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United States Patent (19) 11) 4,388,177 Bowes Et Al

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United States Patent (19) 11) 4,388,177 Bowes Et Al United States Patent (19) 11) 4,388,177 Bowes et al. 45) Jun. 14, 1983 54 PREPARATION OF NATURAL FERRIERTE (56) References Cited HYDROCRACKING CATALYST AND HYDROCARBON CONVERSION WITH U.S. PATENT DOCUMENTS CATALYST 3,663,430 5/1972 Morris................................. 208/111 3,928,174 12/1975 Bonacci et al. ....................... 208/80 (75) Inventors: Emmerson Bowes, Woodstown; 4,025,575 5/1977 Chang et al......................... 585/640. Bruce P. Pelrine, Trenton, both of 4,278,564 7/1981 Pelrine ................................ 252/450 N.J. 4,335,019 6/1982 Bowes et al. ....................... 252/450 73 Assignee: Mobil Oil Corporation, New York, Primary Examiner-Delbert E. Gantz N.Y. Assistant Examiner-G. E. Schmitkons Attorney, Agent, or Firm-C. A. Huggett; M. G. Gilman; (21) Appl. No.: 355,439 S. Aksman 22 Filed: Mar. 8, 1982 57) ABSTRACT Related U.S. Application Data A shape-selective hydrocracking catalyst prepared by making a composite of a hydrogenation component and (62) Division of Ser. No. 225,079, Jan. 13, 1981, Pat. No. a natural ferrierite that has been treated with oxalic acid 4,335,019. to impart thereto catalytic activity for converting (51) Int. Cl............................................... C10G 47/18 slightly branched as well as straight chain hydrocar (52) U.S. C. ............................. 208/111; 208/DIG. 2; bons. The catalyst is useful for hydrodewaxing and for 208/59; 208/138 upgrading naphtha. (58) Field of Search .................. 208/111, DIG. 2, 59, 208/138 14 Claims, No Drawings 4,388,177 1. 2 4,016,245) and zeolite ZSM-38 (U.S. Pat. No. PREPARATION OF NATURAL FERRERTE 4,046,859). HYDROCRACKING CATALYST AND It is well known in the prior art that certain zeolites HYDROCARBON CONVERSION WITH such as zeolites A, X, or Y and the naturally occurring CATALYST zeolites chabazite, erionite, faujasite and mordenite can be stability-enhanced by methods comprising ion ex This is a division of copending application Ser. No. change and/or heating. U.S. Pat. Nos. 3,354,077; 225,079, filed Jan 13, 1981 now U.S. Pat. No. 4,335,019. 3,375,065; and 3,402,996 describe such methods. U.S. BACKGROUND OF THE INVENTION Pat Nos. 3,997,474 and 4,054,511 to Miale et al, on the O other hand, describe a method for activating naturally 1. Field of the Invention occurring ferrierite to make it selective primarily for This invention relates to a method for modifying the cracking normal paraffins by treatment with ammonium activity and shape selectivity of natural ferrierite so that ions and HF. The preparation and use of synthetic ferri hydrocarbons are cracked selectively. In particular, it is erite to increase the octane number of reformates is concerned with a method for making a shape-selective 15 described by Gianetti et al in Ind. Eng. Chem., Process hydrocracking catalyst from natural ferrierite, and with Design Dev, Vol. 14, No. 1, 1975, pp. 86-92, the entire a process for upgrading certain hydrocarbons by shape content of which, including literature cited, is incorpo selectively cracking the paraffins contained therein. rated herein by reference. Also incorporated by refer The process may be used to increase the octane number ence is Re.28,398 to Chen et al which describes shape of reformate, or to dewax a waxy-hydrocarbon to re 20 selective dewaxing with zeolite catalysts. duce its pour point. 2. Description of the Prior Art SUMMARY OF THE INVENTION Zeolitic materials, both natural and synthetic, have In accord with the present invention, a method of been demonstrated in the past to have catalytic proper modifying the shape selectivity of natural ferrierite, ties for various types of hydrocarbon conversions. Cer 25 allowing branched-chain hydrocarbons to be cracked tain zeolitic materials are ordered, porous crystalline selectively, has been found which comprises contacting aluminosilicates having a definite crystalline structure natural ferrierite with oxalic acid under controlled con as determined by X-ray diffraction. Within these crys ditions of time and temperature. By this method, the tals there are numerous small cavities which are inter catalytic properties of naturally occurring ferrierite connected by a number of still smaller channels or 30 may be enhanced in that the treated ferrierite exhibits a pores. These cavities and pores are precisely uniform in more open pore system with respect to the untreated size and placement within a specific zeolitic material. ferrierite allowing hydrocarbons, other than normals, to Since the dimensions of these pores are such as to ac be cracked. Moreover, by exchanging the above treated cept for absorption only molecules of certain dimen ferrierite with diammonium oxalate, a more useful cat sions while rejecting those of larger dimensions, these 35 ion (ammonium) is exchanged into the ferrierite while materials have come to be known as "molecular sieves' . simultaneously chelating the exiting cation. Thus, any and may be utilized to take advantage of this property. iron present as an impurity is removed as a chelate Such molecular sieves, both natural and synthetic, thereby eliminating excess methane production for cer include a wide variety of positive ion-containing crys tain reactions. For purposes of this invention, the modi talline aluminosilicates. These aluminosilicates can be 40 fied natural ferrierite is composited with a hydrogena described as rigid three-dimensional frameworks of tion-dehydrogenation metal, preferably platinum. The SiO4 and AlO4 tetrahedra that are cross-linked by the catalyst is a very effective shape-selective hydrocrack sharing of oxygen atoms whereby the ratio of the total ing catalyst, and it may be used for catalytic dewaxing aluminum and silicon atoms to oxygen atoms is 1:2. The or for upgrading the octane number of reformates. electrovalence of the tetrahedra containing trivalent 45 aluminum is balanced by the inclusion in the crystal of DESCRIPTION OF PREFERRED a cation such as an alkali metal or an alkaline earth metal EMBODIMENTS cation. This can be expressed wherein the ratio of alu The zeolite useful in the practice of this invention is minum to the number of various cations, such as Ca/2, natural ferrierite. The naturally occurring ferrierite has Sr/2, Na, K or Li is equal to unity. One type of cation SO been described by Graham (Roy. Soc. Canada, Proc. may be exchanged either entirely or partially by an and Trans., 3rd Ser, 12, 185-190) and by Staples (Am. other type of cation utilizing ion exchange techniques in Mineral, 40 1095-99). The formula of the natural min a conventional manner. By means of such cation ex eral ferrierite is given as (Na,/K)4Mg2(Si30Als)O72 change, it has been possible to vary the properties of a (OH)2.18H2O. The oxide formula is given in "Zeolite given aluminosilicate by suitable selection of the cation. 55 Molecular Sieves', John Wiley and Sons, Inc. (1974) as The cavities and channels of the crystal are occupied by (Na2, Mg)O.Al2O3.11.1SiO2.6.5H2O. molecules of water prior to dehydration. The ferrierite ore employed as starting material in the Prior art techniques have resulted in the formation of method of this invention is an ore having about 95% a great variety of synthetic aluminosilicates. These alu ferrierite which has a very low hexane cracking activity minosilicates have come to be designated by letter or 60 (a <1). When it is ion exchanged to its ammonium form other convenient symbols, examples of which are zeo and calcined, this material is stable, moderately active lite A (U.S. Pat. No. 2,882,243), zeoliteX (U.S. Pat. No. (a ranging from 25-200) and selective for cracking 2,882,244), zeolite Y (U.S. Pat. No. 3,130,007), zeolite straight chain hydrocarbons. These characteristics of ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4 (U.S. Pat. ammonium ferrierite are not altered by successive con No. 3,314,752), zeolite ZSM-5 (U.S. Pat. No. 3,702,886), 65 ventional ion exchanges with ammonium salts. zeolite ZSM-11 (U.S. Pat. No. 3,709,979), zeolite ZSM Cracking activity is also indicated quantitatively by 12 (U.S. Pat. No. 3,832,449), zeolite ZSM-23 (U.S. Pat. the term alpha (o) which is a measure of the relative No. 4,076,842), zeolite ZSM-35 (U.S. Pat. No. activity of the catalyst for cracking normal hexane com 4,388,177 3 4. pared to a highly active amorphous silica alumina active and inactive materials and synthetic or naturally cracking catalyst taken as C. = 1. occurring zeolites as well as inorganic materials such as The ol-test is further described in a letter to the editor clays, silica and/or metal oxides. The latter may be entitled "Superactive Crystalline Aluminosilicate Hy either naturally occurring or in the form of gelatinous drocarbon Cracking Catalysts' by P. B. Weisz and J. N. precipitates, sols or gels, including mixtures of silica and Miale, Journal of Catalysis, Vol. 4, pp. 527-529 (August metal oxides. Frequently, the zeolite materials have 1965). For additional description of the a-test see U.S. been incorporated into alumina or naturally occurring Pat, No. 3,354,078 issued to Miale and Weisz, the con clays, e.g. bentonite and kaolin. These materials, i.e., tents of which are herein incorporated by reference. clays oxides, etc., function, in part, as binders for the In carrying out the present process, natural ferrierite 10 catalyst. It is desirable to provide a catalyst having good is subjected to contact, in one embodiment, with aque crush strength, because in a petroleum refinery the ous oxalic acid followed by exchange with an aqueous 1 catalyst is often subjected to rough handling, which M diammonium oxalate solution.
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