ZEOLITE AND CATALYTIC CONVERSION THEREWITH

Abstract: A new metal-containing high siliceous porous crystalline material related to the structure of zeolite beta, a method of making same and the use thereof in catalytic conversion of organic compounds. The anhydrous form of the new metal-­ containing crystal has a calculated composition, expressed in terms of moles of anhydrous oxides per 100 moles of silica, as follows: (W)Q₂O · (X)M 2/n O · (y)L₂O₃ · 100 SiO₂ wherein Q₂O is the oxide form of an organic compound containing an element of Group 5-B of the Periodic Table, said organic compound having at least one alkyl or aryl group at least one of which is an ethyl, M is an alkali metal, W =<5, X =<2, Y=<4, and L = Al, Cr, Fe, or La and mixtures thereof, provided that at least one of Cr, Fe and La is present and Y is >zero. The new crystal is prepared from a reaction mixture comprising a source of silica, chromium and/or iron compounds and/or lanthanum oxide, a source of organic compounds of Group 5-B, having at least one ethyl group, and water, in the absence of any added alumna in the recipe.

Description: ZEOLITE, METHOD OF PREPARING SAME, AND CATALYTIC CONVERSION THEREWITH This invention relates to a novel highly siliceous porous crystalline zeolite related to zeolite beta, to a method for its preparation and to its use in catalytic conversion of organic compounds. Previously, zeolite beta has been prepared from mixtures containing silica and alumina and yielding a product SiO2/A1203 ratio of 5 but less than 100 as disclosed in U.S. Patent 3,308,069. The materials of the present invention use Fe; and/or Cr and/or La as substitute for added A1203 in the synthesis and can yield a product with a silica to alumina ratio greater than 100 up to infinity. In the as-synthesized form, the material has a calculated composition, in terms of moles of oxides, after dehydration, per 100 moles of silica, as follows: (w)Q2O # (x)M2/nO # (y)L2O3 # 100 SiO2 wherein Q20 is the oxide form of an organic compound containing an element of Group 5-8*, e.g., N, P, preferably N, containing at least one alkyl or aryl group having between 1 and 7 carbon atoms, preferably between 2 and 5, more preferably containing at least one ethyl group and still more preferably Q20 is a quaternary ammonium compound containing at least one ethyl group, M is an alkali metal having a valence n, e.g. Na or K, n = valence of M, W = < 5, X = < 2, * National Bureau of Standards (Fischer Scientific Co. Table of the .Elements) Y < 4 and L = Al, Cr, Fe, or La, or mixtures thereof. When any two of Cr, Fe, or La are not present, the other must be. The material may have Al, Fe, La and/or Cr in positions of tetrahedral substitution within the silica lattice, requiring a balancing cationic valence for preservation of electrical neutrality. These cations, if present, may be replaced at least in part by other ions using conventional ion exchange techniques. Ions introduced to replace the original alkali, and/or organic cations may be any that are desired so long as they can pass through the channels within the crystals. 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 materials according to the present invention has the following significant lines: TABLE 1 Interplanar Relative Intensity d-spacinq (A') 11.5 + 0.3 M-S 7.4 t 0.2 W 6.6 + 0.15 W 4.15 + 0.10 W 3.97 , 0.1 VS 3.0 1 0.07 W 2.05 + 0.05 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 used0 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 10 is the intensity of the strongest line or peak, and 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 = moderate and W = weak. This X-ray diffraction pattern is characteristic of all the species of zeolite beta compositions. The sodium form, as well as other cationic forms, reveals 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 aluminum ratio of the particular sample, as well as its degree of thermal treatment. The new zeolite can be prepared from a reaction mixture containing an intentional source of silica, Q20, an alkali metal oxide, e.g. sodium, a chromium, iron, or lanthanum compound, water, and no added alumina, and having a composition, in terms of mole ratios of oxides, falling within the following ratios: REACTANTS BROAD PREFERRED SiO i2 = 2 to 50 4 to 15 M20/Q20 = 0.0 to 10 0.5 to 4 (Cr203 + Fe203 + La2O3)Q2O = 0.05 to 5 0.08 to 0.2 H2O/Q2O = 50 to 500 150 to 300 wherein 0 is the oxide form of an organic compound of an element of Group 5-8 of the Periodic Table (e.g. N, P) and can be an organic compound containing at least one ethyl group and M is alkali metal and maintaining the mixture at crystallization temperature until crystals of the highly siliceous crystal material are formed. As mentioned above, no alumina is added to the recipe. The only aluminum present occurs as an impurity in some other component of the crystallization medium. Crystallization can be carried out at either static or stirred condition in polypropylene jars at 990C (210oF) or in Teflon) lined stainless steel autoclaves. The total useful range or 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 utilizing materials which supply the appropriate oxide. Such compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, chromic potassium sulfate or ferric ammonium sulfate or lanthanum chloride, and an organic compound. The organic compounds can include any element of Group 5-8 such as nitrogen or phosphorous, preferably nitrogen. The preferred compounds are quaternary compounds generally expressed by the following formula: EMI4.1 wherein J is an element of Group 5-8 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 is an ethyl group. While normally each alkyl or aryl group will be the same, it is not necessary that each group have the same number of carbon atoms in the chain. The oxide of the quaternary compound is generally supplied by introducing into the reaction mixture a composition such as the hydroxide or chloride of the tetraalkyl derivative of the desired 5-8 element. In preparing an ammonium species, tetraethyl ammonium chloride or bromide or, less preferably, hydroxide is useful. In preparing the phosphonium species, tetraethyl phosphonium chloride is particularly desirable as a means of incorporating the quaternary compound into the crystal. The other elements of Group 5-8 behave similarly. The oxide can be supplied from more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time will vary with the nature of the reaction mixture employed and the crystallization conditions. In all cases, synthesis may be facilitated by the presence of at least 0.01 percent, preferably 0.10 percent and still more preferably at least 1.0 percent, seed crystals (based on total weight) of crystalline product. Catalysts comprising crystals prepared by the Instant invention can be formed in 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 catalyst is molded, such as by extrusion, the crystal can be extruded before drying or partially dried and then extruded. Thermal treatment of the zeolites before and after base exchange can be performed by heating one of these forms in an atmosphere such as air, nitrogen, hydrogen or steam at a temperature of at least 371oC (700 OF) for at least 1 minute and generally not greater than 20 hours. 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 5380C (10000F). The thermally treated product is particularly useful in the catalysis of certain hydrocarbon conversion reactions. The zeolite can 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 desired, such component being introduced by exchange into the composition, impregnation or physical intimate mixing. Such component can be impregnated for example, in the case of platinum, by treating the zeolite with a solution containing a platinum metal-containing ion. Suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. It is frequently desirable to composite a zeolite with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such compositing practices and materials are fully described in our EP-A-1695. Employing a catalytically active form of the novel crystal catalyst of this invention which may contain additional hydrogenation components, reforming stocks can be reformed employing a temperature between 3710C (7000F) and 5380C (1000at). 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. Other reactions which can be accomplished employing the zeolite of this invention in association with a metal, e.g. platinum, include hydrogenation-dehydrogenation reactions and desul furization reactions, olefin polymerization (oligomerization) and other organic compound conversion such as the conversion of alcohols (e.g. methanol) to hydrocarbon. The following Examples illustrate the nature of the invention and the manner of practicing it. In them, whenever adsorption data are set forth for comparison of sorptive capacities for water, cyciohexane and n-hexane, they were determined as follows: A weighed sample of the calcined adsorbant was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to < 1 mm and contacted with 12 mm Hg of water vapor or 20 mm Hg of cycolhexane or n-hexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at room temperature. The pressure was kept constant (within about + 0.5 mm) by addition of adsorbate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorbate was adsorbed by the crystal, the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to ble 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/l00 g of calcined adsorbant. EXAMPLES 1-11 In these examples, the starting gel reaction mixture was prepared from sources of silica such as Q-Brand sodium silicate (28.8% SiO2, 8.9% Na20) and S-35 sodium silicate (25.3S SiO2, 6.8% Na20). Fume silica (HiSil 91.3% SiO2) may also be used. The source of tetraethylammonium organic cation was supplied by either the hydroxide (40S solution) or by salts such as halide. The metal salts used were chromic potassium sulfate, ferric ammonium sulfate and lanthanum chloride. Other salts such as chlorides and nitrates can be used. Moles of h0 were excess Na20 after neutralization of moles of mineral acid added to the mixture. Crystallization was carried out at static conditions in stainless steel autoclaves. After crystals formed, the product was filtered, water washed and dried at 110 C (2300F). The amounts of starting material identification of same, product compositions, and adsorption data are listed in Tables 2 and 3 set forth immediately hereinbelow. TABLE 2 Crystalisation Experiments - Cr Beta Crystal Static System Stainless Steel Reactors Example 1 2 3 4 5 6 Reaction Mixture, gms A. Q Brand (28.8% SiO2; 8.9% Na2O) 30.5 H2O 20.0 S-35 Silicate (25.3% SiO2, 6.8% Na2O) 64.0 64.0 64.0 64.0 64.0 B. CrK (SO4)2 # 12H2O 4.7 1.3 1.3 1.3 1.3 1.3 H2SO4 0.5 1.0 1.0 1.0 1.0 1.0 H2O 57.0 40.0 40.0 40.0 40.0 40.0 C. 40% Tetraethylammonium hydroxyde 26.0 Tetraethylammonium bromide 12.0 12.0 12.0 12.0 12.0 Reaction Composition (1), moles R2O (1) 1.0 1.0 1.0 1.0 1.0 1.0 Na2O 0.57 1.90 1.90 1.90 1.90 1.90 Cr2O3 0.13 0.04 0.04 0.04 0.04 0.04 K2O 0.13 0.04 0.04 0.04 0.04 0.04 SiO2 4.17 9.44 9.44 9.44 9.44 9.44 H2O 178 266 266 266 266 266 Crystalisation Conditions Temperature F 280 270 275 270 270 270 Days 15 21 21 21 15 21 X-Ray Analysis Beta Beta+ Beta Beta Beta+ Beta 95% Modernite 70% + 90% Modernite 80% + + Modernite + Modernite Quartz + Quartz + Quartz Quartz TABLE 2 (continued) Example 1 2 3(3) 4 5 6 Not Run Product Composition, Wt% N 1.47 ----1.60---- 1.25 1.55 Na 0.71 ----0.44---- 0.50 0.29 Cr 0.31 ----0.27---- 0.35 0.24 K 0.05 ----0.05---- 0.15 0.01 SiO2 76.29 ----74.55--- 77.21 76.0 Al2O3 1.37 ----1.28---- 1.20 1.50 Ash 85.3 ----84.75--- 84.3 Production Composition, mole ratio Al2O3 1.06 1.01 0.92 1.12 SiO2 100 100 100 100 Na2O 1.22 0.77 0.85 0.50 Cr2O3 0.23 0.21 0.27 0.19 Q2O(2) 4.19 4.60 3.48 4.35 Adsorption, Wt% (after calcination at 1000 F 16 hours) 12.7 11.8 10.4 12.8 Cyclohexane 11.3 11.6 9.8 12.0 n-Hexane 18.0 19.3 13.1 15.9 H2O 400 407 361 434 Surface Area, m2/gm 434 (1) Reaction composition calculated from added components (2) Q = tetraethylammonium (3) Examples 3 and 4 combined for composition analyses TABLE 3 Crystalization Experiments - (Fe, La) Beta Crystal Static System Stainless Steel Reactors Example 7 8 9 10 11 Reaction Mixture, gms A. S-35 Sodium Silicate 64.0 64.0 64.0 64.0 64.0 H2O 53.0 53.0 26.0 53.0 53.0 B. FeNH4(SO4)2 # 12H2O 1.3 1.3 1.3 LaCl3 # 6H2O 1.0 0.9 H2SO4 1.0 1.0 1.0 1.0 1.0 H2O 40.0 40.0 40.0 40.0 40.0 C. Tetraethylammonium bromide 12.0 12.0 12.0 12.0 12.0 Reaction Composition (1), moles Q2O (2) 1.0 1.0 1.0 1.0 1.0 Na2O 1.90 1.90 3.11 3.16 3.17 Fe2O3 0.047 0.047 0.047 La2O3 0.049 0.044 SiO2 9.44 9.44 14.2 9.44 9.44 H2O 266 266 256 266 266 Crystalisation Conditions Temperature F 270 270 270 268 275 Days 20 20 20 21 21 X-Ray Analysis Beta + Beta+ Beta Beta Beta+ Modernite Modernite 60% + 55% + Modernite + UCM (3) Modernite + Quartz + Quartz Quartz (1) Reaction composition calculated from added components (2) Q = tetraethylammonium (3) UCM = unindentified crystalline material TABLE 3 (continued) Example 7 8 9 10 11 Product Composition, Wt.% N 1.68 1.43 1.32 1.43 1.23 Na 0.52 0.64 0.40 0.50 0.57 Fe 0.40 0.44 0.46 La2O3 1.46 1.35 SiO2 78.0 76.8 78.2 74.75 77.72 Al2O3 1.2 1.26 1.20 1.26 1.32 Ash 85.4 87. 86.1 84.3 86.75 Production Composition, mole ratio Al2O3 0.91 0.96 0.91 1.0 1.0 SiO2 100 100 100 100 100 Na2O 0.87 1.09 0.67 0.88 0.96 Fe2O3 0.27 0.31 0.32 La2O3 0.36 0.32 Q2O 4.62 3.99 3.64 4.11 3.40 Adsorption, Wt.% (after calcination at 1000 F 16 hours) Cyclohexane 11.7 10.7 9.3 11.1 10.2 n-Hexane 10.2 9.6 8.4 11.4 9.3 H2O 18.3 15.1 12.5 17.5 13.5 Surface Area 400 387 349 390 340 A review of the foregoing data in Tables 2 and 3 shows that the Al2O3 content (after drying) of the as-synthesized materials varied from 0.92 (Example 5) to 1.12 Wt.% (Example 6). Al2O3 was due solely to its presence, if any, as an impurity in the reactants. Table IV set forth hereinbelow summarizes in tabular form the significant lines of the respective X-ray diffraction patterns obtained from the X-ray analysis of the products of Examples 1-11 inclusive. TABLE 4 CR-BETA FE-BETA LA-BETA EX. 1 EX. 2 EX. 3+4 EX. 5 EX. 6 EX. 7 EX. 10 EX. 11 D INT D INT D INT D INT D INT D INT D INT D INT 11.41 23 11.48 45 11.56 27 11.48 26 11.56 26 11.63 27 11.56 29 11.71 36 7.47 2 7.56 4 7.56 3 7.53 3 7.56 3 7.56 3 7.56 3 7.56 4 6.56 2 6.58 3 6.56 3 6.56 5 6.56 3 6.61 9 6.56 4 6.56 6 4.11 16 4.12 16 4.11 17 4.12 18 4.10 17 4.13 16 4.13 18 4.12 18 3.93 100 3.93 100 3.93 100 3.93 100 3.93 100 3.93 100 3.93 100 3.93 100 2.99 12 3.00 11 3.01 12 3.00 12 3.00 12 3.00 12 2.99 12 3.00 13 2.05 6 2.06 5 2.06 6 2.06 6 2.06 5 2.06 6 2.06 6 2.06 6 EXAMPLES 12-15 The compositions obtained from the exercise of Examples 3 and 4 (combined), 5, 9 and 10 were tested four relative hexane cracking activity i-values)*, at 7380C (1000 F), and are the subject of the instant examples, respectively. Pertinent details, i.e., conditions of base exchange treatment of the catalysts, compositions after base exchange and calcination, test results and the like, are listed in Table 5 set forth hereinbelow. Catalytic cracking activity is indicated by the weight percent conversion of hexane to lower boiling C1-C5 hydrocarbons, while isomerization activity is indicated by weight percent conversion to hexane isomerizationq Cracking activity is also indicated quantitatively by the term "alpha" (o() which is an indication of the relative catalytic cracking activity of the catalyst compared to a standard catalyst. ci is the relative rate constant (rate of n-hexane conversion per unit volume of oxides composition per unit time). It is based on the activity of highly active silica-alumina cracking catalyst taken as 6(= 1. * The o(-test is further described in a letter to the editor, entitled "Superactive Crystalline Aluminosilicate Hydrocarbon Cracking Catalysts", by P.8 Weisz and J.N. Miale, Journal of Catalysis, Vol. 4, pp. 527-529 (August 1965) and in U.S. Patent 3,354,078. TABLE 5 Beta-Type Crystal Exchange and Catalytic Data Example 12 13 14 15 Catalyst Description Product of ------------------------------ Ex. 3,4(1) Ex. 5(1) Ex. 9(2) Ex.10(2) Pre-exchange Treat T12-538 C ------------------------------ (T10-1000 F) Exchange 10 % NH4Cl ) 5 # 1 hrs. ) ---------------------------- 185 - 190 F) Composition, Wt. % Na < 0.01 0.01 0.01 0.02 Cr 0.04 0.08 La 0.45 Al2O3 1.5 1.51 SiO2 90.5 91.2 Ash 94.9 96.48 TABLE 5 (continued) Beta-Type Crystal Exchange and Catalytic Data Example 12 13 14 15 Surface Area, m2/gm (after 538 C (1000 C) treat) 439 401 424 442 &alpha;-Test 538 C (1000 C) n-Hexane Conversion, Wt % 5 minutes 50.0 63.1 50.9 42.2 25 minutes 32.4 46.8 33.2 28.6 &alpha; ;-Value 5 minutes 13.2 38.0 27.1 42.0 25 minutes 7.5 24.0 15.4 25.8 (1) See Table 2 (2) See Table 3 A review of the data obtained in Table 5 reveals that n-hexane conversion after 5 minutes ranged from 42.2 (Example 15) to 63.1 (Example 13) wt.%. &alpha;-values ranged after 5 minutes from 13.2 (Example 12) to 42.0 (Example 15).

Claims: CLAIMS: 1. A zeolite having as synthesized, having a composition, expressed in terms of moles of anhydrous oxides, as follows: (W)Q O (X)M,,O (y)iO 100 SiC2 wherein Q20 is the oxide form of an organic compound containing an element of Group 5-8 of the Periodic Table, said organic compound having at least one alkyl or aryl group having between 1 and 7 carbon atoms, at least one of which is an ethyl radical, M is an alkali metal having a valence n, W =(S, X = < 2, Y = < 4, and L = Al, Cr, Fe, or La, or mixtures thereof, provided that at least one of said Cr, Fe or La is present and Y is > zero, said zeolite having the X-ray diffraction pattern set forth in Table 1 of the specification. 2. A zeolite according to Claim 1 wherein M is hydrogen, ammonium, phosphonium, or a metal of Groups 1-8 of the Periodic Table or mixtures thereof. 3. A zeolite according to Claim 1 or Claim 2 wherein Q2 is a quaternary ammonium or phosphonium oxide containing at least one ethyl group. 4. A zeolite according to Claim 3 wherein said quaternary ammonium compound is a tetraethylammonium or phosphonium compound and M is sodium or potassium. 5. A zeolite according to any preceding Claim wherein substantially no alumina is present. 6. A method for preparing the zeolite claimed in Claim 1 which comprises preparing a reaction mixture containing a source of an alkali metal oxide, an oxide of chromium, iron, or lanthanum or mixtures thereof, silica, Q2 and water and having a composition, in terms of mole ratios of oxides, falling within the following ranges: SiO2/Q2O = 2 to 50 M2O/Q2O = 0.0 to 10 (Cr203 + La2 3 + Fe2 3)Q20 = 0.05 to 5 H2O/Q2O = 50 to 500 wherein QO is the oxide form of an organic compound containing an element of Group 5-B of the Periodic Table, said organic compound having at least one alkyl or aryl group having between 1 and 7 carbon atoms, at least one of which is an ethyl, and M is an alkali metal and maintaining said mixture until crystals of the zeolite form. 7. A method according to Claim 6 wherein said mixture has a composition, in terms of moles of oxides, falling within the following ranges: SiO2/Q2O = 4 to 15 M2O/Q2O= = 0.5 to 4 (Cr2O3 + La2O3 + Fe2O3)/Q2O = 0.08 to 0.2 H2O/Q2O = 150 to 300 wherein Q20 and M are as before. 8. A method according to Claim 6 or 7 wherein said Q2 is the oxide form of a quaternary ammonium or phosphonium compound. 9. A method according to Claim 8 wherein said quaternary ammonium or phosphonium compound is tetraethylammonium or phosphonium compound and M is sodium or potassium. 10. Use in converting an organic charge of a catalyst comprising a zeolite as claimed in any of Claims 1 to 5.

Inventors: PLANK, CHARLES JOSEPH, ROSINSKI, EDWARD JOSEPH, RUBIN, MAE KOENIG
Applicants: MOBIL OIL CORPORATION
Application year: 1982
Main classification: C01B33
IPC codes: C07C2, C01B39, B01J29, C07C67, C07B61, C10G45, C07C1