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Home , Lithium oxide, Sodium oxide

3,415,736 United States Patent Office Patented Dec. 10, 1968 1. 2 3,415,736 It is contemplated that the silica may exceed 4.5 moles, LTHUM-CONTAINING CRYSTALLINE going up to 5.5 to 6 moles, and also that it may be as ALUMINOSILICATE low as 2.0 moles. Preferably the composition is defined Julius Ciric, Pitman, N.J., assignor to Mobil Oil as follows: 'Corporation, a corporation of New York Filed Sept. 20, 1965, Ser. No. 488,443 0.3-0.8LiO: 0.7-0.2Na2O:Al2O3: 16 Claims. (C. 208-111) 2.8-4SiO2:0-9H2O (III) For convenience, the new material, which may comprise a number of species as is evident from Formula (II), ABSTRACT OF THE DISCLOSURE O may be referred to as Zeolite ZSM-3, or simply as ZSM A new zeolite composition having a characteristic X 3. Zeolite ZSM-3 may be identified and distinguished by ray diffraction pattern and having a composition, in X-ray diffraction analysis as well as by composition. terms of mole ratios of : Following are data of an X-ray powder diffraction pat 0.05-0.8LiO:0.95-0.2Na2O:Al2O3:2.0-6SiO2:0-9H2O tern of a typical example of ZSM-3, it being understood a process for making the same and a process for utilizing 15 that all species thereof exhibit essentially the same pat a catalyst comprising the same for hydrocarbon con tern. version. TABLE 1. Interplanar Relative Comment SSSS Spacing, d.A.* Intensity

This invention relates to a novel class of crystalline 15.50 111 14.37 S aluminosilicates and to methods for preparing the same. 13,39 ??? More specifically, it relates to new crystalline 8.89 1 7.53 aluminosilicates and their preparation. 7.38 ??1 Very broad Both natural and synthetic crystalline aluminosilicates 5.77 ??1 Broad. 5.0 W are known and may generally be described as alumino 4.81 w of ordered internal structure having the follow 4.42 ?l 4.2.1 ?y" Do. ing general formula: 4.5 W" Do. 3.82 w Very broad. 3.75 w Broad. 3.47 w Do. t (I) 3.34 ?1 3.23 W ID?. where M is a cation, n is its valence, Y the moles of silica, 3, 20 W D0. and Z the moles of the of hydration. 3.05 O. When water of hydration is removed from the crys 2.94 W7 talline aluminosilicates, highly porous crystalline bodies 35 NOTE.-w=weak; S=Strong; m=medium; www = very, very weak. are formed which contain extremely large adsorption Standard techniques were employed to obtain the fore areas inside each crystal. Cavities in the crystal struc going data. The radiation was the Kalpha C doublet of ture to internal pores and form an interconnecting , and a Geiger counter spectrometer with a strip network of passages. The size of the pores is substantially chart pen recorder was used. The peak heights, I and constant, and this property has led to the use of crystalline 40 the positions as a function of 2 times theta, where theta aluminosilicates for the separation of materials accord is the Bragg angle, were read from the spectrometer ing to molecular size or shape. For this reason, the crys chart. From these, the relative intensities, 100 I/I where talline aluminosilicates have sometimes been referred I is the intensity of the strongest line or peak, and d to as molecular sieves. They are also Zeolitic. (obs.), the interplanar spacing in A., corresponding to the The crystalline structure of Such molecular sieves con 45 sists basically of three-dimensional frameworks of SiO4 recorded lines, were calculated. In Table 1 the relative and AlO4 tetrahedra. The tetrahedra are cross-linked by intensities are given in terms of the symbols w=weak, the sharing of atoms, and the electrovalence of S=strong, m= medium, and vyw=very, very weak. the tetrahedra containing aluminum is balanced by the in Zeolite ZSM-3 is a large pore Zeolite of the faujasite clusion in the crystal of a cation (M in Formula I), e.g., 50 type, by which is meant that it exhibits an X-ray diffraction or alkaline metal or other cationic pattern similar to that of faujasite, although there are metals and various combinations thereof. These cations significant differences. The pores are large enough to sorb are generally readily replaced by conventional -ex cyclohexane. Thus, a specific ZSM-3 zeolite (completely change techniques. dehydrated) of the formula: The spaces in the crystals between the tetrahedra 55 0.4NaO:0.6LiO: AlO3:3.1SiO, (IV) ordinarily are occupied by water. When the crystals are was observed to adsorb 16.1 g. cyclohexane per 100 g. treated to remove the water, the spaces remaining are of zeolite; it also adsorbed 25.2 g. water per 100 g. of available for adsorption of other molecules of a size and zeolite. Crystals of ZSM-3 have a hexagonal shape, as shape which permits their entry into the pores of the determined by electron miscroscopy. The lithium in structure. 60 ZSM-3 is zeolitic and completely exchangeable; its Molecular sieves have found application in a variety of amount exceeds 0.05, preferably 0.3 equivalent of lithium processes which include ion exchange, selective adsorp per gram atom of aluminum, i.e., the aluminum that is tion and separation of compounds having different molec present in the framework structure of the aluminosilicate. ular dimensions such as hydrocarbon isomers, and the Zeolite ZSM-3 is capable of being ion exchanged to catalytic conversion of organic materials, especially cata 65 lytic cracking processes. partially or completely replace the sodium cation by other According to the invention, the composition of the new cations. During this step, part or all of the lithium cation aluminosilicate, in terms of mole ratios of oxides, may is also replaced by the replacing cation. It will be under be set forth as follows: stood that the spatial arrangement of the aluminum, 70 , and oxygen atoms, which form the basic crystal 0.05-0.8LiO:0.95-0.2Na2O:AlO3: lattice of ZSM-3, remains essentially unchanged by the 2.8-4.5SiO2:0-9H2O (III) described replacement of sodium and lithium, and that 3,415,736 3. 4. the X-ray powder diffraction pattern of the ion-exchanged association with one of the above components, preferably material is essentially the same as that set forth in Table a platinum metal. 1. The replacing cations include monovalent, divalent, The zeolite may also be employed as an adsorbent, trivalent, quadrivalent cations, and they may be selected after at least partial dehydration, a step which may be from ions of the following: metals of Group IA of the carried out by heating the zeolite to 200-600 C. in an Periodic Table, such as ; metals of Group IB, inert atmosphere, such as air or , under such as ; metals of Group IIA, such as , atmospheric or reduced pressure, or by maintaining the and ; metals of the transition metals, zeolite under vacuum at room temperature or above for such as those of atomic numbers 21-28, 39-46, and 72-78, a suitable time. As an example, zeolite ZSM-3 may serve inclusive; metals of the actinide series; and rare earth to adsorb and remove water from natural gas. metals such as , , , 10 Zeolite ZSM-3 may be suitably prepared by forming a , and mixtures thereof with each reaction mixture containing lithium , , other and the other rare . Other useful replacing alumina, silica, and water and having a composition, in cations are ammonium, alkylammonium, and arylam terms of mole ratios of oxides, falling within the follow monium cations, these leading to a product which, on ing ranges: calcining, decomposes to the form. Ion ex TABLE 2 change of the zeolite may be accomplished conventionally, as by packing the zeolite in the form of beds in a series Preferred Broad Li2Of Li2O-Na2O.--- -- 0.25:1 to 0.82:---- 0.2:1 to 0.9:1. of vertical columns and successively passing through the Li2O.--Na2OfSiO2 - 0.6:1 to 1.33:1 0.55:1 to 2.5:1. beds a water solution of a soluble salt of the cation to 20 SiO2/Al2O3------4:1 to 16:1-- 2:1 to 32:1. be introduced into the Zeolite; and then to change the H2O/Li2O-H-Na2 --- 40:1 to 120:1------20:1 to 300:1. flow from the first bed to a succeeding one as the zeolite Satisfactory crystallization can be carried out by main in the first bed becomes ion exchanged to the desired taining the mixture at temperatures of about 20 to 120 extent. C., the pressure being atmospheric or at least that cor It will be seen from the preceding paragraph that responding to the vapor pressure of water in equilibrium Zeolite ZSM-3 may be more broadly defined, in terms of with the mixture of reactants. The reaction period may oxides, as follows: extend from several hours to several days. At lower tem peratures in the foregoing range, and at lower alkali to silica ratios, the reaction period tends to be longer. In 30 any event, the mixture is kept at the selected temperature where M represents at least one cation having a valence until the desired crystalline zeolite product is formed. of not more than 3 or 4, and n represents the valence of The zeolite crystals are then separated from the mother M. As noted, the silica may be as high as 5.5 to 6 moles liquor and washed, preferably with distilled water, until and as low as 2.0 moles. If the replacing cation described 3 5 the effluent wash water in equilibrium with the product in the preceding paragraph replaces only part of the has a pH of preferably below 11. It is of course advan sodium and lithium, it will be seen that M may represent tageous to employ soluble initial reactant materials, Such three different cations; and if the replacing cation replaces as aqueous solutions of sodium aluminate, aluminum all of the sodium and lithium, then M represents one chloride, sodium , , lithium cation. Also, if a mixture of cations is used to replace 40 chloride, , etc. Also useful are silica Sodium and lithium, then M can represent more than three hydrosol, silica gel, and silicic acid. The reaction mixture cations depending on the number of cations in the mixture. can be, and preferably is, prepared continuously. As indicated, M is at least one cation chosen from Referring to the foregoing method, the preferred com metals of Groups I and II of the Periodic Table, rare position of the reaction mixture may be defined more or earth metals, transition metals, metals of the actinide less graphically in terms of the composition diagram Series, and ammonium, alkylammonium, and aryl illustrated in the accompanying drawing. This comprises ammonium cations. The essential limitation of the zeolites a ternary plot of the system Na2O-Li2O-SiO2, in terms defined by Formula (V) is that they exhibit essentially of mole percent, and is to be interpreted in conjunction the same X-ray powder diffraction pattern as Table 1. with the notation appearing thereon to the effect that the ZSM-3 is of use as a catalyst in the catalytic cracking 50 silica: alumina ratio of the mixture varies from 4:1 to of hydrocarbons. Owing to its large pores, it can admit 16:1 and the water: alkali ratio varies from 40:1 to 120:1. branched chain and cyclic hydrocarbons as well as As will be recognized, in this system the line KL repre straight chain hydrocarbons. In a useful procedure for sents 0 mole percent silica and the point M represents 100 this purpose, the Zeolite is subdivided, mixed with a porous mole percent silica; the line LM represents 0 mole percent inorganic matrix to form a mass, dried, and heated to 55 sodium oxide and the point K represents 100 mole percent 500-1500 F. for one hour, preferably 1 to 48 hours. sodium oxide; and line KM represents 0 mole percent Suitable procedures for distributing or suspending the and the point L represents 100 mole percent Zeolite in the matrix, and also suitable matrix materials, lithium oxide. The lines parallel to KL and extending are described in U.S. Patents 3,140,249, 3,140,251, and toward point M represent increasing concentrations of 3,140,253. The mass is then steamed as this tends to 60 silica, the first of such lines denoting 10 mole percent, increase the selectivity of the catalyst. Steaming may be the second 20 moie percent, and so on. The lines parallel done at 1000-1300 F. for 2 to 100 hours in an at to LM and KM have a similar meaning in relation to mosphere containing at least about 10% by volume of sodium oxide and lithium oxide, respectively. Attention is steam, and usually containing air or other inert gas. now called to the area ABCDEA. Mixtures having a com The catalytic effect of a ZSM-3 containing catalyst is 65 position falling within this area and characterized by hav illustrated in Examples 4 and 5. The Zeolite is also of use ing a SiO2/Al2O3 ratio of 4:1 to 16:1 and a in other hydrocarbon conversion reactions such as hydro cracking, where it may be used either in the assynthesized HO/LiO--Na2O form or, preferably, having impregnated therein or there ratio of 40:1 to 120:1 comprise the preferred reaction on a hydrogenating component like , , 70 mixtures which lead to the formation of Zeolite ZSM-3. , , , , , man A preferred method of preparing the new zeolite com ganese, and platinum metals, and also compounds of prises making use of a solution or mixture, for con said metals. The last five components in particular may venience deisgnated crystallization directing agent, or also be ion-exchanged into the zeolite. It is of further CDA, which contains sodium oxide, alumina, silica, and use in reactions like hydroisomerization, particularly in water. It is found that use of this mixture to better 3,415,736 5 6 yields and appears to provide silica and alumina in and water, giving a mixture having suspended therein a desirably reactive form. As will appear, the CDA may be gelatinous precipitate. The precipitate is then filtered off, in the form of a clear solution, or a slurry or a filter cake. washed, and the cake recovered. The wet amorphous Three alternative methods may be described respecting cake is then divided into two parts identified as cake I the use of the CDA and the addition of the lithium oxide 5 and cake II. Cake I is placed to one side, while cake II containing source compound to it. According to the first is treated with a solution containing a lithium salt, such as alternative, the CDA is in the form of a clear Solution, , and water to introduce lithium into the and the first addition to it comprises a solution containing material by ion exchange, after which it is washed. The the lithium compound. According to the second alter two wet cakes are then mixed, a solution containing lithi native, additions are made to the CDA so that a slurry 10 um oxide and water is added, and after a suitable time forms which is filtered, and the lithium compound is added crystalline ZSM-3 is formed and may be recovered. This to the filter cake. According to the third alternative, a non method is of interest because it enables lower ratios of lithium containing filter cake is formed which contains alkali (lithium oxide plus sodium oxide) to silica to be the CDA, and this cake is divided into two parts, to one used in the preparation of the zeolite. of which the lithium compound is added, after which The invention may be illustrated by the following the two parts are mixed and heated in the presence of a examples. solution containing lithium oxide and water to effect crystallization of the Zeolite. Example 1 Considering the first alternative in more detail, a Zeolite ZSM-3 was synthesized in the following way. solution of the CDA is formed containing sodium oxide, 20 Four solutions were prepared, identified as A, B, C, and alumina, silica, and water and having a composition, in D terms of mole ratios of oxides, within the following Solution A, or CDA solution: Grams rangeS: Sodium aluminate ------2.4 TABLE 3 Sodium hydroxide pellets ------19.3 25 ------34.4 Preferred Broaôi Water ------76.5 Na2OfSiO2. 1.85:1. 1.5:1 to 2.2:1. Solution B: SiO2, Al2O3. ---- 16:1 12:1 to 22:. Lithium hydroxide monohydrate ------75 H2O/Na2O.------18:l 15:1 to 25:1. Water ------'600 30 Solution C: The ingredients of the CDA mixture are heated to a Sodium aluminate ------28.8 temperature in the range of 40-70° C., preferably about Water ------100 60° C., for a time ranging from 15 minutes to 72 hours, Solution D: preferably 0.5 hour. At lower ratios of sodium oxide to Sodium silicate ------411 silica, longer times and higher temperatures are preferred. Water ------155 Then a solution containing lithium oxide and water is mixed with one containing sodium oxide, silica, and Solution A had the following calculated composition, in water, and the resulting mixture is added to the CDA terms of mole ratios of oxides: mixture. There is then added a solution containing sodi um oxide, alumina, and water to form a reaction mixture 40 NaO/SiO 1:85:1 having a composition falling within the ranges set forth SiO2/Al2O3 16:1 above in Table 2. The resulting reaction mixture is main H2O/Na2O 18:1 tained at a temperature of 20 to 120° C. for a time Suf ficient to form crystals of Zeolite ZSM-3, and the crystals Solution A, which was clear, was heated at 60° C. for are separated, washed as described, and recovered. The 45 0.5 hour. Solution B was added to solution D, and then method is illustrated in Example 1. to the resulting mixture solution A was added under According to the second alternative, a CDA solution is vigorous stirring in a 1-gallon Waring Blendor. Finally formed as described in the first alternative. To this solu Solution C was added so that the over all mixture had tion there is added a solution containing sodium oxide, the following composition, in terms of mole ratios of silica, and water, and then there is added a solution con 50 oxides: taining alumina and water to form a slurry. The latter, after treatment as by heating and stirring to make filtra LiO/LiO--NaO 6/10-6.7 or 0.36:1 tion more rapid, is filtered, and there is then added to LiO--Na2O/SiO2 10-6.7/16.3 or 1.02:1 the filter cake a solution containing lithium oxide and SiO/Al2O3 16.3:1 water, thereby forming a reaction mixture having a com 55 HO/LiO--NaO 450/10-J-6.7 or 27:1. position as set forth in Table 4, below. Addition of solution C resulted in formation of a gel, and TABILE 4 the over all mixture was then heated at 60° C. for 5 days, filtered, and the filter cake washed to a filtrate pH of 10.5. Preferred Broad 60 The crystalline product, comprising particles of 2 to 3 Li2O/Li2O--Na2O.------0.2:1 to 0.8:1.-- 0.:l to 0.8:1. microns diameter, was dried at 110° C. In a series of Li2O-Na2OfSiO2 0.3:1 to 1.5:1 0.25:1 to 3:1. three sorption tests the product adsorbed 17.7%, 18.8%. SiO2, Al2O3------. 3:1 to 6 : l2:1? ?? to 10:. and 17.8% by weight of cyclohexane, respectively, and HOf LiO--Na2O 20:1 to 300: in another series it adsorbed 28.4%, 31.3%, and 30.0% by weight of water, respectively. Ignoring water of hydra This reaction mixture is heated as described to form a 65 crystalline slurry which is then filtered, the crystalline tion, chemical analysis, in terms of mole ratios of oxides, product washed as described, and the product recovered. showed the product to have the formula: The method is illustrated in Example 2. The third alternative method for preparing ZSM-3 in 0.43Na2O:0.62Li2O:Al2O3:3.1SiO, (VI) volves mixing two filter cakes. In general, a first solution 70 It exhibited the X-ray powder diffraction pattern of is prepared containing sodium oxide, silica, and water, Table 1. and this is mixed with a CDA solution as described in Example 2 Table 3. To the resulting mixture there is added a second solution comprising an acidic solution containing alumina 75 Zeolite ZSM-3 was also synthesized as follows: Four 3,415,736 7 8 solutions were again prepared, identified as A, B, C, and a matrix comprising McNamee clay in such amounts D: as to give a resulting mass comprising 15% of the alu minosilicate and 85% clay, weight basis. The Sodium Solution A, or CDA solution: Grams content of the mass was 0.10% by weight. The mass was Sodium aluminate ------19.2 5 heated for 10 hours in air at 1000 F. and then steamed Sodium hydroxide pellets ------154.4 for 24 hours in an atmosphere of 100% steam at 1200 Sodium silicate ------275.2 F. and 15 p.S.i.g. Water ------61.2 The steamed catalyst mass was then used (Cat D test) Solution B: to catalyze the cracking of a Midcontinent gas oil having Sodium silicate ------1100 a range of 450-950 F. and a specific Water ------800 O gravity of 0.88 g/cc. The gas oil was vaporized and Solution C: preheated to 875 F., and then pumped at a rate of Aluminum chloride ------85.6 5 cc./min. through a 100 cc. bed of the catalyst mass Water ------1600 maintained at 875 F. by external heat. The duration Solution D: of the run was 10 minutes, the liquid hourly space velocity Lithium hydroxide monohydrate ------48 was 3, and the catalyst-to-oil ratio was 2. Reactor effluents Water ------350 were condensed and separated into C4-free gasoline, dry Solution A had the same composition, in terms of mole gas comprising C1-C3 material, a C4 fraction, and un ratios of oxides, as solution A in the preceding example. cracked oil. Solution A was added to solution B in the Waring Blendor, 20 The following data were observed: and then solution C was added rapidly, with stirring Conversion ------percent volume.-- 46.0 continued for about 1 minute. The resulting slurry was C4-free gasoline ------do---- 42.7 heated at 100° C. for 0.5 to 1 hour, filtered, the filter Total C4's ------do---- 6.9 cake heated at 100° C. for 3 hours, and filtered again. Dry gas ------percent weight- 2.4 The new filter cake was then washed with 2000 ml. 25 of water. Solution D was mixed with the cake as intimately Coke ------do---- 1.4 as possible, and the mixture heated at 60° C. for 16 H2 SSSS SSSSSSS SSSS SS SS SS SSLSLSMSSSMSSSMSSSS SS SSSSSSMSSSLSSSMSSSLSSSMSSSSSSS SSS LSdo---- 0.06 hours and then at 100° C. for 1 hour. The resulting Example 5 crystalline slurry was filtered and washed until the wash This example illustrates another catalytic cracking ings had a pH of less than 11. In a series of three 30 operation. Zeolite ZSM-3, corresponding to species No. sorption tests the product adsorbed 15.2%, 16.6%, and CSF-163 of Table 5, was subjected to ion exchange by 16.6%, respectively, by weight of cyclohexane, and in lanthanum, using the procedure described in the preceding another series it absorbed 23.6%, 25.4%, and 26.0% by example. The resulting aluminosilicate contained, besides weight of water, respectively. Chemical analysis, in terms lanthanum, about 0.19% lithium oxide and 2.51% sodium, of mole ratios of oxides, showed the product to be weight basis. It was mixed with McNamee clay to give included by the formula: a mass containing 15% of the aluminosilicate and 85% 0.50--0.20NaO:0.50-h-0.20LiO:AlO:3.7-4.0SiO, of clay, with the sodium content being reduced to 0.35% (VII) by weight. The mass was heated for 18 hours in air at 1000 F. and then for 24 hours in an atmosphere of again ignoring water of hydration. It exhibited the X-ray 40 100% steam at 1200 F. and 15 p.si.g. diffraction pattern of Table 1. The mass was used to catalyze the catalytic cracking Example 3 of another sample of Midcontinent gas oil, as in the preceding example, using the same conditions. Several additional species of ZSM-3 were prepared and The following data were obtained: are identified in the table below in their dehydrated state. 45 Of these, approximately half were prepared substantially Conversion ------percent volume-- 69.1 in accordance with the method of Example 1, and the rest C4-free gasoline ------do---- 58.0 Total C4's ------do---- 13.8 in accordance with the method of Example 2. Dry gas ------percent weight--, 5.7 TABILE 5.-SO) BPTION' AND9NANTITATIVE ANALYSIS OE 50 Coke ------do---- 2.3 H SS SSSSSSS S S SSSLSLS S S SS S SLLSSS SS SS S S SSSSS LS SSSSS SSSLS S SSSdo---- 0.08 Sorption, Wt.% Quantitative Analysis No. The periodic table classifications as used herein are Water Cyclohexane Na2O Li2O Al2O3 SiO2 based on the arrangement distributed by E. H. Sargent 25.6 16.7 .485 .324 1. 3.67 & Co. and further identified by the legend “Copyright 1962 23.6 15.2 .598 .385 1. 3.65 55 25.4 16.6 .682 .360 3.75 Dyna-Slide Co.' 26.0 6.6 . 630 .355 3.59 It will be understood that the invention is capable 29.9 19.4 .77 09 1. 3.20 29.9 20.0 .80 .22 1. 2,95 of obvious variations without departing from its scope. 27.4 18.9 ,755 270 1. 3.57 In the light of the foregoing description, the following is claimed: 60 1. A synthetic crystalline lithium-sodium aluminosilicate Example 4 having a composition, in terms of mole ratios of oxides, Use of ZSM-3 as a cracking catalyst is demonstrated as follows: as follows. Zeolite ZSM-3 having the following oxide formula: 0.3 to 0.8Li,? : 0.7 to 65 0.2Na2O: AlO3: 2.8 to 4.5SiO: 0-9HO 0.64NaO 0.37LiO : Al?O3 :3 .66SiO:zHO (VIII) said aluminosilicate having an X-ray powder diffraction where z has a value of 0 to 9, was ion exchanged by pattern essentially the same as that shown in Table 1 of lanthanum to replace part of the sodium and lithium. the specification. The ion exchange was carried out by subjecting the 2. A synthetic crystalline lithium-sodium aluminosilicate zeolite to three treatments with an aqueous solution con 70 having a composition, in terms of mole ratios of oxides, taining about 5% by weight of lanthanum chloride, as follows: followed by washing and drying. Chemical analysis of the resulting aluminosilicate showed it to contain. 23.2% 0.05 to 0.8LiO: 0.95 to , 0.11% lithium oxide, and 0.52% 0.2Na2O: Al2O3: 2.8 to 4.5SiO: 0-9HO sodium, weight basis. It was then intimately mixed with 75 said aluminosilicate having an X-ray powder diffraction

3,415,736 11 12 comprising the crystalline aluminosilicate defined in placed by at least one cation from the group comprising claim 3. metals of Groups I and II of the Periodic Table, rare 14. A crystalline synthetic lithium-sodium alumino earth metals, metals of the actinide series, transition silicate having silicon and aluminum present in such metals, and ammonium, alkylammonium, and arylam proportion that the ratio of silica to alumina is 2.0:1 to monium cations. 6:1, said aluminosilicate having an X-ray powder diffrac tion pattern esentially the same as that shown in Table 1. References Cited 15. A process for converting a hydrocarbon charge UNITED STATES PATENTS which comprises contacting the same under conversion 3,123,441 3/1964 Haden et al. ------23-113 conditions with a catalyst comprising the crystalline 0. 3,236,761 2/1966 Rabo et al. ------208 120 X aluminosilicate defined in claim 14. 16. A crystalline synthetic lithium-sodium alumino DANIEL E. WYMAN, Primary Examiner. silicate having silicon and aluminum present in such proportion that the ratio of silica to alumina is 2.8:1 to C. F. DEES, Assistant Examiner. 6:1, said aluminosilicate having an Xray powder diffrac 5 tion pattern essentially the same as that shown in Table 1, U.S. Cl. X.R. at least a portion of the Sodium and lithium being re 252-455; 23-1.12; 208-120