PREPARATION OF ZEOLITE ZSM-12

Abstract: A method of preparing zeolite ZSM-12 which comprises forming a reaction mixture comprising a source of alkali or alkaline earth metal oxide, a source of silica which contains no more than 0.5 g alumina per 100 g silica, Q₂O and water, said mixture containing no added alumina and having an initial pH of 12 to 13.5 and an initial composition (in terms of mole ratios of oxides) within the following ranges: SiO₂/Al₂O₃: 200 to 00 M₂O/(Q₂O+M₂O):  to 0.8 OH⁻/SiO₂: 0.1 to 1.2 H₂O/(Q₂O+M₂O): 50 to 250 where Q₂O is the oxide form of an organic compound con­ taining an element of Group 5-B of the periodic table and having at least one alkyl or aryl group containing from 1 to 7 carbon atoms, provided that said compound contains at least one ethyl group, and M is an alkali or alkaline earth metal, and maintaining the mixture under crystallisation conditions until crystals of the zeolite form.

Description: PREPARATION OF ZEOLITE ZSM-12 This invention relates to a new method for preparing zeolite ZSM-12. Many crystalline zeolites are known, in most cases as aluminosilicates. Some occur (at least so far) only in nature, for instance paulingite and merlinoite; some occur only as a result of synthesis, for instance zeolites A and'ZSM-5; and some occur in both natural and synthetic forms, for instance mordenite, a synthetic counterpart of which is known as Zeolon, and faujasite, synthetic counterparts of which are known as zeolites X and Y. Counterparts are of course demonstrated as such by correspondence of their X-ray diffraction data, the indicia by means of which the individuality of a zeolite is established. Such data are a manifestation of the particular geometry of the threedimensional lattice, formed of SiO4 and in most cases Al04 tetrahedra crosslinked by the sharing of oxygen atoms and including sufficient cationic complement to balance the resulting negative charge on any A104 tetrahedra, of which a zeolite may consist. The chemical formula of an aluminosilicate zeolite is thus: MX/n: (A102)x: (si 2)y where M is a cation of valence n and x and y are the number of aluminium and silicon atoms, respectively, in the unit cell (the geometric unit which repeats throughout the extent of the lattice). This expression is however frequently transmuted into the 1,mole ratio of oxides" form, M2/nO : A1203 : 2y/x SiO2 which is of course empirically ascertainable and thus the only formula which can be ascribed to a zeolite when its unit cell contents are unknown. Since the only significant quantity -in such a formula is the term 2y/x, and since this term (which is almost invariably a range) can usually be satisfied by many zeolites of widely differing lattice geometry, chemical formula is not uniquely restrictive in establishing the identity of a zeolite. Furthermore, such a formula frequently expresses artefact when empirically derived, the cationic-valence/aluminium-atoms ratio deviate from unity, and it fails to provide for zeolites whose lattice structure can be brought into existence from reaction mixtures from which alumina is excluded. Moreover, both the unit cell formula and the "mole ratio of oxides" formula imply that the geometrical identity which persists between succeeding unit cells is accompanied by their compositional identity. ZSN-12, the zeolite synthesised according to the invention, is described in DE-OS 2,213,109 and defined by the X-ray diffraction data presented therein. It is known to be capable of existence in an extremely siliceous form, realised by the use of reaction mixtures to which no alumina has been added as such. The present invention aims to produce zeolite ZSM-12 having a silica/alumina lattice mole ratio certainly greater than 225, preferably greater than 500, still more preferably greater than 2000. So far as we are aware the zeolite can exist in the complete absence of lattice aluminium, but proof of this phenomenon must await the advent of a perfectly-aluminium-free siliceous reagent for use in the forming solution. According to the invention, therefore, a method of preparing zeolite ZSM-12 comprises forming a reaction. mixture comprising a source of. alkali or alkaline earth metal oxide, a source of silica which contains no more than 0.5g alumina per lOOg silica, Q20 and water, said mixture containing no added alumina and having an initial pH of 12 to 13.5 and an initial composition (in terms of mole ratios of oxides) within thefollowing ranges: SiO2/A1203 @ 200 to X ^2Qt(Q2 + M20) . 0 to 0.8 OH-/SiO2 : Q.1 to 1.2 H20/(Q20 + M20) : 50 to 250 where Q20 is the oxide form of an organic compound containing an element of GroupS-B of the Periodic Table and having at least one alkyl or aryl group containing from 1 to 7 carbon atoms, provided that said compound contains at least one ethyl group, and M is an alkali or alkaline earth metal, and maintaining the mixture under crystallisation conditions until crystals of the zeolite form. If alumina contamination of silica source is the only source of alumina in the reaction mixture the mole ratio Si02/A1203 in the reaction mixture is at least 340. Preferably, however, the mixture has the composition, in terms of mole ratios of oxides: SiO2/A1203 : 400 to CC M20/(Q20 + M20) : 0.2 to 0.6 OH-/SiO2 : 0.2 to 1.0 H2 /(Q2 + M20) : 60 to 200 The crystallisation conditions usually comprise a temperature of 80 to 1800C for a period of 6 hours to 150 days, and Q20 is preferably the oxide form of a quaternary compound, particularly a methyltriethylammonium compound, whilst M is preferably sodium or potassium. The method is most effectively implemented if the initial pH is 12.5 to 13.2. The source of silica advantageously contains no more than 0.4g alumina per lOOg silica, preferably no more than O.lg alumina per lOOg silica. Commercially available silica sources which fulfill the above-stated requirements regarding alumina content include Ludox "AS" and "LS" (0.03 to 0.07g alumina/lOOg silica); "Q-brand" (0.02g alumina/lOOg silica); and Degussa silica (0.2g alumina/ lOOg silica). By contrast the material known as "Hi-Sil" contains about 0.57g alumina/lOOg silica. These quantities of alumina which we cite in respect of the various materials identified by their trade names are, of necessity, approximate. Zeolite ZSM-12 can be additionally recognised by the formula, in terms of mole ratios of oxides, after dAydration, as follows: (l-QiO.4)M2/nO A12 3 (20-X) SiO2 wherein M is at least one cation having a valence n. It may have Al, Fe, and/or Cr in positions of tetrahedral substitution within the silica lattice. To this extent the latter possesses a negative charge, one excess electron for each such hetero-atom which is balanced by cations. These cations, if present, may be replaced at least in part by other ions using conventional ion exchange techniques. It may be necessary to calcine the crystals prior to ion exchange. Ions introduced to repiace the original alkali, alkaline earth and/or organic cations may be any that are desired so long as they can pass through the zeolite's pores. Desired replacing ions are those of hydrogen, ammonium and metals of Groups I through VIII of the Periodic Table. Among the metals, those particularly preferred are rare earth metals, manganese, zinc and those of Group VIII of the Periodic Table. The X-ray diffraction pattern of ZSM-12 has the following significant lines: TABLE 1 Interplanar Spacing D (A) Relative Intensity 11.9 + 0.2 .. .. .. .. M 10.1 + 0.2 .. .. .. .. M 4.7 + 0.1 .. .. .. .. W 4.29 + 0.08.. .. .. .. VS 3.98 + 0.08.. .. .. .. M 3.87 + 0.07.. .. .. .. VS 3.49 + 0.07.. .. .. .. W 3.38 +0.O7.. .. .. .. M 3.20 + 0.06.. .. .. .. W 3.05 + 0.05.. .. .. .. W 2.54 + 0.03.. .. .. .. W These values were determined by standard techniques. The radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used. The peak heights, I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with the spectrometer. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d(obs.), the interplanar spacing in A, corresponding to the recorded lines, were determined. In Table 1, the relative intensities are given in terms of the symbols VS=very strong, S=strong, M=medium, and W=weak. This X-ray diffraction pattern is characteristic of all species of ZSM-12. The sodium form as well as other cat ironic forms reveal substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur, depending on the silicon to aluminium ratio of the particular sample, as well as its degree of thermal treatment. When, as here, no alumina is added to the forming solution, the only aluminium present in ZSM-12 is derived from impurity in some other component of the crystallisation medium (with the reagents used in the examples hereinbelow, alumina impurities present therein resulted in up to 615 ppm alumina content in the product). Crystallisation of the zeolite can be carried out at either static or stirred condition in polypropylene jars at 21O0F or in teflon-lined stainless steel autoclaves. The total useful rante of temperatures is 800C to about 1800C for about 6 hours to 150 days. Thereafter, the crystals are separated from the liquid and recovered. The composition can be prepared utilising materials which supply the appropriate oxide. Such compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, and an organic compound. The organic compounds contain any element of Group 5-B such as nitrogen or phosphorus, preferably nitrogen. The preferred compounds are quaternary compounds generally expressed by the following formula: EMI6.1 wherein J is an element of Group 5-B of the Periodic Table, e.g., N or P, preferably N, and each R is an alkyl or aryl group having between 1 and 7 carbon atoms, and preferably at least one R group isan ethyl group. The oxide of the quaternary compound is generally supplied by introducing into the reaction mixture a composition such as the hydroxide, chloride or bromide of the tetraalkyl derivative of the desired 5-B element, e.g. methyltriethylammonium chloride (MTEACL). The other elements of Group 5-B behave similarly and thus the new crystals containing the same can be prepared by the same manipulative procedure substituting the other Group 5-B element for nitrogen. It should be realised that the oxide can be supplied from more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallisation time of the new crystalline material will vary with the nature of the reaction mixture employed and the crystallisation conditions. Synthesis may be facilitated by the presence of at least 0.001 per cent, preferably at least 0.10 per cent and still more preferably at least 1.0 per cent, seed crystals (based on total weight) of crystalline product. The zeolite prepared in accordance with the invention can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where particles are molded, such as by extrusion, the composition can be extruded before drying or partially dried and then extruded. The zeolite, especially in its metal, hydrogen, ammonium, alkylammonium and arylammonium forms, can be beneficially converted to another form for use as a catalyst or an adsorbant by thermal treatment. This thermal treatment is generally performed by heating one of these forms in an atmosphere such as air, nitrogen, hydrogen, steam, etc., at a temperature of at least 7000F for at least 1 minute and generally not greater than 20 hours to remove part or all of the water and the organic constituent. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment can be performed at a temperature up to about 17000 F. The thermally treated product is particularly useful in the catlysis of certain hydrocarbon conversion reactions. The zeolite can also be used as a catalyst in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be exchanged into the composition, impregnated therein or physically intimately admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating the zeolite with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinumtetrammine complex. Simple dehydration can also be performed at lower temperatures, such as room temperature, merely by placing the ZSM-12 zeolite in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration. In the case of many catalysts, it is desired to incorporate the new crystal with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive material and synthetic or naturally occurring materials as well as inorganic materials such as clays, silica and/or metal oxides, and are described at length in our EP-A-1695. Employing a catalytically active form of ZSM-12 prepared in accordance with this invention which may contain additional hydrogenation components, reforming stocks can be reformed employing a temperature between 7000F and 10000 F. The pressure can be between 100 and 1000 psig, but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0.1 and 10, preferably between 0.5 and 4, and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20, preferably between 4 and 12. The zeolite can also be used for hydroisomerisation of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerisation is carried out at a temperature between 2000F and 8000F, preferably 3000F to 7500 F, with a liquid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50, employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1. Aditionally, the zeolite can be used for olefin or aromatic isomerisation, employing temperatures between 300F and 7000F. Other reactions which can be accomplished employing the zeolite of this invention containing a metal, e.g. platinum, include hydrogenation-dehydrogenation reactions and desulfurisation reactions, olefin polymerisation (oligomerisation) and other organic compound conversion such as the conversion of alcohols (e.g. methanol) to hydrocarbon. In order to illustrate the nature of the invention and the manner of practising it, the following Examples show preparation of highly siliceous zeolite ZSM-12 of good crystallinity. In the Examples, adsorption data were determined as follows: A weighed sample of the calcined adsorb ant was contacted with adsorbate vapour in an adsorption chamber, evacuated to < 1 mm Hg and contacted with 12mm Hg of water vapour or 20 mm Hg of n-hexane or cyclohexane vapour, pressures less than the vapour-liquid equilibrium pressure of the respective adsorbate at room temperature. The pressure was kept constant (within about + 0.5mm) by addition of adsorb ate vapour controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorbate was sorbed the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapour to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbant. Examples 1-3 are summarised in Table 2 wherein sodium hydroxide was dissolved in water, and the methyl triethylammonium chloride solution was added. Finally, Ludox LS (colloidal silica, 30% Si02) was added. TABLE 2 Preparation of Highly Siliceous Crystals with MTEAC1 Example No. 1 2 3 Reaction Mixture Comp. MTEACi, 50%, g 25 35.5 35.5 NaOH, 97.6%, g 4.5 2.0 2.0 Ludox LS, 30% SiO2, g 144 38s2 38.2 HO 130 178 178 Moles/Mole of MTEAC1: NaOH 1.33 0.417 0.417 Si02 8.73 1.63 1.63 H20 164 106 106 Initial pH 13.19 13.12 13.11 Aged, Hrs./OC -/- 144/50 144/50 Crystallised, Hrs./OC 210/160 141/160 141/170 Final pH 11.30 11.45 10.93 Product Properties Crystallinity of ZSM-12 by X-ray Diff., % 90 85 95 Sorption, g/100 g: Cyclohexane, 20 Torr 6.0 6.8 7.9 n-Hexane, 20 Torr 5.4 6.0 6.4 Water, 12 Torr 9.7 3.9 1.7 Chemical Composition: : Si02, Wt.% 88.0 87.6 90.9 A123' ppm 540 540 490 Na20, Wt. % 0.51 0.31 0.22 N, Wt. % 0.77 1.08 0.92 Ash, Wt. % 90.2 87.6 91.8 SiO2/Al203, molar 2770 2760 3150 EXAMPLE 4 Sodium hydroxide (97.6%), 2.0 g., and 1.5 g of oxalic acid were dissolved in 140 g of water. A 50% solution of methyltriethylammonium chloride, 35.5 g, and, finally, a mixture of 38.2 g of Ludox LS and 40 g of water were added. The pH was adjusted to 13.0 with NaOH. The mixture was then heated at 1600C for 162 hours. The final pH was 11.31. The product gave the X-ray diffraction pattern of ZSM-12 (110% crystallinity compared with the reference ZSM-12 sample). It had the following properties: Sorption Capacity, g/10Og: Cyclohexane, 20 Torr 7 8 n-Hexane, 20 Torr 6.5 Water, 12 Torr 5.0 Chemical Composition: SiO2, wt. % 89.3 Al203, ppm 595 Na20, wt. % 0.26 N, wt. % 0.84 Ash, wt. % 91.2 SiO2/A1203 2550 EXAMPLE 5 Sodium hydroxide (97.6%), 2.0 g, and 4.0 g of sodium fluoride were dissolved in 140 g of water. A 50% solution of methyltriethylammonium chloride, 35.5 g, and, finally, a mixture of 38.2 g of Ludox LS (30% SiO2) and 40 g water were added. The mixture was heated at 1600C for 185 hours. The final pH was 11.69. The product, well developed crystals of up to 10 micron length, gave the X-ray diffraction pattern of ZSM-12 (100% crystallinity compared with the reference ZSM-12 sample) and contained a trace of ZSM-5 as impurity. It had the following properties: Sorption Capacity, g/100 g: Cyclohexane, 20 Torr 7.0 n-Hexane, 20 Torr 6.9 Water, 12 Torr 4.3 Chemical Composition: SiO2, wt. % 88.1 A12 3' ppm 615 Na20, wt. % 0.59 N, wt. % 0.99 F, wt. % 0.16 Ash, wt. % 89.7 Si02/Al203, Molar 2435 EXAMPLE 6 A 50% methyltriethylammonium chloride solution, 35.5 g, was diluted with 100 g of water. Solutions of 2.0 g of sodium hydroxide (97.6%) in 10 g of water and of 4.5 g of Na2HP04 in 30 g of water were added. A mixture of 38.2 g of Ludox LS (30% Si02) and 40 g of water was added and the reaction mixture was heated at 160"0 for .185 hours. The final pH was 11.41. The X-ray diffraction pattern of the product was that of ZSM-12 of 80% crystallinity and an unidentified impurity. The material consisted of crystals of the same size and morphology as the product of the previous example, and some crystals of ZSM-5 morphology. The properties were: Sorption Capacity, g/100 g: Cyclohexane, 20 Tor 7.3 n-Hexane, 20 Torr 7.8 Water, 12 Torr 4.2 Chemical Composition: six2, wt. % 88.5 Awl203, ppm 580 Na20, wt. % 0.50 N, wt. % 0.91 P, wt. % 0.01 Ash, wt. % 90.6 Si02/Al203 Molar 2594 EXAMPLE 7 Sodium hydroxide (97.6%), 2.3 g, was dissolved in 123.9 g of water, and the solution was mixed with 25.5 g of 50% solution of methyltriethylammonium chloride. Finally, 75.0 g of Ludox LS (30% SiO2)was added. The reaction mixture was heated at 160"0 for 387 hours. The final pH was 11.54. The product gave the X-ray diffraction pattern of ZSM-12 (95% crystallinity compared with the reference ZSM-12 sample). It consisted of well-developed crystals, up to 20 microns long, and contained no recognisable crystalline impurity. The properties were: Sorption Capacity, g/100 g: Cyclohexane, 20 Torr 7.6 n-Hexane, 20 Torr 6.9 Water, 12 Torr 3.6 Chemical Composition: Si02, wt. % 88.1 Al2O3, ppm 515 Na2O, wt. % 0.42 N, wt. % 0.92 Ash, wt. % 89.23 SiO2/A1203, Molar 2908 EXAMPLE 8 Sodium hydroxide (97.6%), 2.1 g, was dissolved in 66.9 g of water. A 50% solution of methyltriethylammonium chloride, 36.0 g, and, finally 100 g of Ludox LS (30% Six2) were added. The mixture was heated at 1600C for 326 hours. The final pH was 11.44. The product gave the X-ray diffraction pattern of ZSM-12 (100% crystallinity compared with the reference ZSM-12 sample) and contained a trace of ZSM-5. It had the following properties: Sorption Capacity, g/100 g: Cyclohexane, 20 Torr 8.5 n-Hexane, 20 Torr 8.5 Water, 12 Torr 2.7 Chemical Composition: Si02, wt. % 90.1 Al2O3, ppm 519 Na2O, wt. % 0.44 N, wt. % 0.91 Ash, wt. % 90.0 SiO2/Al203, Molar 2950 Reaction mixture ratios of Examples 1-8 are summarised in Table 3. TABLE 3 Reaction Mixture Ratios Moles/Mole MTEACl Ex. SiO2 NaOH Anion H2O OH-/SiO2 Na/Na + MTEA H2O/Na+MTEA 1 8.73 1.33 - 164 0.152 0.571 70 2 1.63 0.42 - 106 0.256 0.294 75 3 1.63 0.42 - 106 0.256 0.294 75 4 1.63 0.50 0.10 106 - 0,333 71 5 1.63 0.42 0.81 106 - 0.551 48 6 1.63 0.42 0.27 106 - 0.499 54 7 4.46 0.67 - 125 0.15 0.4 75 8 4.21 0.43 - 72 0.10 0.3 45

Claims: CLAIMS 1. A method of preparing zeolite ZSM-12 which comprises forming a reaction mixture comprising a source of alkali or alkaline earth metal oxide, a source of silica which contains no more than 0.5g alumina per lOOg silica, Q20 and water, said mixture containing no added alumina and having an initial pH of 12 to 13.5 and an initial composition (in terms of mole ratios of oxides).ithin the following ranges: SiO2/A1203 : 200 to CC Oft(Q2O + M20) : O to 0.8 OH /SiO2 : 0.1 to 1.2 H20/(Q20 + M2O) : 50 to 250 where Q20 is the oxide form of an organic compound containing an element of Group 5-B of the periodic table and having at least one alkyl or aryl group containing from 1 to 7 carbon atoms, provided that said compound contains at least one ethyl group, and M is an alkali or alkaline earth metal, and maintaining the mixture under crystallisation conditions until crystals of the zeolite form. 2. A method according to claim 1 wherein the mole ratio Si02/Al203 in the reaction mixture is at least 340. 3. A method according to claim 1 or claim 2 wherein the reaction mixture has the composition, in terms of mole ratios of oxides: SiO2/Al203 : 400 to 4 M20/(Q20+M20) : 0.2 to 0.6 OH-/SiO2 : 0.2 to 1.0 H2O/2O+M2O) : 60 to 200 4. A method according to any preceding claim wherein the crystallisation conditions comprise a temperature of 80 to 180 C for a period of 6 hours to 150 days. 5. A method according to any preceding claim wherein Q20 is the oxide form of a quaternary compound. 6. A method according to claim 5 wherein the quaternary compound is a methyltriethylammonium compound and M is sodium or potassium. 7. A method according to any preceding claim wherein the initial pH is 12.5 to 13.2. 8. A method according to any preceding claim wherein the source of silica contains no more than 0.4 g alumina per lOOg silica. 9. A method according to any preceding claim wherein the source of silica contains no more than O.lg alumina per lOOg silica.

Inventors: KUEHL, GUENTER HINRICH
Applicants: MOBIL OIL CORPORATION
Application year: 1983
Main classification: C01B33
IPC codes: C01B39, B01J29, C01B37