried out using any water soluble salts containing the appropriate cation. In order to prepare a catalyst,zeolite Nu-4 may be used in association with an inorganic matrix, or with 'other materials which can be either inert or catalytically active. The matrix may be present simply as a binding agent to hold the small zeolite particles (0.005 to 10 microns) together, or it.may be added as a diluent to control the amount'of conversion in a process which may otherwise proceed at too high a rate, leading to catalyst fouling as a result of excessive coke formation. Typical inorganic diluents include catalyst support materials such as alumina, silica, kaolinic clays, bentonites, montmorrilonites, sepiolite, attapulgite, Fullers earth, synthetic porous materials such as Si02-A1203, SiO2-ZrO2, SiO2-ThO2, Si02-BeO, SiO2-TiO2 or any ccmbination of these oxides. An effective way of mixing zeolite Nu-4 with such diluents is to mix appropriate aqueous slurries in a mixing nozzle and then to spray-dry the slurry. Other ways of mixing can be used. If zeolite Nu-4 in any cationic form; or as a catalytic composite is exchanged or impregnated with hydrogenation/dehydrogenation components, such as Ni, Co, Pt, Pd, Re, Rh, hydrocracking and reforming catalysts can be made, especially if the Na20 content is less than 0.3% w/w. A wide range of hydrocarbon conversion catalysts can be prepared from zeolite Nu-4 by ion exchange or impregnation with cations, or oxides, selected from the following, Cu, Ag, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, noble metals. Usually the Nu-4 catalyst will be in acid form, thus stoichiometry is maintained by H+ or H30+ as an additional balancing cation, or as sole cation. Such catalysts may find application in the following processes catalytic cracking, hydrodesulphurization, hydrodenitrification, catalytic dewaxing, alkylation of alkanes or aromatics, dealkylation, disproportionation, isomerisation of alkanes and alkylbenzenes, dehydration reactions, oxidation and polymerisation. We have found that zeolite Nu-4 is especially useful as a catalyst for xylenes isomerisation. As is well known, the major aim in xylenes isomerisation is to increase the para-xylenes content of the feedstock at the expense of. other isomers since para-xylene is a particularly useful and valuable product. The mixed xylenes feedstocks commonly available for xylenes isomerisation usually contain amounts of the three xylene isomers as well as ethylbenzene. Hitherto, some of the mixed xylenes feedstock available has contained relatively small amounts of ethylbenzene but it is anticipated that in the future such feedstocks will become more expensive and that resort will have to bs made to feedstocks containing rather larger amounts s ethylbenzene, say up to about 25% ethylbenzene. In our copending UK Application No. 8115411 we disclose the use of Nu-4 as a superior xylenes isomerisation catalyst. Zeolite Nu-4 may also find applications in the separation of aromatics and. cycloparaffins, and in pollution control by its ability to remove organic contaminants from aqueous effluents. The invention is illustrated by the following Examples. Example 1 Preparation of sodium tetraethylenepentamine CTEPA) Nu-4 and sodium hydrogen Nu-4. The synthesis mixture had the following molar composition: 11.4 Na20, 29.3 TEPA, A12031 100.7 Si02, 4058 H20, 54.7 NaCl. 37.8 g TEPA were dispersed in 142 g colloidal silica (SYTON X 30)(Na20, 0.395 A1203, 85.6 Si02, 689 HzO) Next 1.3 g sodium aluminate (1.19 Na20, A1203, 1.29 H20) dissolved in 20 g water (containing 5g sodium hydroxide) was stirred into the silica suspension followed by 23.5 g sodium chloride dissolved in 378 g water. The resulting slurry was reacted for 2 days at'18O0C in a stirred 1 litre stainless steel autoclave under autogenous pressure. After cooling to about 600C the slurry was filtered and washed with 2 litres of distilled water at 606C and dried overnight at 1200C. The product was sodium TEPA Nu-4 and had the X-ray diffraction data shown in Table 1 and molar composition 0.7 Na20, 2.2 Q, A1203, 64 SiO2, 15 H20. The bulk of this product was calcined in air for 17 hours at 5500C and had an X-ray diffraction pattern very similar to the asmade Nu-4 and nitrogen and carbon contents less than 0.1. The product was sodium hydrogen Nu-4 and the crystals were prismatic of average size 17 x 10 x 8 mv and having a substantial degree of twinning. Example 2 Preparation of hydrogen Nu-4. The calcined product of Example 1 was slurry-exchanged for 1 hour at 2500C with 4 ml of N hydrochloric acid per g of zeolite. The resulting hydrogen Nu-4 was washed with 10 ml of distilled water per g of zeolite, dried overnight at 1200C and at 4500C for 6 hours. Example 3 In a second synthesis experiment, the mixture had the following molar composition 1.91 Na20, 20 TEPA, A1203, 60 SiO2, 2400 H20, 32 NaCl. The reaction was carried out exactly as described in Example 1 except that the weights of reactants used were as follows: 44.5 g TEPA, 145 g SYTON X-30, 2.7g sodium aluminate, 18g water, 22g sodium chloride, 387 g water. The product was identified as zeolite Nu-4 from X-ray analysis (Table 4) and its as made composition was 0.38 Na2O, 2.5 Q, At2031 41 SiO2, 12.5 H20. Again the crystals were prismatic with average size 12 x 8 x 5 mv and a substantial level of twinning. Example 4 Part of the product of Example 3 was calcined for 17 hours in air at 5500C and then exchanged with N hydrochloric acid as in Example 2. The resulting hydrogen Nu-4 after calcination at 4500C for 6 hours had the following molar composition 0.014 Na2O, A1203 40.1 SiO2. This sample was used in the sorption and catalytic experiments. Example 5 In this Example, lOg of the as-made product of Example 1 was heated in a stirred 1 litre stainless steel autoclave with 500 ml of 10% sodium chloride solution (aqueous) at l800C for 6 hours. The slurry product was filtered, and washed with 1 litre of distilled water at 600C, and dried TABLE 4 - AS MADE ZEOLITE Nu-4 OF EXAMPLE 3 EMI16.1 dA <SEP> 11.2 <SEP> 10.07 <SEP> 9.98 <SEP> 9.79 <SEP> 9.31 <SEP> 9.02 <SEP> 7.45 <SEP> 7.09 <SEP> 6.72 <tb> 100I/I0 <SEP> 30 <SEP> 26 <SEP> 8 <SEP> 10 <SEP> 1 <SEP> 1 <SEP> 4 <SEP> 2 <SEP> 4 <tb> dA <SEP> 6.38 <SEP> 6.06 <SEP> 6.01 <SEP> 5.97 <SEP> 5.73 <SEP> 5.55 <SEP> 5.38 <SEP> 5.14 <SEP> 4.99 <tb> 100I/I0 <SEP> 8 <SEP> 5 <SEP> 7 <SEP> 7 <SEP> 9 <SEP> 8 <SEP> 3 <SEP> 5 <SEP> 6 <tb> dA <SEP> 4.890 <SEP> 4.726 <SEP> 4.609 <SEP> 4.558 <SEP> 4.495 <SEP> 4.461 <SEP> 4.370 <SEP> 4.272 <SEP> 4.126 <tb> 100I/I0 <SEP> 1 <SEP> 1 <SEP> 10 <SEP> 3 <SEP> 1 <SEP> 3 <SEP> 10 <SEP> 16 <SEP> 7 <tb> dA <SEP> 4.086 <SEP> 4.047 <SEP> 4.023 <SEP> 3.950 <SEP> 3.880 <SEP> 3.837 <SEP> 3.765 <SEP> 3.736 <SEP> 3.610 <tb> 100I/I0 <SEP> 4 <SEP> 2 <SEP> 8 <SEP> 2 <SEP> 100 <SEP> 78 <SEP> 35 <SEP> 24 <SEP> 4 <tb> overnight at 12O0C. The X-ray data for this product was identical with the as made Nu-4. However, from chemical analysis this treatment removed all the TEPA and converted the zeolite to the sodium¯ form. The molar composition of the dried product was 0.92 Na20, A1203, 72 SiO2, 20.7 H20. Example 6 In another synthesis experiment, the mixture had the following molar composition 40 Na20, 8 TEPA,A1203, 150 SiO2, 3770 H20, 35 H2S04. In this example 15.1 g TEPA were stirred into 288 g Q-79 waterglass (Na20, 0.1 A1203-3.775 SiO2, 24 H20). Next 3.8 g aluminium sulphate (A1203, 3 S03, 16 H20) and 3.2 g 98% sulphuric acid in 503 g water were stirred into the silicate solution. The resulting slurry was reacted at 1800C for 4 days in a stirred, stainless steel autoclave. The product was again identified as zeolite Nu-4 of molar composition 0.16 Na2O, 5.8 0, A1203, 120 SiO2, 40 H20. Example 7 In this example, the reaction mixture had the following molar composition after pre-evaporation at 105 C. 2.34 Na2O, 27 TEPA, A1203, 96.3 SiO2, 1926 H20, 54.8 NaCI, 38g TEPA were dispersed in 142 g colloidal silica. Next 1.6g sodium aluminate (1.25 Na2O, Al203, 3 H20) were dissolved in log water and stirred into the silica suspension. Finally 23g sodium chloride dissolved in 388g water were stirred in. The resulting gel/slurry had an H20/SiO2 ratio of 40, but by deliberately evaporating with stirring at 105 C, 250g of water were distilled off to give an H20/Si02 ratio of 20. This mixture was refluxed with stirring in a pyrex flask for 4 days at 105 0C. The product was an excellent sample of zeolite Nu-4, having X-ray data as shown in Table 5. When an identical preliminary reaction mixture was made up as above, but omitting the deliberate evaporation stage, i.e. running the reaction at 105 0C under reflux at H20/Si02 ratio of 40, then after 40 days TABLE 5- X-RAY DATA FOR AS MADE ZEOLITE Nu-4 OF EXAMPLE 7 EMI18.1 dA <SEP> 11.3 <SEP> 10.2 <SEP> 9.93 <SEP> 9.90 <SEP> 7.47 <SEP> 6.73 <SEP> 6.39 <SEP> 6.10 <SEP> 6.03 <tb> 100I/I0 <SEP> 39 <SEP> 25 <SEP> 6 <SEP> 8 <SEP> 3 <SEP> 4 <SEP> 6 <SEP> 4 <SEP> 6 <tb> dA <SEP> 5.72 <SEP> 5.63 <SEP> 5.59 <SEP> 5.37 <SEP> 5.16 <SEP> 5.01 <SEP> 4.910 <SEP> 4.623 <SEP> 4.48 <tb> 100I/I0 <SEP> 5 <SEP> 6 <SEP> 6 <SEP> 2 <SEP> 2 <SEP> 3 <SEP> 1 <SEP> 8 <SEP> 3 <tb> dA <SEP> 4.460 <SEP> 4.375 <SEP> 4.271 <SEP> 4.120 <SEP> 4.077 <SEP> 4.004 <SEP> 3.867 <SEP> 3.850 <SEP> 3.779 <tb> 100I/I0 <SEP> 2 <SEP> 14 <SEP> 11 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 100 <SEP> 70 <SEP> 25 <tb> dA <SEP> 3.754 <SEP> 3.731 <SEP> 3.655 <SEP> 3.605 <SEP> 3.493 <SEP> 3.447 <SEP> 3.401 <SEP> 3.357 <SEP> 3.314 <tb> 100I/I0 <SEP> 32 <SEP> 49 <SEP> 26 <SEP> 1 <SEP> 6 <SEP> 11 <SEP> 4 <SEP> 6 <SEP> 9 <tb> dA <SEP> 3.255 <SEP> 3.143 <SEP> 3.053 <SEP> 2.988 <SEP> 2.945 <SEP> 2.867 <SEP> 2.788 <SEP> 2.739 <SEP> 2.611 <tb> 100I/I0 <SEP> 3 <SEP> 2 <SEP> 10 <SEP> 12 <SEP> 3 <SEP> 2 <SEP> 1 <SEP> 3 <SEP> 3 <tb> dA <SEP> 2.515 <SEP> 2.491 <SEP> 2.417 <SEP> 2.398 <SEP> 2.015 <SEP> 1.998 <tb> 100I/I0 <SEP> 2 <SEP> 3 <SEP> 2 <SEP> 3 <SEP> 8 <SEP> 8 <tb> the product was zeolite Nu-10 containing no detectable zeolite Nu-4. Example 8 In this example, the mixture had the following molar composition: 1.81 Na2O, 47.6 TETA, A1203, 50.6 SiO2, 2028 H20 91.5g triethylene tetramine were stirred into 373g water followed by 137g colloidal silica. Finally 3g sodium aluminate (1.25 Na2O, A1203, 3H20) dissolved in lOg water were stirred in until homogenous (30 minutes). The reaction was as for Example 1 except that the reaction time was 5 days. The product was zeolite Nu-4 having X-ray data as shown in Table 6, and having a molar composition 0.3 Na20, 1.4 TETA, A1203, 40 SiO2, 12 H20. Example 9 The reaction mixture had the following molar composition: 0.50 Na2O, 20.4 TEPA, A1203, 61.8 SiO2, 2446 H20 32.6 NaCl, 1.47 Na2SO4. 44.5g TEPA were dispersed in 142g colloidal silica. Next 2.3g sodium aluminate (1.19 Na2O, A1203, 1.29 H20) were dissolved in 18g water and then stirred into the silica suspension. Finally 22g sodium chloride and 1.7g concentrated sulphuric acid in 388g water were stirred in. The mixture was homogenized, and then reacted as in Example 1, but for a period of 5 days at 180 C. The product was an excellent sample of zeolite Nu-4 having the X-ray data shown in Table 7. Example 10 The reaction mixture had the following molar composition: 4.64 Na2O, 20.4 TEPA, A1203, 61.8 Six2, 2446 H20 32.6 NaCl. The mixture was as for Example 9, except that 2.5 g sodium hydroxide were added to the sodium aluminate, and no sulphuric acid was added to the mixture. The reaction was as for example 9 except that zeolite Nu-4 crystallised in only 1 day instead of the 5 days required for Example 9. X-ray data for the product is given in Table 8. TABLE 6 - X-RAY DATA ZEOLITE Nu-4 OF EXAMPLE 8 EMI20.1 dA <SEP> 11.7 <SEP> 11.26 <SEP> 10.8 <SEP> 10.11 <SEP> 9.85 <SEP> 9.13 <SEP> 7.47 <SEP> 6.97 <SEP> 6.76 <SEP> 3.314 <tb> 100I/I0 <SEP> 2 <SEP> 6 <SEP> 10 <SEP> 21 <SEP> 28 <SEP> 19 <SEP> 1 <SEP> 15 <SEP> 4 <SEP> 16 <tb> dA <SEP> 6.01 <SEP> 5.58 <SEP> 5.37 <SEP> 5.15 <SEP> 5.02 <SEP> 4.618 <SEP> 4.376 <SEP> 4.360 <SEP> 4.287 <SEP> 3.878 <tb> 100I/I0 <SEP> 13 <SEP> 20 <SEP> 4 <SEP> 14 <SEP> 14 <SEP> 11 <SEP> 20 <SEP> 15 <SEP> 13 <SEP> 100 <tb> dA <SEP> 3.846 <SEP> 3.747 <SEP> 3.660 <SEP> 3.498 <SEP> 3.457 <SEP> 3.375 <SEP> 3.329 <SEP> 3.328 <SEP> 3.051 <SEP> 2.830 <tb> 100I/I0 <SEP> 72 <SEP> 60 <SEP> 32 <SEP> 15 <SEP> 15 <SEP> 14 <SEP> 15 <SEP> 9 <SEP> 13 <SEP> 16 <tb> dA <SEP> 2.623 <SEP> 2.520 <SEP> 2.430 <SEP> 2.216 <SEP> 2.067 <SEP> 2.028 <SEP> 2.011 <SEP> 1.889 <SEP> 1.683 <SEP> 1.638 <tb> 100I/I0 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 1 <SEP> 2 <SEP> 13 <SEP> 23 <SEP> 4 <SEP> 5 <SEP> 4 <tb> TABLE 7 - X-RAY DATA FOR ZEOLITE Nu-4 OF EXAMPLE 9 EMI21.1 dA <SEP> 11.26 <SEP> 11.13 <SEP> 10.08 <SEP> 9.99 <SEP> 7.50 <SEP> 7.16 <SEP> 6.76 <SEP> 6.41 <SEP> 6.04 <tb> 100I/I0 <SEP> 16 <SEP> 6 <SEP> 16 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 2 <SEP> 5 <SEP> 6 <tb> dA <SEP> 6.00 <SEP> 5.73 <SEP> 5.61 <SEP> 5.43 <SEP> 5.17 <SEP> 5.03 <SEP> 5.02 <SEP> 4.633 <SEP> 4.381 <tb> 100I/I0 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 4 <SEP> 7 <SEP> 12 <tb> dA <SEP> 4.287 <SEP> 4.101 <SEP> 4.028 <SEP> 3.876 <SEP> 3.859 <SEP> 3.743 <SEP> 3.725 <SEP> 3.665 <SEP> 3.654 <tb> 100I/I0 <SEP> 10 <SEP> 4 <SEP> 7 <SEP> 100 <SEP> 76 <SEP> 59 <SEP> 52 <SEP> 27 <SEP> 20 <tb> dA <SEP> 3.634 <SEP> 3.462 <SEP> 3.367 <SEP> 3.328 <SEP> 3.270 <SEP> 3.260 <SEP> 3.152 <SEP> 3.061 <SEP> 2.991 <tb> 100I/I0 <SEP> 5 <SEP> 8 <SEP> 7 <SEP> 11 <SEP> 4 <SEP> 4 <SEP> 2 <SEP> 11 <SEP> 16 <tb> dA <SEP> 2.984 <SEP> 2.952 <SEP> 2.876 <SEP> 2.838 <SEP> 2.792 <SEP> 2.792 <SEP> 2.744 <SEP> 2.692 <SEP> 2.570 <tb> 100I/I0 <SEP> 14 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 1 <SEP> 4 <SEP> 1 <SEP> 4 <SEP> 5 <tb> dA <SEP> 2.523 <SEP> 2.496 <SEP> 2.424 <SEP> 2.406 <SEP> 2.187 <SEP> 2.086 <SEP> 2.017 <SEP> 2.009 <SEP> 2.001 <SEP> 1.960 <SEP> 1.922 <tb> 100I/I0 <SEP> 5 <SEP> 6 <SEP> 3 <SEP> 5 <SEP> 2 <SEP> 2 <SEP> 11 <SEP> 10 <SEP> 12 <SEP> 3 <SEP> 4 <tb> TABLE 8 - X-RAY DATA FOR Nu-4 OF EXAMPLE 10 EMI22.1 dA <SEP> 11.26 <SEP> 11.13 <SEP> 9.98 <SEP> 9.60 <SEP> 8.93 <SEP> 7.44 <SEP> 6.70 <SEP> 6.36 <SEP> 6.02 <SEP> 5.92 <SEP> 5.68 <tb> 100I/Io <SEP> 14 <SEP> 15 <SEP> 18 <SEP> 5 <SEP> 1 <SEP> 1 <SEP> 2 <SEP> 4 <SEP> 4 <SEP> 4 <SEP> 4 <tb> dA <SEP> 5.56 <SEP> 5.37 <SEP> 5.12 <SEP> 5.07 <SEP> 4.993 <SEP> 4.844 <SEP> 4.607 <SEP> 4.521 <SEP> 4.262 <SEP> 4.262 <SEP> 4.083 <tb> 100I/Io <SEP> 4 <SEP> 1 <SEP> 1 <SEP> 3 <SEP> 3 <SEP> 1 <SEP> 6 <SEP> 2 <SEP> 12 <SEP> 9 <SEP> 4 <tb> dA <SEP> 4.010 <SEP> 3.989 <SEP> 3.843 <SEP> 3.813 <SEP> 3.766 <SEP> 3.728 <SEP> 3.652 <SEP> 3.634 <SEP> 3.477 <SEP> 3.450 <SEP> 3.348 <tb> 100I/Io <SEP> 7 <SEP> 6 <SEP> 100 <SEP> 72 <SEP> 49 <SEP> 55 <SEP> 24 <SEP> 18 <SEP> 8 <SEP> 8 <SEP> 8 <tb> dA <SEP> 3.318 <SEP> 3.256 <SEP> 3.140 <SEP> 3.051 <SEP> 2.983 <SEP> 2.979 <SEP> 2.942 <SEP> 2.869 <SEP> 2.735 <SEP> 2.608 <SEP> 2.565 <tb> 100I/Io <SEP> 10 <SEP> 4 <SEP> 2 <SEP> 10 <SEP> 15 <SEP> 13 <SEP> 5 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 2 <tb> dA <SEP> 2.516 <SEP> 2.502 <SEP> 2.490 <SEP> 2.418 <SEP> 2.400 <SEP> 2.081 <SEP> 2.019 <SEP> 2.011 <SEP> 1.998 <SEP> 1.957 <SEP> 1.920 <tb> 100I/Io <SEP> 3 <SEP> 5 <SEP> 6 <SEP> 3 <SEP> 4 <SEP> 2 <SEP> 10 <SEP> 8 <SEP> 11 <SEP> 3 <SEP> 4 <tb> Example 11 The reaction mixture had the following molar composition: 34.5 Na20, 280.5 TETA, At203, 300 Six2, 11320 H20, 166 NaCl 91.5g triethylene tetramine were dispersed in 137g colloidal silica. Next,0.45g sodium aluminate (1.25 Na20, A1203 3 H20) and 5.3g sodium hydroxide were dissolved in 20g water and stirred into the silica suspension. Finally, 21.8g sodium chloride dissolved in 363 g water were stirred in and the resulting gel/slurry was homogenised for 30 minutes and then reacted as in Example 1 but for 1 day at l800C. The product was an excellent sample of zeolite Nu-4 having the X-ray data shown in Table g and a Si02/A1203 ratio of 200. Example 12 The reaction mixture had OH-/SiO2 = 0 and a molar composition: 20.4 TEPA, A1203, 61.8 SiO2, 2446 H20, 32.5 Nail, 1.88 Na2S04 43g of TEPA were dispersed in 141g colloidal silica. Next, 2.2g sodium aluminate (1.22 Na20, At203, 1.2 H20) were dissolved in lOg water and stirred into the siliceous mix. Finally, 21.lg sodium chloride and 2.lg concentrated sulphuric acid in 380g water were stirred in, and the resulting slurry was homogenized for 30 minutes and then reacted for 9 days at 1800C in a stirred stainless steel autoclave. The product was zeolite Nu-4 having an Si02/A120 ratio of 52. Examples 13 to 16 In these Examples, additives were introduced into reaction mixtures of composition as for Example 1. All of the additives were dissolved in the sodium chloride solution except the antimonjous oxide, which was dispersed in the final reaction mixture. TABLE 9 EMI24.1 dA <SEP> 11.23 <SEP> 11.15 <SEP> 10.01 <SEP> 8.71 <SEP> 7.47 <SEP> 6.73 <SEP> 6.39 <SEP> 6.02 <SEP> 5.67 <SEP> 5.15 <tb> 100I/Io <SEP> 15 <SEP> 20 <SEP> 17 <SEP> 2 <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 3 <SEP> 2 <tb> dA <SEP> 5.01 <SEP> 5.00 <SEP> 4.624 <SEP> 4.360 <SEP> 4.273 <SEP> 4.101 <SEP> 4.019 <SEP> 3.870 <SEP> 3.851 <SEP> 3.741 <tb> 100I/Io <SEP> 3 <SEP> 3 <SEP> 6 <SEP> 21 <SEP> 14 <SEP> 15 <SEP> 14 <SEP> 80 <SEP> 100 <SEP> 55 <tb> dA <SEP> 3.659 <SEP> 3.649 <SEP> 3.630 <SEP> 3.499 <SEP> 3.444 <SEP> 3.353 <SEP> 3.252 <SEP> 3.201 <SEP> 3.156 <SEP> 3.058 <tb> 100I/Io <SEP> 29 <SEP> 20 <SEP> 5 <SEP> 11 <SEP> 17 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 3 <SEP> 9 <tb> dA <SEP> 2.989 <SEP> 2.980 <SEP> 2.947 <SEP> 2.887 <SEP> 2.806 <SEP> 2.754 <SEP> 2.699 <SEP> 2.623 <SEP> 2.509 <SEP> 2.475 <tb> 100I/Io <SEP> 15 <SEP> 12 <SEP> 6 <SEP> 2 <SEP> 1 <SEP> 3 <SEP> 2 <SEP> 5 <SEP> 14 <SEP> 11 <tb> dA <SEP> 2.413 <SEP> 2.344 <SEP> 2.296 <SEP> 2.249 <SEP> 2.140 <SEP> 2.090 <SEP> 2.021 <SEP> 2.004 <SEP> 1.995 <SEP> 1.965 <tb> 100I/Io <SEP> 5 <SEP> 1 <SEP> 9 <SEP> 5 <SEP> 8 <SEP> 2 <SEP> 11 <SEP> 14 <SEP> 11 <SEP> 3 <tb> In Example 13, the additive was 5g of potassium chrome alum. The dried product was zeolite Nu-4 containing 0.4% w/w Cr203. In Example 14, the additive was 3g of boric acid, the Nu-4 product contained 0.5% w/w B203. In Example 15, the additive was 6.5g of disodium hydrogen posphate and the Nu-4 product contained 0.6% w/w P. In Example 16, the additive was 3g of antimonious oxide and the product contained 4% w/w Sb203. Example 17 This Example demonstrates that certain diamines can be used in zeolite Nu-4 synthesis. The synthesis mixture had the following composition: 2.32 Na2O, 26Q, A1203, 96.3 SiO2, 3862 H20,548 Nazi. 21.6g TETA were dispersed in 142g colloidal silica. Next, 1.6g sodium aluminate were dissolved in lOg water and stirred into the siliceous mix. Finally, 23g sodium chloride in 398 g water were stirred in. The mixture was reacted for 3 days at 180 C ina stirred stainless steel autoclave. The product was highly crystalline zeolite Nu-4 having an SiO2/Al203 ratio of 80 and the X-ray data shown in Table 10. By contrast, if symmetrical N, Nl-diethyl ethylene diamine is used in reactions like Example 17, then the product is a mixture of approximately equal amounts of zeolites Nu-4 and Nu-10. If potassium is used as main cation then the product is pure zeolite Nu-10 (see Example 16 of our copending UK Application No 8115410). Example 18 The reaction mixture had the following molar composition: 45 Na20, 100 TEPA, A1203, 300 SiO2, 11,000 H20 350g TEPA and 175g Syton X30 were mixed with 374g water. Next, 0.Sg sodium aluminate and 8.4g sodium hydroxide were dissolved in 21g water. The aluminate was stirred into-the silica suspension and reacted for 2 days at 150 0C in a stirred 1 litre stainless steel autoclave. The suspension was reacted for 2 days at 150 0C in a stirred stainless steel autoclave. The dried product was zeolite Nu-4 having a Si02/A1203 ratio of 250. An identical mixture was reacted at 180 0C and after only 12 hours the product contained approximately equal amounts of zeolite Nu-4, a near-magadiite -.and amorphous material. After 16 hours, the product contained approximately equal quantities of zeolite Nu-4 and magadiite. This latter result illustrates that the temperature of crystallisation of Nu-4 is more critical at higher Si02/A1203 ratios. Example 19 The reaction mixture had the following molar compositon: 31.3, Na20, 25 TEPA, A1203, 100 SiO2, 4058 H20, 19.9 H2S04 42.6g TEPA were mixed into 195g Q-79 waterglass (Na20, 0,0025 A1203, 3.2 SiO2, 24.3 H20) and 414g water. Next, 5.2g aluminium sulphate (Al203, 3S03, 16 H20) and 15.4g concentrated sulphuric acid were mixed into 119g water. The acidic solution was stirred into the siliceous mixture until homogenous C30 minutes). The reaction was carried out for 2 days at 150 0C in a stirred stainless steel 1 litre autoclave. The dried zeolite Nu-4 product had a SiO2/A1203 ratio of 87. TABLE 10 X RAY DATA FOR ZEOLITE Nu-4 OF EXAMPLE 17 EMI27.1 dA <SEP> 11.11 <SEP> 11.08 <SEP> 9.97 <SEP> 9.96 <SEP> 9.71 <SEP> 8.98 <SEP> 7.42 <SEP> 7.07 <SEP> 6.71 <SEP> 5.99 <SEP> 5.74 <SEP> 5.66 <SEP> 5.60 <SEP> 5.355 <SEP> 5.131 <SEP> 5.020 <SEP> 4.988 <tb> 100I/IO <SEP> 28 <SEP> 24 <SEP> 33 <SEP> 36 <SEP> 12 <SEP> 1 <SEP> 4 <SEP> 2 <SEP> 2 <SEP> 11 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 2 <SEP> 3 <SEP> 3 <SEP> 6 <tb> dA <SEP> 4.857 <SEP> 4.652 <SEP> 4.606 <SEP> 4.543 <SEP> 4.447 <SEP> 4.360 <SEP> 4.257 <SEP> 4.073 <SEP> 4.010 <SEP> 3.841 <SEP> 3.810 <SEP> 3.742 <SEP> 3.719 <SEP> 3.644 <SEP> 3.586 <SEP> 3.477 <tb> 100I/IO <SEP> 1 <SEP> 3 <SEP> 4 <SEP> 2 <SEP> 2 <SEP> 8 <SEP> 12 <SEP> 5 <SEP> 7 <SEP> 100 <SEP> 63 <SEP> 39 <SEP> 49 <SEP> 22 <SEP> 3 <SEP> 6 <tb> dA <SEP> 3.442 <SEP> 3.314 <SEP> 3.246 <SEP> 3.185 <SEP> 3.1454 <SEP> 3.114 <SEP> 2.938 <SEP> 2.732 <SEP> 2.804 <SEP> 2.593 <SEP> 2.588 <SEP> 2.509 <SEP> 2.485 <SEP> 2.412 <SEP> 2.394 <SEP> 2.077 <SEP> 2.011 <SEP> 1.992 <tb> 100 <SEP> 8 <SEP> 10 <SEP> 4 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 7 <SEP> 4 <SEP> 4 <SEP> 2 <SEP> 2 <SEP> 3 <SEP> 6 <SEP> 3 <SEP> 4 <SEP> 1 <SEP> 11 <SEP> 11 <tb> I/O <tb>

Claims: CLAIMS 1. A synthetic zeolite material having a molar composition expressed by the formula: 0.1 to 7.5 M10 : 0.2 to 2.5 Y203 : 100 X02 : O to 50 H20 2 23 wherein M1 is a monovalent cation or 1/n of a cation of valency n, X is silicon or germanium, Y is aluminium, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium, or boron, and H20 is water of hydration additional to water notionally present when M1 is H, and having an X-ray pattern substantially as set out in Table 1. 2. A synthetic zeolite material according to claim 1 having a molar compostion expressed by the formula: 0.1 to 7.5 M20 : 0.5 to 2 Y203 : 100 X02 : O to 50 H20 3. A synthetic zeolite material according to claim 1 or claim 2 wherein M1 is or includes hydrogen. 4. A method of making a synthetic zeolite material as defined in claim 1 which comprises reacting an aqueous mixture containing at least one oxide X02, at least one oxide Y203 and at least one polyalkylene polyamine having the formula EMI28.1 wherein each of R1 and R , independently, represents hydrogen or a C1 - C6 alkyl group, x is an integer from 2 to 6 and y is an integer from 0 to 10, provided that when y is 0 and R1 and R2 are both alkyl groups, x is 2 to 5 and that when y is 0 and R1 and R2 are not both alkyl groups, x is 4 or 5. 5. A method according to claim 4 wherein the aqueous mixture has the molar composition: X02/Y203 40 to 1000 Q/X02 0.01 to 4.0 MÚOH/XO2 0 to 2.0 H2O/XO2 10 to 200 2 M Z/X02 0 to 4.0 wherein X and Y have the meanings given in claim 1, M1 is an alkali metal optionally with ammonium and/or hyrogen, M2 is an alkali metal, ammonium or hydrogen, Q is the polyalkylene polyamine and Z is a strong acid radical. 6. A method according to claim 5 wherein the aqueous mixture has the molar composition: X02/Y203 40 to 70 Q/X02 0.1 to 4.0 MlOH/XO2 0 to 1.0 H2O/XO2 15 to 45 MêZ/XO2 0 to 2.0 7. A method according to claim 5 wherein the aqueous mixture has the molar composition: X02/Y203 70 to 120 Q/XO2 0.1 to 4.0 M1OH/XO2 0.04 to 1.0 H2O/XO2 20 to 30 ZêZ/XO2 0 to 2.0 8. A method according to claim 5 wherein the aqueous mixture has the molar composition: X02/Y203 70 to 120 Q/X02 0.1 to 4.0 MÚOH/XO2 0.1 to 1.0 H2O/XO2 30 to 40 MêZ/XO2 0 to 2.0 9. Amethod according to claim 5 wherein the aqueous mixture has the molar composition: X02/Y203 70 to 120 Q/X02 0.1 to 4.0 MÚOH/XO2 0.18 to 1.0 H2O/XO2 40 to 60 MêZ/XO2 0 to 2.0 10. A method according to claim 5 wherein the aqueous mixture has the molar compostion: X02/Y203 120 to 300 Q/X 2 0.05 to 4.0 M1OH/XO2 0.08 to 1.0 H2O/XO2 20 to 60 MêZ/XO2 0 to 2.0 11. A method according to claim 5 wherein the aqueous mixture has the molar composition: X02/Y203 300 to 500 Q/X 2 0.02 to 4.0 M1OH/XO2 0 to 1.0 H2O/XO2 10 to 70 MêZ/XO2 0 to 2.0 12. A method according to any. one of claims 4 to 11 wherein the polyamine is triethylene tetramine, tetraethylene pentamine or N, N-diethyl ethylene diamine. 13. A catalyst composing a synthetic zeolite material as claimed in any one of claims 1 to 3 14. A catalytic process employing the catalyst claimed in.claim 13.

Inventors: WHITTAM, THOMAS VINCENT
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1982
Main classification: C01B33
IPC codes: C01B39, B01J29, C10G11, C10G49