NZ228425A

NZ228425A - Method of synthesising a crystalline molecular sieve comprising oxides of aluminium and phosphorus, and other elements

Info

Publication number: NZ228425A
Application number: NZ228425A
Authority: NZ
Inventors: Clarence Dayton Chang; John Dennis Lutner
Original assignee: Mobil Oil Corp
Priority date: 1988-04-08
Filing date: 1989-03-21
Publication date: 1990-11-27
Also published as: JPH03503881A; KR900700385A; EP0442879A1; DK279590D0; AU3549189A; DK279590A; WO1989009749A1

Description

<div id="description" class="application article clearfix"> 22 8 4 2 5 Priority Detafs): • * » • • • H* • *>■* • » ••••••■• •«• • • • •••••••••• Cot».H.cv,B Specification Class- <2^17^7°^-; Wwjm. • v»T> i • • • « # i|» • • • • • r« ••••••••• Sa • •h*i» ^V* •••••#•••• Col S^AjZb- ••••••• «jAVH W #f • •> • T • • • • M •••••• ||4<y| • L l I1UV UND Pubficetion Date: P.O. Journal. No: AS3& No.: Oitc: NEW ZEALAND PATENTS ACT. 1953 COMPLETE SPECIFICATION ,S^H7 0*s iy o\ ^198* j s&"CE^ <dJ SYNTHESIS OF A CRYSTALLINE MOLECULAR SIEVE .f/We. H08IL OIL CORPORATION, a corporation organised under the laws of the State of New York, United States of Anerlca, of 150 East 42nd Street, New York, State of New York, United States of Anerlca, hereby declare the invention for which *t7 we pray that a patent may be granted to p>e/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 -(followed by page la) 22 8 4 2 5 r 4703(4704,4703) - l«=c- SYNTKESIS OF A CRYSTALLINE MOLECULAR SIEVE This invention relates to a method for synthesizing a crystalline molecular sieve having pore windows measuring greater than 10 Angstroms in diameter, such as, for example, greater than 12 Angstroms in diameter. Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are cavities which may be interconnected by channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as 'toolecular sieves" and are utilized in a variety of ways to take advantage of these properties. SUch molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline aluminosilicates. These aluminosilicates can be described as rigid three-dimensional frameworks of Si04 and AlOj in which the tetrahedra are cross-linked hy the sharing of oxygen atoms whereby the ratio of the total alimeinum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, te, K or Li, is equal to unity. Qte type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it is possible to vary the properties of a given aluminosilicate by suitable selection of the cation. 22 8 4 2 5 P-4783(4T84,478» Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. The zeolites have come to be designated by letter or other convenient syabols, as illustrated by zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent 2,882,244), zeolite Y (U.S. Patent 3,130,007), zeolite ZK-S (U.S. Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-U (U.S. Patent 3,709,979), zeolite ZSM2 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983), zeolite ZSM-3S (U.S. Patent 4,016,245), zeolite ZSM-38 (U.S. Patent 4,046,8S9), and zeolite ZSM-23 (U.S. Patent 4,076,842). Porous aluainophosphates and their synthesis with the aid of organic directing agents are disclosed in U.S. Patent Nos. 4,310,440 and 4,385,994, whereas the synthesis of silicophosphoaluainates of various structures are disclosed in U.S. Patents 4,440,871 and 4,673,559. Methods for synthesizing crystalline aetalloaluainophosphates are described in U.S. Patent Kb. 4,713,227. Hie present invention resides in a method for synthesizing a crystalline Molecular sieve having an X-ray diffraction pattern with lines shoui in Tfeble 1A of the specification, which comprises (i) preparing a Mixture comprising sources of oxides of aluainua, phosphorus, and optionally one or aore elements (M) other than aluminum or phosphorus, water and a directing agent (DA), and having a coaposition, in tens of sole ratios, within the following ranges: 0 to 0.5 0.5 to 1.25 10 to 100 0.5 to 1.5 wherein M is a compound of the foraula: 228425 wherein X is an anion and R, R', R" and R'•' are the sane or different and are selected from -CH^X and -CH^CH^X wherein X is the same element (s) as the anion, (ii) maintaining said mixture under conditions including a temperature of 100°C to 145*C for a period of time of up to 80 hours and (iii) recovering the crystalline product from step (ii). the crystalline molecular sieve produced according to the method of the invention has a framework topology which exhibits, even after being heated at U0°C or higher, a characteristic X-ray diffraction pattern having the following lines: Table 1A Interplanar d-Spacings (A) 16.4 ♦ 0.2 8.2" 0.1 4.74 7 0.05 Relative Intensity vs w w and more specifically the following characteristic values: Table IP Interplanar d-Spacings (A) 16.4 + O.f T 8.2 7 0.1 Pelative Intensity V5 W W 5.48 ♦ 0.05 4.74♦ 0.05 w w and even more specifically the following characteristic values: 22 8 4 25 T 4703(4704,4705) Table 1C Interplanar d-Spacings (A) 16.4 ♦ 0.2 8.2 + 0.1 Relative Intensity vs v °-°5 w 5.48 ♦ O.OS 4.74 ♦ 0.05 4.10 ♦ 0.04 4.0S ♦ 0.04 w W W V 8:«)-n-04 w 3.76 ♦ 0.03 3.28 ♦ 0.03 v v The X-ray diffraction lines in Tables 1A, IP and 1C identify a crystal fraaework topology in the conposition exhibiting large pore windows of 18-aeabered ring size. The pores are at least 10 Angstroas in diaaeter, such as for exaaple at least 12 Angstroas, e.g. 12-13 Angstroas, in diaaeter. These lines distinguish this topology froa other crystalline aluainosilicate, aluainophosphate and silicoaluainophosphate structures. It is noted that the X-ray pattern of the present coaposition is void of a d-spacinp value at 13.6-13.3 Angstroas with any significant intensity relative the strongest d-spacing value. If a d-spacing value in this range appears in a saaple of the present coaposition, it is due to iapurity and will have a weak relative intensity. These X-ray diffraction data were collected with conventional X-ray systeas, using copper K-alpha radiation. The positions of the peaks, expressed in degrees 2 theta, where theta is the Bragg angle, were deterained by scanning 2 theta. The interplanar spacings, d, measured in Angstroa units (A), and the relative intensities of the lines, I/IQ, where IQ is one-hundredth of the intensity of the strongest line, including subtraction of the background, were derived. The relative intensities are given in terms of the syabols vs ■ very strong (75-1001), s * strong (50-74t), a » aediua (25-491) and w » weak (0-24%). It should be understood that this X-ray diffraction 22 8 4 2 5 r-JW4;«4,4;ai>) --5— pattern is characteristic of all the species of the present compositions. Ion exchange of cations with other ions results in a composition which reveals sifcstantially the same X-ray diffraction pattern with some minor shifts in interplanar spacing and variation 5 in relative intensity. Relative intensity of individual lines may also vary relative the strongest line when the composition is ^ chemically treated, such as by dilute acid treatment. Other variations can occur, depending on the composition component ratios of the particular sample, as well as its degree of thermal 10 treatment. The relative intensities of the lines are also susceptible to changes by factors such as sorption of water, hydrocarbons or other components in the channel structure. Rirther, the optics of the X-ray diffraction equipment can have significant effects on intensity, particularly in the low angle region. 15 Intensities may also be affected by preferred crystallite orientation. More specifically, the rolecular sieve produced by the method of the invention comprises a three-dimensional framework structure composed of tetrahedral units of AIO2, P02 and 20 optionally M02, where M is at least one element other than aluminum or phosphorus. Khere the element M is absent, the O molecular sieve has the following composition, in terms of mole ratios of oxides: A1203:xP2pS:nH2° 25 where x is 0.S to 1.5, and n is O-lOO and preferably ft-10. Nhere present, M is preferably silicon alone, in which case the molecular sieve has the following composition in terms of mole ratios of oxides: A120j: xP20s: ySi O2: nH20 30 where x is 0.5 to 1.5, y is 0.01 to 0.5 and n is 0-100 and preferably 0-10. Alternatively M includes an element other than silicon, such that the sua of the aluminum and phosphorus exceeds the number 22 8 4 2 5 F-4783(4784,4785) —6— of M atoms and the nolecular sieve has the following conposition, in the anhydrous state and in terns of sole ratios of oxides: («o-)1.x:<rop1_y;(Mor')x.y together with anions and/or cations necessary for electrical neutrality and where n is the valence (or weighted average valence) of M, x and y satisfy the following relationship: z » y - x *(4 ♦ n) . (x ♦ y) and z is greater than -I and less than *1. Mien z is greater than 0, the Molecular sieve will behave as a cation exchange Material with potential use an an acidic catalyst. When z is less than 0, the Molecular sieve will behave as an anion exchange material with potential use as a basic catalyst. In sone cases silicon nay also be present such that the ratio of silicon:non-silicon atons is less than 1, preferably less than 0.5. The elenent M in this alternative eabodinent has an oxidation nunber of fron *2 to *6, and an ionic "Radius Patio" of 0.15 to 0.73, except that when the oxidation nunber of M is *2, the Radius Ratio of the elenent V is 0.52 to 0.62. The tern "Radius Patio" is defined as the ratio of the crystal ionic radius of the elenent M to the crystal ionic radius of the oxygen anion, 0"2. fedius Ratio • crystal Ionic radius of the elewnt M crystal ionic radius of 0"2 The crystal ionic radii of elements are listed in the CRC Handbook of Chen is try and Physics» 61st edition, CRC Press, Inc., 1980, pages F-216 and F-217. In determining the Radius Patio, it is necessary to use crystal ionic radii of the V a ton and oxygen anion «T2) which have been neasured by the sane nethod. _ \ w ^ _ 22 8 4 2 5 F-47g3(47847i3&5> —7— Examples of element M useful herein include: 10 15 M Valence Radius 1 As ♦3 0.44 B ♦3 0.17 Bi ♦3 0.73 Co ♦2 0.55 CU ♦2 0.54 Fe ♦2 0.56 Fe ♦3 0.48 Ge ♦2 0.55 fe ♦4 0.40 In ♦3 0.61 MK ♦2 0.61 Sb ♦3 0.57 Sn ♦4 0.54 Ti ♦3 0.58 n ♦4 0.52 V ♦3 0.56 V ♦4 0.48 V ♦5 0.45 Zn ♦2 0.56 include: Bcaaples of elements not included as M of the present Invention 20 C 25 30 Elenent Valence Radius 1 B ♦1 0.26 Ba ♦1 1.16 Ba ♦2 1.02 Ce ♦3 0.78 Cd ♦1 0.86 Cd ♦2 0.73 Cr ♦1 0.61 Cr ♦2 0.67 CU ♦1 0.73 La ♦1 1.05 Mg ♦1 0.62 Mb ♦2 0.50 Ho ♦1 0.70 Ski ♦2 0.70 Sr ♦2 0.85 Th ♦4 0.77 TI ♦1 0.73 Ti ♦2 0.71 Zn ♦1 0.67 22 8 4 2 5 T 4703(4704,4705)' —8— As synthesized, the crystalline conposition will generally comprise structural aluminum, phosphorus and element M, and will exhibit an M/(aluminum plus phosphorus) atonic ratio of less than unity and greater than zero, and usually within the range of fron 0.001 to 0.99. The phosphorus/aluninun atonic ratio of such naterials nay be found to vary fron 0.01 to 100.0, as synthesized. It is well recognized that aluninun phosphates exhibit a phosphorus/aliotinun atonic ratio of about unity, and essentially no elenent M. Also, the phosphorus-substituted zeolite compositions, sonetimes referred to as "aluminosilicophosphate" zeolites, have a silicon/aluminum atomic ratio of usually greater than inity, and generally from 0.66 to 8.0, and a phosphorus/alwinun atonic ratio of less than utity, and usually fron 0 to 1. According to the invention, the molecular sieve described above is synthesized from a reaction mixture hydrogel containing sources of aluninun, phosphorus and optionally the non-aluminum, non-phosphorus element M, an organic directing agent, and water and having a conposition, in terns of mole ratios, within the following ranges: Broad Preferred Most Preferred P2O5/AI2O3 0.5 to 1.25 0.9 to 1.1 0.9 to 1.1 H2O/AI2Q3 10 to 100 20 to P0 30 to 60 DA/AI2O3 0.2 to 0.8 0.3 to 0.7 0.4 to 0.6 and when the element M is present: M/AI2O3 0.01 to 0.5 0.01 to 0.2 0.01 to 0.1 The directing agent PA is a compound represented by the formula: 01 • fl 228-125 —9— wherein X is an anion such as hydroxide or halide (e.g. chloride or bromide) R, R', R'■ and R'1' are the same or different and are selected fron -CH^X and -CH2CH2X wherein X is the same element (s) as the anion. Preferred examples of these compounds include tetrakis (2-hydroxyethyl) asnoniu hydroxide, tetrakis (2»chloroethyl)am>niuB chloride and tetrakis(hydroxyaethyl)aBaoniua broaide. Reaction conditions involve heating the foregoing reaction ■ixture to a temperature of 100°C to 145°C for 1 hour to 80 hours. A more preferred temperature range is froa 130°C to 145*C with the aaount of time at temperature being froa 10 hours to 30 hours. If the teaperature is higher than 14S'C and/or the tiae exceeds 80 hours, the product conposition will contain less of the desired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, IB and 1C. Also iaportant in the synthesis procedure is the ratio of ^$^2^3 *n reaction "ixture. Mien the ratio is greater than about 1.2S, especially if the teaperature is higher than 145*C, product coaposition will contain decreased aaounts of the desired crystalline aaterial. The solid product coaposition coaprising the desired aolecular sieve is recovered froa the reaction aediua, such as by cooling the whole to rooa teaperature, filtering and water washing. The organic directing agent can then be reaoved froa the product by conventional calcination procedures. Hie synthesis aethod of the present invention is facilitated by the presence of seed crystals, such as those having the structure of the product crystals, in the reaction Mixture. The use of at least O.Olt, preferably 0.101, and even aore preferably 1% seed crystals (based on total weight) of crystalline aaterial in the reaction aixture will facilitate crystallization in the present aethod. 22 8 4 I~ 4783(4704,4703) —10— The reaction mixture conposition for the present method is prepared utilizing materials which supply the appropriate oxide. Useful sources of aluminum oxide include, as non-1initing examples, any known form of aluninun oxide or hydroxide, organic or inorganic salt or conpound, e.g. alumina and aluninates. Such sources of aluninun oxide include pseudo-boehnite and aluminum tetraalkoxide. Useful sources of phosphorus oxide include, as non-limiting examples, any known form of phosphorus acids or phosphorus oxides, phosphates and phosphites, and organic derivatives of phosphorus. Useful sources of elenent M include, as non-1initing examples, any known form of non-aluninun, non-phosphorus elenent, e.g. metal, its oxide or hydride or salt, alkoxy or other organic conpound containing M. It will be understood that each oxide conponent utilized in the reaction mixture can be supplied by one or more essential reactants and they can be nixed together in any order. For exanple, any oxide can be supplied by an aqueous solution. The reaction nixture can be prepared either batchwise or continuously. Crystal size and crystallization tine for the product conposition conprising the desired metalloalmonophosphate will vary with the exact nature of the reaction nixture employed within the above-described limitations. Khile the molecular sieve of the present invention ray be used as an absorbent or as a catalyst conponent in a wide variety of organic compound, e.g. hydrocarbon conpound, conversion reactions, it is notably useful as a catalyst in the processes of cracking, hydrocracking, isomerization and reforming. Other conversion processes for which the present conposition nay be utilized as a catalyst conponent include, for exanple, dewaxing. The crystalline nolecular sieve prepared in accordance herewith can be used either in the as-synthesized form, the hydrogen form or another univalent or multivalent cationic form. It can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, 22 8 4 2 5 T 470S(4704,470S) --11-- chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. SUch components can be exchanged into the composition, impregnated therein or physically intimately admixed therewith. Such components can be impregnated in or on to the crystalline composition such as, for example, by, in the case of platinum, treating the material with a platinum metal-containing ion. Suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. Combinations of metals and methods for their introduction can also be used. The present composition, when employed either as an adsorbent or as a catalyst in a hydrocarbon conversion process, should be dehydrated at least partially. This can be done by heating to a temperature in the range of from 6S°C to 31S°C in an inert atmosphere, such as air and nitrogen, and at atmospheric or subatmospheric pressures for between 1 and 48 hours. Dehydration can be performed at lower temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a particular degree of dehydration. The thermal decomposition product of the newly synthesized composition can be prepared by heating same at a temperature of froa 200*C to 550°C for from 1 hour to 48 hours. As above mentioned, synthetic metalloaluminophosphate prepared in accordance herewith can have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical replacing cations include hydrogen, aamonium and metal cations including mixtures thereof. Of the replacing metallic cations, particular preference is given to cations of metals such as rare earths and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB AND VIII of the Periodic Table of Elements, especially Mi, Ca, Hp, Zn, Cd, Pd, tii, CU, Ti, Al, Ski, Fe and Co. 22 8 4 2 5 f *4783(4784 >4783) —12— A typical ion exchange technique would be to contact the synthetic material with a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates. Nhen used as a catalyst, it may be desirable to incorporate the molecular sieve of the invention with another material resistant to the temperatures and other conditions employed in organic conversion processes. &ich matrix materials Include active and inactive materials and synthetic or naturally occurring zeolites as well as incorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter nay be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Use of an active material in conjunction with the present molecular sieve, i.e. combined therewith, may enhance the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction. Frequently, crystalline catalytic materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing. Naturally occurring clays which can be composited with the present molecular sieve include the montmorillonite and kaolin families which include the sUbbentonites, and the kaolins co—only known as Dixie, Mctamee, Georgia and Florida clays, or others in tdiich the main mineral constituent is halloysite, kaolinite. 22 8 4 2 5 F 4703(1781,1785) —13 — dickite, nacrite or anauxite. Such clays can be used In the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. In addition to the foregoing materials, the crystals hereby synthesized can be composited with a porous Matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alwina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. A mixture of these components could also be used. The relative proportions of finely divided crystalline material and matrix vary widely with the crystalline material content ranging from 1 to 90 percent by weight, and nore usually in the range of 2 to 50 percent by weight of the composite. Baploying a catalyst comprising the molecular sieve of this invention containing a hydropenation component, reforming stocks can be reformed employing a teaperature between 450*C and 550*C. The pressure can be between 44S and 3S50 kPa (50 and 500 psig), but is preferably between 890 and 2170 kPa (100 and 300 psig). The liquid hourly space velocity is generally between 0.1 and 10 hr*1, preferably between 1 and 4 hr"* and the hydrogen to hydrocarbon aole ratio is generally between 1 and 10, preferably between 3 and 5. A catalyst comprising the present coaposition can also be used for hydroisomerization of noraal paraffins, when provided with a hydrogenation component, e.g. platinua. tydroisoaerisation is carried out at a teaperature between 2S0*C to 4S0*C, preferably 300°C to 425°C, with a liquid hourly space velocity between 0.1 and 10 hr~*, preferably between 0.5 and 4 hr*1, eaploying hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and 10. Additionally, the catalyst can be used for olefin or aroaatics isoaerization eaploying temperatures between 0*C and 550*C. A catalyst coaprising the molecular seive of this invention can also be used for reducing the pour point of gas oils. This 22 8 4 2 5 •f' 4703(4704—14 — process is carried out at a liquid hourly space velocity between 0.1 and 5 hr"1 and a temperature between 300°C and 425°C. This invention will now be more particularly described with reference to the Examples and the accompanying drawings in which Figures 1-8 are X-ray diffraction patterns of the calcined product of Examples 1 to 8 respectively. Example 1 A mixture containing 103.5 g of 8SI orthophosphoric acid (HjF04) in 155 g water was nixed with 50.8 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 105.5 g tetrakis(2-hydroxyethyl)ammonium hydroxide (DA) in 150 g water, giving a final reaction nixture composed as follows: P2O5/AI2OJ - 1.26 H2O/AI2&3 • 52 DA/AI2O3 ■ 0.7 The reaction mixture was placed in a 1000 cc autoclave. Crystallization in the autoclave was at 140°C under 2170 kPa (300 psig) nitrogen for 16 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. Hie product was calcined at S38*C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 2 and Figure 1. 22 8 4 2 5 F <7Q3( <70< t178S) —15— Table 2 Interplanar Observed Relative d»Spacings (A) 2xTheta Intensities (I/Ift) 19.62633 4.502 2.0 16.50637 5.354 100.0 11.95308 7.396 7.1 8.24634 10.728 27.2 6.20381 14.277 12.9 4.74095 18.717 12.7 4.33935 20.467 1.4 4.19087 21.200 4.5 4.08690 21.746 57.1 4.06799 21.848 67.2 3.96914 22.399 42.0 3.95098 22.504 46.0 3.79405 23.447 13.3 3.77009 23.598 24.3 3.58563 24.831 5.7 3.50222 25.433 0.4 3.47553 25.631 1.4 3.43484 25.940 2.2 3.41076 26.126 1.0 3 28214 27.169 32.2 3.17008 28.149 4.9 3.15501 28.287 4.4 3.08670 28.926 14.2 3.08117 28.979 11.1 3.033S1 29.445 2.3 2.95461 30.249 9.2 2.95086 30.289 10.4 2.91456 30.675 1.4 2.81518 31.786 0.9 2.73786 32.709 12.7 2.73145 32.788 7.4 Cheaical analysis of the extracted Btaaple 1 product indicated the following coaposition: A1 19.63 wt.l P 21.04 wt.l Si 0.026 wt.l Na 0.029 wt.l 22 8 425 f '1703(<78iM705) *16" Fxaaple 2 A nixture containing 115 g of 851 orthophosphoric acid (HjFOj) in 155 g water was nixed with 71 g aluninun oxide source (pseudo-boehnite). The nixture was heated to 80°C with stirring for 3 hours. To this Mixture was added 105.5 g tetrakis(2>hydroxyethyl)aanoniua hydroxide (PA) in 150 g water, giving a final reaction nixture composed as follows: The reaction nixture was placed in a 1000 cc autoclave. Crystallization in the autoclave was at 142°C under 2170 kPa (300 psig) nitrogen for 17 hours. The solid product was filtered, washed and dried. Hashing was acconplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530*C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Tbble 3 and Figure 2. P>0c/Al,0j H207A176J DA/Al-jOj 1 40 0.5 r* r* 5 V, 10 15 20 C 25 22 8 4 2 5 •F <703(4704t4705)~ —17— The reaction aixture was placed in an autoclave. Crystallization in the autoclave was at 138°C wder 2170 kPa (300 psig) nitrogen for 14 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530*C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and Figure 3. Table 3 Interplanar d-Spacings (A) 16.57941) 16.43716/ 8.21396 6.16367 4.73769 4.09134 4.05906: 3.96168 3.93658j 3.77338 3.42679 3.28000 3.19718 3.16223 3.07912 2.95194 2.9478S 2.89369 2.73464 2.58822 Observed Pelative 2xlheta Intensity 5.330 75.6 5.376 100.0 10.771 23.9 14.370 13.9 18.730 12.8 21.722 45.6 21.897 56.6 22.442 30.8 22.587 34.6 23.578 18.3 26.002 1.9 27.188 30.3 27.906 1.1 28.221 5.3 28.999 12.3 30.277 10.7 30.320 12.1 30.902 3.2 32.748 13.5 34.6S8 0.6 Cheaical analysis of the extracted Exanple 2 product indicated the following coaposition: Al 19.46 wt.l P 16.63 wt.l Si 0.046 wt.l to 0.033 wt.l 22 8 4 2 5 r 4703(4704,470D) —18— Example 3 A mixture containing S7.5 g of 8St orthophosphoric acid (H3FO4) in 77.5 g water was nixed with 35.5 g aluminum oxide source (pseudo»boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 52.75 g tetrakis (2»hydroxyethyl)ammonium hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows: The reaction nixture was placed in an autoclave. Crystallization in the autoclave was at 138°C under 2170 kPa (300 psig) nitrogen for 14 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530*C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and Figure 3. 1 41 0.5 DA/AI2O3 22 8425 -F <783( 1701,4705) —19— Table 4 Interplanar Observed Relative d>Spacings (A) 2xlheta Intensiti< 16.33147 5.411 100.0 8.19161 10.800 24.4 6.15847 14.382 13.7 4.73260 18.750 13.5 4.46994 19.863 1.1 4.07984 21.784 54.7 4.05933 21.895 61.4 3.95056 22.506 38.3 3.93839 22.576 39.4 3.77224 23.S85 16.9 3.76217 23.649 23.5 3.62809 24.536 8.9 3.58473 24.838 8.0 3.27475 27.232 34.8 3.16219 28.221 8.4 3.07736 29.016 14.9 3.02653 29.514 8.7 2.94680 30.331 16.9 2.89666 30.869 8.4 2.88632 30.983 9.2 2.74261 32.650 11.0 2.73319 32.766 12.4 2.72987 32.807 9.7 Chemical analysis of the extracted &tample 3 product indicated the following composition: A1 21.33 wt.l P 20.13 wt.l Si 0.028 wt.l Na 0.021 wt.l Bcample 4 (Comparative) A mixture containing 61 .S g of 851 orthophosphoric acid (H3P04) in 92.1 g water was mixed with 30.2 g aluninun oxide source (pseudo-boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 62.7 g tetrakis(2-hydroxyethyl)aMoniun hydroxide (DA) in 89.2 g water, giving a final reaction nixture composed as follows: — >«.. i-t. 22 84 2 7-4783(4784,4785) --20-- PtOC/AI 2O3 - 1.28 H2O/AI2O3 » 52 DA/AI2O5 » 0.71 The reaction nixture was placed in an autoclave. Crystallization in the autoclave was at 160°C under 2170 kPa (300 psig) nitrogen for 5 hours. The solid product was filtered, washed with water and dried. The product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 5 and Figure 4. Table 5 Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities 11.83947 7.467 56.4 6.83277 12.957 9.2 5.91531 14.977 23.9 4.46975 19.863 57.5 4.23470 20.978 47.9 3.94108) 22.561 56.7 3.95335) 22.490 100.0 3.59716 24.750 5.1 5.41379 26.103 36.8 3.30072 27.014 0.0 3.07036) 29.083 13.3 3.06S1S> 29.134 11.7 2.95580 30.237 21.4 2.65608 33.746 5.0 2.58051 34.765 17.1 The product of Bcanple 4, crystallized fron the indicated reaction nixture at 160*C was found to be prinarily A1F04~S, void of any significant amount of the large pore aluninophosphate crystals of the present synthesis invention. Btanple 5 A nixture containing 56.4 g of 851 orthofhosphoric acid (H3FO4) in 77.5 g water was nixed with 35.5 g aluninun oxide source (e.g. pseudo-bochnite) and 0.6 g silicon oxide source (e.g. 22 8 4 F 4783(4704,4705-) —21-- HiSil). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 52.75 g tetrakis(2~hydroxyethyl)ammoniua hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows: The reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 142°C under 2170 kPa (300 psig) nitrogen for 17 hours. The solid product was filtered, washed and dried. Hashing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530*C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 6 and Figure 5. Si02/Al205 0.04 1 41 0.5 22 8 4 2 5 r"4783(4704,4785) —22— Table 6 Interplanar Observed Relative d-Spacings (A) 2xTheta Intensiti 16.68787) S.296 58.5 16.26226) 5.434 100.0 8.89212 9.947 7.3 8.17058 10.828 20.6 6.13784 14.431 11.1 5.46353 16.223 1.8 4.73902) 18.724 9.0 4.70722) 18.852 8.4 4.07994) 21.783 67.3 4.07134) 21.830 61.1 4.0S0S5 21.943 53.7 3.96029) 22.450 32.3 3.947291 22.525 38.9 3.92603J 22.649 46.9 3.75873 23.671 16.2 3.62657 24.547 3.4 3.33667 26.717 2.3 3.31352 26.907 2.4 3.27994 27.188 21.1 3.26921 27.279 23.0 3.15S04 28.286 3.8 3.07718 29.018 8.4 3.02872 29.492 2.4 3.01346 29.645 1.2 2.98113 29.974 0.4 2.9S16S 30.280 6.5 2.94100 30.393 9.0 2.82514 31.671 0.0 2.75903 32.451 2.0 Cheaical analysis of the extracted ficaaple 5 product indicated the following composition: A1 P Si Na 22.09 vt.l 18.84 wt.l 0.29 wt.l 0.04 wt.l 22 8 4 2 5 P 4703(4704,470S) -23- Fxample 6 (Comparative) A mixture containing 55,8 g of 851 orthophosphoric acid (HjPO^) in 77.5 g water was mixed with 35.5 g alisinum oxide source (e.g. pseudo-boehmite) and 1.0 g silicon oxide source (e.g. HiSil). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 52.75 g tetrakis (2-hydroxyethyl hwonium hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows: The reaction mixture was placed in a 300 cc autoclave. Crystallisation in the autoclave was at 151°C under 2170 kPa (300 psig) nitrogen for 20 hours. Hie solid product was filtered, wa nitrogen for 16 hours. The solid product was filtered, washed and dried at 110°C for 17 hours. The product was analysed by X-ray powder diffraction and found to be crystalline and to show the pattern of "fable 7 and Figure 6. Si Oj/A1 <>03 p^Oc/Aifo H)0/A1 i6j DA/AI2P5 V 0.068 1 41 0.S Table 7 Interplanar d-Spacings (A) Observed 2xTheta Pelative Intensities (I/I«) 11.87357 6.84887 5.92402 4.47513 4.22879 3.9S662 3.59569 3.41744 3.25865 3.07050 2.95952 2.65784 2.58301 7.445 12.926 14.955 19.839 21.008 22.471 24.761 26.074 27.369 29.082 30.198 33.722 34.730 56.6 9.S 26.1 60.8 57.8 100.0 4.9 35.1 0.5 15.8 19.3 5.0 15.4 22 8 4 25 P=4?ft3^781,1785) —24— The product of Example 6, crystallized froa the indicated reaction mixture at 151°C for 20 hours was primarily SAFO-5 and was void of any significant amount of the large pore silicoaluminophosphate crystals of the present synthesis invention. A nixture containing 56.6 g of 851 orthophosphoric acid (H3FO4) in 77.5 g water was mixed with 0.46 g of vanadium pentoxide The mixture was heated to 50°C with stirring for 30 minutes until complete dissolution of the vanadium pentoxide. Then, 35.5 g of aluminum oxide source (e.g. pseudo-boehmite) was added and the mixture was heated to 80°C for 1 hour. To this mixture was added 52.75 g tetrakis(2-hydroxyethyl)annoniuin hydroxide (EA) in 75 g water, giving a final reaction mixture composed as follows: The reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 142*C at autogenous pressure for 17 hours. The solid product was filtered, washed and dried. Mashing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at S30°C in air for 10 hours. The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Tfeble 8 and Figure 7. Example 7 M/AliO* 0.01 1 40 0.5 • ir-n*r i i m -•'*nnnT"Tmrmfw(>niil,. .*-« •O T*4783(4704,4705) —25— Table 8 /"""N Interplanar Observed d-Spacings (A) 2xTheta 16.57872) 5.330 16.35191\ 5.404 14.10361 6.267 r* 5 8.24762 10.727 6.16987 14.356 5.70737 15.526 5.49256 16.137 5.13743 17.261 4.83746 18.340 4.63375 19.154 l0 4.48486 19.796 4.44217 19.988 4.38940 20.231 4.09681 21.693 3.95979 22.453 3.93834 22.577 3.92046 22.681 3.55416 25.055 3.52731 25.249 3.45606 25.778 3.43090 25.970 3.40681 26.1S7 3.32695 26.797 3.28900 27.112 3.26948 27.277 - ?0 3.1S962 28.244 3.09672 28.830 3.08958 28.898 3.08135 28.977 3.02691 29.510 2.98840 29.899 2.95680 30.226 2.94644 30.335 25 2.90223 30.809 2.82792 31.639 2.77318 32.281 2.73918 32.692 2.72426 32.877 2.67483 33.502 2.60065 34.487 ,A 2.57558 34.833 22 84 Relative Intensities (I/Ift) 44.6 53.7 2.6 9.0 6.1 4.1 1.8 1.5 1.8 O.S 7.2 3.4 0.2 100.0 44.6 56.9 38.3 8.4 4.2 0.9 0.6 1.7 6.0 15.8 18.3 0.8 4.9 6.3 7.0 9.7 5.1 1.5 0.4 2.4 2.4 2.2 5.5 2.3 0.7 1.1 0.3 22 8 4 2 5 *T»4703( 47Q4,4703^ —26 Chenical analysis of the extracted Exanple 7 product indicated the following conposition: A nixture containing S6.6 g of 851 orthophosphoric acid (HjF0|) in 77.5 g water was nixed with 0.46 g of vanadiun pentoxide (V,05). The nixture was heated to 50#C with stirring for 30 ninutes until conplete dissolution of the vanadiun pentoxide. Then, 3S.5 g of aluninun oxide source (e.g. pseudo-boehnite) was added and the nixture was heated to 80°C for 1 hour. To this nixture was added 52.75 g tetrakis (2-hydroxyethyl )annoniun hydroxide (DA) in 7S g water, giving a final reaction nixture cocposed as follows: The reaction nixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 147*C at autogenous pressure for 17 hours. The solid product was filtered, washed with water and dried at 110*C for 17 hours. The product was analysed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 9 and Figure 8. A1 P V Si 18.75 wt.t 17.39 wt.t 0.19 wt.* 0.17 wt.t Exanple 8 (Conparative) DA/A120J 0.01 1 40 0.5 22 8 4 11 T 1703(47041< 785)"" --27-- Table 9 Interplanar Observed Relative d-Spacings (A) 2x1heta Intensitii 11.86314 7.452 56.5 6.84404 12.935 10.0 5.925IS 14.952 24.7 4.47602 19.835 57.1 4.20617 21.122 51.4 3.95363 22.488 100.0 3.58446 24.840 3.1 3.41877 26.064 34.6 3.19075 27.963 0.4 3.06316 29.153 14.7 2.96016 30.191 17.9 2.65390 33.774 4.4 2.58432 34.712 13.7 The product of foaaple 8 was composed priaarily of crystals having the structure of A1F04*S, with only a svall amount of the large pore aetalloaluvinophosphate crystals of the present invention </div>

Claims

<div id="claims" class="application article clearfix printTableText"> 228-125 --28-- r> 10 IS c 20 WHAT l/WE CLAIM IS; 1. A method for synthesizing a crystalline nolecular sieve having an X-ray diffraction pattern with lines shown in Tfcble 1A of the specification, which conprises (i) preparing a Mixture comprising sources of oxides of aluminum, phosphorus, and optionally one or more elements (M) other than aluainua or phosphorus, water and a directing agent (DA), and having a conposition, in teras of mole ratios, within the following ranges: M/ai2o3 P2O5/AI2O3 H2O/AI2O3 DA/A120J wherein DA is a compound of the formula: R' X 0 to 0.S 0.S to 1.2S 10 to 100 0.S to 1.5 i» • • wherein X is an anion and R, R', R" and R* • • are the saao or difforont and are selected froa -CH^X and -CHjCH^X whoroin X is the same element (s) as the anion, (ii) maintaining said mixture under conditions including a temperature of 100* C to 14? C for a period of tiao of up to 80 hours and (iii) recovering the crystalline product from step (ii). u 2. The aethod of claia 1 wherein M is present in the reaction aixture and M/A^O^ is 0.01 to O.S. 3. The aethod of claia 1 wherein the aixture has the following coaposition ranges: P2°S/M2°5 °'9 t0 1,1 HgO/AljOj 20 to 80 DA/A12Qj O.Jjto 0.7 --29 4. The method of claim 3 wherein M is present in the reaction mixture and M/A1203 is 0.01 to 0.2 5. The method of Claim 1 wherein said mixture has the following composition ranges: 6. The method of claim S wherein M is present in the reaction mixture and M/A120j is 0.01 to 0.1 7. The method of claim 2 wherein M includes an element other than silicon having an oxidation number *2 and an ionic radius ratio of 0.52 to 0.62 or an oxidation number of +3 to *6 and an ionic radius ratio of 0.15 to 0.73. 9. The method of claim 2, wherein M also includes silicon such that the ratio of silicon:non-silicon atoms in the MQ2 conponent is less than 1. 10. The method of claim 1 wherein the directing agent VA is tetrakis(2-(hydroxyethyl)ammonium hydroxide. 11. A method for synthesizing a crystalline molecular sieve having an X-ray diffraction pattern with lines shown 1n Table IA of the specification substantially as herein described with reference to examples i» 2, 3, 5 and 7. P?0r/Al-,0, H.O/Al.O. da/ai2o3 0.9 to 1.1 30 to 60 0.4 to 0.6 </div>