CONVERSION OF METHANOL AND METHYL ETHER TO LIGHT OLEFINS

Abstract: A process is provided for converting a feedstock com­ prising methanol and/or methyl ether to product comprising light olefins over a catalyst comprising a synthetic porous crystalline zeolite material designated zeolite ZSM-45 in the presence of a diluent selected from water, hydrogen-­ containing gas, nitrogen, helium, carbon monoxide, carbon dioxide or mixtures of such diluents.

Description: CONVERSION OF METHANOL AND METHYL ETHER TO LIGHT OLEFINS This invention relates to an improved process for converting methanol and/or methyl ether to light olefins over particular types of crystalline aluminosilicate zeolite catalysts. A remarkable growth in the production of synthetic flowers, plastics and rubber has taken place in recent decades. Such growth, to a large extent, has been supported and encouraged by an expanding supply of inexpensive petroleum raw materials such as ethylene and propylene. However, increasing demand for these light olefins nas, from time to time, led to periods of shortage, either due t(3 a diminished supply of suitable feedstocks or to limited processing capacity. In any event, it is now considered highly desirable to provide efficient means for converting raw materials other than petroleum to light olefins. One such non-petroleum source of light olefins is coal-derived methanol and methyl etner. In tnis respect, it is known tnat methanol or methyl etner can be catalytically converted to olefin-containing hydrocarbon mixtures by contact under certain conditions with particular types of crystalline zeolite catalyst materials. U.S. Patent 4,025,575, issued May 24, 1977, to Chang et al and U.S. Patent 4,083,889, issued April 11, 1978 to Caesar et al, for example, both disclose processes whereby methanol and/or methyl ether can be converted to an olefin-containing product over a ZSM-5 type (constraint index 1-12) zeolite catalyst. ZSM-5, in fact, converts metnanol and/or methyl ether to hydrocarbons containing a relatively high concentration of light (C2 and r C3) olefins with prolonged catalyst lifetime before catalyst regeneration becomes necessary. It is also known that other types of zeolite catalysts can be used to convert methanol and/or methyl ether to olefin-containing hydrocarbon products containing even higher proportions of light olefins than can be realized by methanol/methyl ether conversion over ZSM-5. For example, U.S. Patents 4,079,095 and 4,079,096, botn issued March 14, 1978, to Givens, Plank and Rosinski, disclose that zeolites of the erionite-offretite type, and especially ZSM34, can usefully be employed to promote conversion of methanol and/or methyl ether to products comprising a major amount of C2 and C3 light olefins. However, while erionite-offretite type catalysts are highly selective to light olefins production, such smaller pore zeolites tend to age rapidly in comparison to ZSM-5 when used for methanol/methyl ether conversion. Thus in spite of the existence of methanol conversion processes utilizing a variety of zeolite catalysts, there is a continuing need to develop new procedures suitable for selectively converting an organic charge comprising methanol and/or methyl ether over zeolites catalysts to light olefin products with both high light olefin selectivity and prolonged catalyst lifetime. Accordingly, it is an object of the present invention to provide a process for converting methanol and/or methyl ether over a zeolite-based catalyst to olefin-containing products with high selectivity to production of light olefins. It is a further object of tne present invention to provide such a selective process wherein lifetime of the zeolite catalyst is enhanced for methanol/methyl ether conversion. It is a further object of the present invention to provide such a methanol/methyl ether conversion process employing a particular type of zeolite catalyst, readily available reactants and diluents and commercially practical reaction conditions. In accordance with the present invention, a process is provided for the catalytic conversion of an organic reactant feed comprising the organic reactants methanol and/or methyl ether to a hydrocarOon reaction product mixture containing light (C2-C4) olefins. The catalyst employed in such a process comprises at least some synthetic porous crystalline material designated as Zeolite ZSM-45. Zeolite ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zeolites, and this distinctive x-ray diffraction pattern for ZSM-45 is shown hereinafter. The porous crystalline Zeolite ZSM 45 can be further identified, in terms of mole ratios of oxides, by the following formula: M2/nO : A1203: x SiO2 wherein x is greater than 8, wherein M is an organic or metallic cation or is a combination of organic and metallic cations, and wherein n is the valence of each respective cation present. Methanol/methyl ether conversion over such a Zeolite ZSM-45-containing catalyst occurs by contacting the organic reactant feed with the zeolite-based catalyst under conversion reaction conditions which are sufficient to produce a light olefin-containing product enriched in C2-C4 olefins, particularly ethylene. Such contacting further occurs in the presence of a gaseous diluent which can be water, hydrogen-containing gas, nitrogen, helium, carbon monoxide, carbon dioxide, or a mixture of such diluents. In a highly preferred invention embodiment, the gaseous diluent comprises hydrogen-containing gas, e.g., hydrogen, which prolongs the lifetime of the zeolite catalyst in such a process. The term "organic reactant feed" as used herein can comprise both the organic material used as reactants, i.e. the organic compounds such as methanol and methyl ether subjected to catalytic conversion to olefins, as well as additional components such as water or other diluents as described more fully hereinafter. Since methanol is miscible with water, the charge to the catalytic reaction zone may actually contain relatively large amounts of water, but only the methanol, methyl ether and associated organic compounds, constitute the reactant portion of the organic reactant feed. Any methanol product comprising at least 60 wt. % of methanol may be used to provide methanol for the organic reactant feed in this invention. Substantially pure methanol, such as industrial grade anhydrous methanol, is eminently suitable. Crude methanol, wnich usually contains from 12 to 20 wt. % water, or more dilute solutions, also may be used. Small amounts of impurities such as higher alcohols, aldehydes, or other oxygenated compounds in the organic reactant feed have little effect on the conversion reaction of this invention. The organic reactant feed may also comprise methyl ether. When this component is present, it can comprise up to 100% of the organic reactant feed or methyl ether can be admixed with methanol and/or water to form the organic reactant feed. For purposes of the present invention, it is contemplated to directly convert methanol and/or methyl ether in the feed to a hydrocarbon mixture characterized by a high content of light olefins, especially ethylene. Such amounts of methyl ether as may be formed concomitantly in the conversion reaction, however, may be recovered and recycled with fresh organic reactant feed. The organic reactant feed as hereinbefore described is catalytically converted to a light olefin containing hydrocarbon product enriched in ethylene by contact with a zeolite-based catalyst composition comprising a particular type of synthetic porous crystalline zeolite material designated ZSM-45. The lattice of any crystalline zeolite, including the particular ZSM-45 of the present invention, can be described as a rigid three-dimentional framework of SiO4 and A104 in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by a cation, for example an alkali metal or alkaline earth metal cation. The ratio of cationic-valence/aluminum is thus unity. One cation may be exchanged for another in conventional manner. By means of such cation exchange it has been possible to vary the properties of a given zeolite. Since the cationic content of a zeolite may thus be regarded as ephemeral, the only significant term in its compositional formula is the ratio of lattice silicon to aluminum, usually expressed as silica/alumina ratio. The SiO2/A1203 ratio of a given zeolite is however often variable. For example, zeolite X can be synthesized with SiO2/A1203 ratios of from 2 to 3; zeolite Y, from 3 to about 6.. In some zeolites, the upper limit of the SiO2/A1203 patio is unbounded. ZSM-5 is one such example wherein the Si02Al203 ratio is at least 5 and up to infinity. U. S. Patent No. 3,941,871 discloses a zeolite made from a reaction mixture containing no added alumina and exhibiting the X-ray diffraction pattern of zeolite ZSM-5. U. S. Patent Nos. 4,061,724, 4,073,865 and 4,104,294 describe zeolites of similar alumina and metal content. Synthetic zeolites sometimes resemble naturally occurring zeolites. Zeolites ZSM-35 and ZSM-38 are, for instance, ferrierite-type zeolites. Zeolites ZK-20 (U. S. Patent No. 3,459,676) is described as being isostructural with the naturally occurring zeolite levynite. European Patent Application No. EP-A-40,016 describes synthetic zeolite Nu-3 which is of the levynite type. Zeolite ZSM-45 is a high silica form of a levynite family of materials which exhibits a composition and properties which distinguish it from natural levynite. Zeolite ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zeolites. It may be said to be levynite-type, however. ZSM-45 has the formula, on an anhydrous basis, in terms of mole ratios of oxides: M2/nO:Al 203:x six2 in which x is 8 or greater and M is an organic or metallic cation of valence n, which cation serves to balance the electrovalence of the tetrahedral aluminum atoms. Zeolite ZSM-45 has an X-ray diffraction pattern containing the following significant lines: Interplanar, D-Spacing (A) Relative Intensity, I/In 8.02 + 0.14 Strong-Very Strong 5.07 + 0.09 Medium-Strong 4.21 + 0.08 Medium-Strong 4.01 + 0.07 Strong-Very Strong 3.78 + 0.07 Medium-Strong 3.11 + 0.06 Medium-Strong 2.751 + 0.05 Medium Strong The derivation of such lines in the X-ray pattern is described more fully hereinafter. In the as-synthesised form, the zeolite ZSM-45 usually conforms to the formula, on an anhydrous basis and in terms of moles ratios of oxides: (0.8-l.8)0: (0.0-0. 3)Na20: (O.O-O.5)K20:A1203:xSi02 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl) trialkylammonium compound where alkyl is composed of one or two carbon atoms and x is greater than 8, usually from 8 to 100. In such an empirical formula for the as-synthesized zeolite, it is understood that there must always be sufficient R, Na and/or K cations to completely balance the electrovalence of the lattice aluminum. In those instances wherein greater amounts of R, Na and/or K are present than are necessary to balance the aluminum charge, the excess amount of R, Na and/or K is present in the zeolite in the form of occluded compounds formed from these cations. The as-synthesized form of ZSM-45 has the X-ray diffraction pattern of Table 1 hereinbelow. TABLE 1 InterplanarO D-Spacing ( ) Relative Intensity, I/Io 10.16 0.18 Weak 8.02 + 0.14 Strong-Very Strong 7.56 + 0.14 Weak 6.55 + 0.12 Medium-Very Strong 5.66 + 0.10 Weak 5.50 + 0.10 Weak 5.07 + 0.09 Medium-Strong 4.95 + 0.09 Weak 4.21 + 0.08 Medium-Strong 4.01 + 0.07 Strong-Very Strong 3.78 + 0.07 Medium-Strong 3.60 + 0.06 Weak 3.54 + 0.06 Weak-Medium 3.42 + 0.06 Weak 3.27 + 0.06 Medium 3.11 + 0.06 Medium-Strong 3.03 + 0.05 Weak 2.812 + 0.05 Weak 2.751 + 0.05 Medium-Strong 2.583 + 0.05 Weak 2.535 + 0.05 Weak 2.521 + 0.05 Weak 2.475 + 0.04 Weak 2.405 + 0.04 Weak 2.362 + 0.04 Weak 2.251 + 0.04 Weak 2.181 + 0.04 Weak 2.133 + 0.04 Weak 2.097 + 0.04 Weak 2.029 + 0.04 Weak 2.006 + 0.03 Weak 1.889 + 0.03 Weak 1.859 + 0.03 Weak 1.843 + 0.03 Weak 1.815 + 0.03 Weak 1.765 + 0.03 Weak 1.721 + 0.03 Weak 1.710 + 0.03 Weak 1.650 + 0.03 Weak 1.637 0.03 Weak 1.617 0.03 Weak 1.606 0.03 Weak 1.559 0.03 Weak These values were determined by standard techniques. The radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used. Tne 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 d (obs.) the interplanar spacing in Angstrom units (it), corresponding to the recorded lines, were determined. In Table 1, the relative intensities are given in terms of tne strongest line being taken as 100.0. It should be understood that this X-ray diffraction pattern is characteristic of all the species of Zeolite ZSM-45 compositions. The sodium form as well as other cationic forms reveal substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur, depending on the silicon to aluminum ratio of the particular sample, as well as its degree of thermal and/or steam treatment. The Zeolite ZSM-45 used herein sorbs significant amounts of commonly used test adsorbate materials, i.e. cyclohexane, n-hexane and water, whereas naturally occurring levynite is not expected to adsorb cyclohexane due to its pore structure. Sorption capacities for Zeolite ZSM-45 will range at room temperature as follows: Adsorbate Capacity, Wt. Percent Cyclohexane 2.2 - 7.0 n-Hexane 7.3 - 12.9 Water 14.5 - 22.9 The original organic and alkali metal cations of the as-synthesized ZSM-45 can be replaced at least in part in accordance with techniques well known in the art, with other cations. Such techniques include thermal treatment and ion exchange. Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof. Particularly preferred cations are those wnicn render the ZSM-45 catalytically active for methanol conversion. These include nydrogen, ammonium, rare earth metals and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of tne Periodic Chart of the Elements. Tne Zeolite ZSM-45 is preferably employed in the methanol conversion process herein in either the ammonium or hydrogen form. The ZSM-45 zeolite may also be utilized in a form wherein some of the active sites have been exchanged with alkali metal, alkaline earth metal or other metal cations. However, the zeolite must contain some acid sites to be effectively utilized in the process of the present invention. Thermal treatment of the as-synthesized zeolite is generally employed to remove all or part of the organic constituent. Such thermal treatment can for example be conducted at temperatures in excess of 2500C for a period of time sufficient to remove the organic constituent to the desired extent. Following thermal treatment the zeolite can then be subjected to ion exchange. A typical ion exchange technique would be to contact the synthetic ZSM-45 with a salt of tne desired replacing cation or cations. Examples of such salts include the halides, e.g. chlorides, nitrates and sulfates. The Zeolite ZSM-45 useful in the methanol/methyl ether conversion process herein can advantageously be dehydrated, at least partially, prior to use. This can be done by heating the zeolite to a temperature in the range of 2000C to 5950C in an inert atmosphere, such as air, nitrogen, etc. and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing ZSM-45 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration. The Zeolite ZSM-45 for use in the present process can be prepared from a reaction mixture containing sources of alkali metal ions (K and Na), an oxide of aluminum, an oxide of silicon, an organic cation (R) derived from a 2-(hydroxyalkyl)trialkylammonium compound wherein alkyl is composed of of one or two carbon atoms and water and having a composition, in terms of mole ratios of oxides and cations, falling within the following ranges: Reactants Useful Preferred SiO2/A1203 10-150 15-80 OH-/SiO2 0.3-1.0 0.3-0.8 H2O/OH- 20-100 20-80 R/R+(K + Na) 0.1-0.8 0.2-0.7 K/K+Na 0.0-0.8 0.05-0.3 wherein R is as above defined. Crystallization of the Zeolite ZSM-45 can be carried out at either static or stirred condition in a suitable reactor vessel, sucn as for example, polypropylene jars or teflon lined or stainless steel autoclaves. A useful range of temperatures for crystallization is from about 800C to about 3500C for a time of about 12 hours to abQut 200 days. Thereafter, the crystals can be separated from the liquid and recovered. The composition can be prepared utilizing materials which supply the appropriate oxides. Such compositions may include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, a source of aluminum, and an appropriate organic compound. It should De realized that the reaction mixture component oxides can be supplied from more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the crystalline Zeolite ZSM-45 will vary with the nature of the reaction mixture employed and the crystallization conditions. In all cases, synthesis of the ZSM-45 crystals is facilitated by the presence of at least 0.01 %, preferably 0.10 % and still more preferably 1 %, seed crystals (based on total weight) of crystalline product. The 2-(hydroxyalkyl)trialkylammonium compound may be the hydroxide or halide, e.g. chloride, iodide or bromide. When the compound is 2-(hydroxyethyl)trimethylammonium chloride, it is called choline chloride, a preferred source of organic cations (R) in the synthesis of Zeolite ZSM-45. Tne ZSM-45 crystals so prepared can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded. It may be desirable to incorporate the Zeolite ZSM-45 with another material resistant to the temperatures and other conditions employed in the methanol/methyl ether conversion process embodiments of the present invention. Such materials include active and inactive material and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material which is active in conjunction with the ZSM-45 crystal, i.e. combined therewith, may improve the conversion and/or selectivity of the catalyst in certain methanol conversion process embodiments. 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 of reaction. These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst composite having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst. Naturally occurring clays which can be composited with the ZSM-45 crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, 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. Binders useful for compositing with the ZSM-45 crystal also include inorganic oxides, notably alumina. In addition to the foregoing materials, the zeolite ZSM-45 can be composited with a porous matrix material such as silicaalumina, silica-magnesia, silica-zirconia, silica-thoria, silicaberyllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the zeolite content ranging from about 1 to about 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight % of the composite. As noted, the ZSM-45 zeolite containing catalyst compositions as hereinbefore described are especially useful for the selective conversion of methanol and/or methyl ether to a light olefin (C2-C4)-containing hydrocarbon product particularly enriched in ethylene. By utilizing a selected combination of the particular ZSM-45 based catalyst along with particular methanol/methyl ether conversion reaction conditions including the presence of certain gaseous diluents, methanol/methyl ether conversion processes can be realized which are more selective to light olefin production tnan are similar processes employing other types of zeolite catalysts. Processes utilizing these particular ZSM-45 based catalysts and certain reaction conditions are also more resistant to catalyst aging or provide enhanced conversion of methanol and/or methyl ether-containing feed to olefins in comparison with other known zeolite-catalyzed methanol/methyl ether conversion processes. Tne process of the present invention can, in fact, yield a light olefin-containing product wherein ethylene is the major light olefin produced. In accordance with the present process invention, a chargestock comprising methanol (methyl alcohol), methyl ether, methanol/methyl ether mixtures can be contacted in the vapor phase with the ZSM-45-based catalyst materials hereinbefore described in a reaction zone in the presence of a gaseous diluent and under reaction conditions suitable for effecting conversion of methanol and/or methyl ether to olefins. Such conditions include an operating temperature between about 260 C (¯500 F) and 540 C (¯1000 F), preferably 300 C and 450 C; a pressure between about 104 Pa (0.1 atmosphere) and 3.0 x 106 Pa (300 atmospheres) preferably 5.0 x 105 Pa and 106 Pa; and a weight hourly space velocity (wHSV) of the organic reactants between about 0.1 and 30, preferably 1 and 10. The gaseous diluent is introduced into the reaction zone along with the organic oxygenate reactant. Such diluents include, for example, hydrogen-containing gas, nitrogen, helium, water, carbon monoxide, carbon dioxide, or mixtures of these gases. Preferred diluents are water and/or hydrogen. The gaseous diluent can be co-fed to the reaction zone using a weight hourly space velocity (WHSV) of from about 0.003 to 20, preferably from about 0.01 to 10. Generally the molar ratio of gaseous diluent to the organic reactants ranges from about 0.05:1 to 40:1, more preferably from about 0.1:1 to 20:1. Water (steam) is an especially useful diluent. Selectivity of the methanol conversion reaction for production of light (C2-C4) olefins can be improved for example by contacting the feedstock with the hereinbefore described zeolite based catalyst in the presence of up to about 20 moles, and preferably from about 1 to 10 moles of steam per mole of organic reactant. Such steam contact is made in the reaction zone under the methanol/methyl ether conversion conditions hereinbefore described. Such steam may be provided directly by injecting the requisite amount of water or steam into the reaction zone. Alternatively, steam may be provided totally or in part by water present in the feedstock in a molar ratio of water to organic reactants of up to about 20:1, preferably from about 1:1 to about 10:1. Such water in tne feedstock to the reaction zone, of course, forms steam in the reaction zone under the conversion conditions of the present invention. Steam can thus be passed to the reaction zone with a WHSV of from about 1 to 20, more preferably of from about 2 to 10. Another especially preferred gaseous diluent is a hydrogen-containing gas which provides a reducing atmosphere in the methanol converSion reaction zone. Such a hydrogen-containing gas can be selected from substantially pure hydrogen and mixtures of hydrogen and carbon monoxide such as are found in synthesis gas. Whatever the nature of particular hydrogen-containing gaseous diluent utilized, it has been found that hydrogen-containing gaseous diluents of the type described herein can usefully be employed to prolong the lifetime and selectivity of the ZSM-45 zeolite Dased methanol/methyl ether conversion catalyst when such catalysts and diluents are employed under reaction conditions suitable for the selective conversion of methanol/methyl ether to light olefins. Oonversion reaction conditions, as well as the nature of the particular catalyst composition and diluent employed, can affect the selectivity of the present methanol/methyl ether conversion process to light olefin and ethylene production as well as percent conversion of organic reactants to hydrocarbon product and can also affect catalyst aging characteristics. However, it has been discovered that for a given set of reaction conditions the ZSM-45 based catalyst used in the present invention, and especially a ZSM-45 based catalyst used in comoination with a hydrogen-containing gaseous diluent, will generally provide improved methanol conversion, light olefin selectivity and/or catalyst aging performance in comparison with similar prior art processes employing either other zeolites or diluent-free reaction conditions. It should be noted that "catalyst lifetime" as used herein refers to the length of time on stream during which a catalyst can be employed before catalytic activity drops to a level such that catalyst regeneration becomes commercially desiraole or necessary. A convenient measurement of catalyst lifetime would be the length of time a catalyst can be employed in the process of the present invention before methanol/methyl ether conversion in the process drops from its initial value to an arbitrarily set lower conversion value, e.g., 50S conversion. For purposes of tne present invention, ennanced catalyst lifetime refers to tne extension of the catalyst lifetime which can be realized with a process using the ZSM-45 gaseous diluent combination in comparison with prior art methanol/methyl ether conversion processes wherein this particular zeolite/diluent combination is not employed. The methanol and/or methyl ether conversion process described herein may be carried out as a batch-type, semi-continuous or continuous operation utilizing a fixed, fluidized or moving bed catalyst system. A preferred embodiment entails use of a catalyst zone wherein the alcohol or ether charge optionally together with added water is passed concurrently or countercurrently through a fluidized or moving bed of particle-form catalyst. The latter after use may be conducted to a regeneration zone wherein catalyst can be regenerated by any of the conventional regeneration methods known to the art and thereafter recycled to the conversion zone for further contact with the methanol and/or ether containing feed. The product stream in the process of the invention contains steam and a hydrocarbon mixture of paraffins and olefins, which mixture can be substantially devoid of aromatics. As noted, the mixture is particularly rich in light olefins, and especially rich in ethylene. Thus, the predominant hydrocarbon product constitutes valuable petrochemicals. The steam and hydrocarbon products may be separated from one another by methods well known in the art. In a preferred embodiment ef the invention, the unconverted methanol and/or methyl ether, as well as at least part of the water in the product, can be recycled to the reaction zone. In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented. In the examples, whenever adsorption data are set forth for comparison of sorptive capacities of ZSM-45 for water, cyclohexane and/or n-hexane, they were determined as follows: A weighed sample of the calcined ZSM-45 adsorbant was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to less than 133.22 Pa (1 mm Hg) and contacted with 1600 Pa (12 mm Hg) of water vapor or 2666.55 Pa (20 mm Hg) of n-hexane, or cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at room temperature. The pressure was kept constant (within about + 66.66 Pa) Dy 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 zeolite crystal, the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was caleulated as the adsorption capacity of the sample in 9/lOO g of calcined adsorbant. When Alpha Value for tne ZSM-45 zeolite is determined, it is noted that the Alpha Value is an approximate indication of the catalytic activity, e.g., cracking activity, of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). It is based on the activity of tne highly active silica-alumina cracking catalyst taken as an Alpha Value of 1 (Rate Constant = 0.016 sex ). The Alpha Test is described in U.S. Patent 3,354,078 and in The Journal of Catalysis, Vol. IV, pp. 522-529 (August 1965). EXAMPLE 1 Three separate components were prepared to comprise ingredients as follows: A. 15.45 grams of A12(504)3 18H20 3.48 grams of H2S04 90.2 grams of H20 8. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent SiO2, 8.8 wt. percent Na2O and 62.7 wt. percent H20) 2.0 grams of 86.4 wt. percent KOH 11.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 990C over 197 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be about 90 percent zeolite ZSM-45 plus about 10 percent unidentified impurities. The complete X-ray pattern data for this zeolite is presented in Table 2, hereinafter. Chemical analysis of the zeolite product of this example proved it to have the following composition: Component Wt. Percent N 2.07 Na 0.28 K 0.35 Awl203 7.40 Six2 89.90 Ash 80.50 SiO2/A12'03, molar 20.7 Sorption capacities of the zeolite product of this example, calcined at 5380C, were: Adsorbate Capacity, Wt. Percent Cyclohexane, 20 Torr (2666.44Pa) 3.5 n-Hexane, 20 Torr (2666.44 Pa) 12.9 Water, 12 Torr (1600 Pa) 18.3 The surface area of tne zeolite ZSM-45 product of this example was measured to be 514 m2/gram. TABLE 2 Degrees Interplanart Relative Intensity, Two Theta D-Spacing (A) I/Ic-- 7.72 11.45 6 8.60 10.28 13 10.91 8.11 50 11.45 7.73 3 11.65 7.60 6 13.41 6.60 36 15.60 5.68 6 16.00 5.54 9 17.38 5.10 81 17.84 4.97 12 20.98 4.23 51 22.08 4.03 100 23.44 3.80 45 25.05 3.55 13 25.53 3.49 5 25.94 3.43 5 27.12 3.29 20 28.53 3.13 47 29.38 3.04 6 31.70 2.823 8 32.45 2.759 40 34.57 2.595 10 35.25 2.546 2 35.46 2.531 2 38.08 2.363 2 38.41 2.344 1 39.80 2.265 3 40.50 2.227 1 41.25 2.189 3 42.23 2.140 3 43.00 ' 2.103 8 44.52 2.035 2 45.10 2.010 4 46.89 1.938 1 47.32 1.921 1 48.02 1.895 6 48.90 1.863 6 49.40 1.845 3 50.10 1.821 7 51.61 1.771 12 52.42 1.745 1 53.00 1.728 2 53.50 1.713 1 54.10 1.695 1 55.00 1.670 1 55.58 1.653 3 56.=02 1.642 8 56.82 1.620 3 57.35 1.607 2 59.15 1.562 5 EXAMPLE 2 About 10 grays of the zeolite ZSM-45 product of Example 1 was calcined in air at 5380C for 10 hours and then contacted with 10 cc/gram zeolite of 5 percent ammonium chloride solution at 85OC five separate times. The resulting zeolite was then dried at about 1100C and calcined at 5380C for 10 nours in air. It was then submitted for evaluation in the Alpha Test, described hereinbefore. Its Alpha Value proved to be 14. EXAMPLE 3 Three separate components were prepared to comprise ingredients as follows: A. 15.45 grams of A12(S04)3 18H20 3.48 grams of H2S04 90.2 grams of H20 B. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent SiO2, 8.8 wt. percent Na2O and 62.7 wt. percent H20) 2.0 grams of 86.4 wt. percent KOH 50.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and component A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 990C over 152 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be zeolite ZSM-45. Chemical analysis of the zeolite product of this example proved it to have the following composition: Component Wt. Percent N 2.25 Na 0.43 K 0.25 A1203 7.60 SiO2 89.00 Ash 78.90 Sorption capacities of the zeolite product of this example, calcined at 5380C, were: Adsorbate Capacity, Wt. Percent Cyclohexane, 20 Torr (2666.44 Pa) 3.8 n-Hexane, 20 Torr (2666.44 Pa) 11.3 Water, 12 Torr (1600 Pa) 16.2 Tne surface area of the zeolite product of this example was measured to be 467 m2/gram. EXAMPLE 4 About 10 grams of the zeolite ZSM-45 product of Example 3 was calcined in air at 5380C for 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 2. It was then submitted for evaluation in the Alpha Test. Its Alpha Value proved to be 6. EXAMPLE 5 Three separate components were prepared to comprise ingredients as follows: A. 28.7 grams of sodium aluminate 36.0 grams of NaOH 10.0 grams of 85 wt. percent KOH 450.0 grams of H20 B. 650.0 grams of colloidal silica (30 wt. percent) C. 190.0 grams of choline chloride Component C was added to component A and component B was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at l210C over 21 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be about 85 percent zeolite ZSM-45 plus about 15 percent unidentified impurities. The complete X-ray pattern data for this zeolite is presented in Table 3, hereinafter. TABLE 3 Degrees InterplanarO Relative Intensity, Two Theta D-Spacing (A) I/Io 7.78 11.36 14 8.67 10.20 11 11.00 8.04 37 11.69 7.57 8 12.60 7.03 4 13.15 6.73 8 13.49 6.60 37 15.55 5.70 6 16.05 5.52 9 17.45 5.08 65 17.88 4.96 20 19.45 4.56 6 20.72 4.29 20 21.07 4.22 47 22.12 4.02 100 23.49 3.79 62 25.14 3.54 38 25.91 3.44 18 26.90 3.31 10 27.19 3.28 27 28.35 3.15 13 28.63 3.12 40 29.40 3.04 7 31.54 2.84 11 31.75 2.819 10 32.51 2.754 35 34.65 2.589 6 35.50 2.529 2 36.25 2.478 5 38.10 2.362 3 39.80 2.265 2 41.25 2.189 2 42.28 2.138 3 43.05 2.101 7 45.17 2.007 3 48.11 1.891 5 48.90 1.863 4 49.45 1.843 3 50.19 1.817 6 51.74 1.767 11 52.94 1.730 1 55.68 1.651 4 56.15 1.638 6 56.94 1.617 1 59.26 1.559 3 Chemical analysis of the zeolite product of this example proved it to have the following composition: : Component Wt. Percent N 2.34 Na 0.49 K 0.58 A1203 6.90 SiO2 72.60 Ash 81.50 Sorption capacities of the zeolite product of this example, calcined at 5380C, were: Adsorbate Capacity, Wt. Percent Cyclohexane, 20 Torr (2666.44 Pa) 5.0 n-Hexane, 20 Torr (2666.44 Pa) 11.0 Water, 12 Torr (1600 Pa) 14.5 The surface area of tne zeolite product of this example was measured to be 484 m2/gram. EXAMPLE 6 About 10 grams of the zeolite ZSM-45 product of Example 5 was calcined in air at 5380C for 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 4. It was then submitted for evaluation in the Alpha Test. Its Alpha Value proved to be 27. EXAMPLE 7 Three separate components were prepared to comprise ingredients as follows: A. 23.2 grams of Al2(S04)3 18H20 5.2 grams of H2504 135 grams of H20 B. 203.1 grams of Q-Brand sodium silicate (28.5 wt. percent SiO2, 8.8 wt. percent Na2O and 62.7 wt. percent H20) 3.0 grams of 86.4 wt. percent KOH 75.0 grams of H20 C. 57.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 1000C over 151 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to oe 100 percent zeolite ZSM-45. The complete X-ray pattern data for this zeolite is presented in Table 4, hereinafter. TABLE 4 Degrees Interplanar. Relative Intensity, Two Theta D-Spacing (A) I/Ic--, 7.77 11.38 4 8.71 10.15 10 11.04 8.02 45 11.71 7.56 6 13.52 6.55 36 15.67 5.66 2 16.11 5.50 10 17.49 5.07 76 17.93 4.95 13 19.57 4.54 4 21.10 4.21 50 22.18 4.01 . . 100 23.54 3.78 47 23.80 3.74 8 25.16 3.54 15 26.08 3.42 5 27.24 3.27 24 28.67 3.11 44 29.46 3.03 7 31.84 2.810 7 32.55 2.750 38 34.72 2.584 9 35.42 2.534 3 35.62 2.520 2 36.28 2.476 5 37.42 2.403 2 38.22 2.355 1 38.48 2.339 1 39.95 2.257 2 40.50 2.227 2 41.36 2.183 3 42.40 2.132 3 43.12 2.098 7 44.70 2.027 6 45.22 2.005 4 47.35 1.920 2 48.16 1.889 5 49.03 1.858 4 49.50 1.841 3 50.23 1.816 6 51.76 1.766 11 53.01 1.727 2 53.75 1.705 2 55.68 1.651 3 56.15 1.638 6 56.99 1.616 2 57.39 1.605 1 59.30 1.558 4 Chemical analysis of the zeolite product of this example proved it to have the following composition: Component Wt. Percent N 2.26 Na 0.37 K 0.79 A1203 7.48 SiO2 85.8 Ash 82.8 SiO2/A1203, molar 19.5 Sorption capacities of the zeolite product of this example, calcined at 5380C, were: Adsorbate Capacity, Wt. Percent Cyclohexane, 20 Torr (2666.44 Pa) 3.4 n-Hexane, 20 Torr (2666.44 Pa) 12.9 Water, 12 Torr (1600 Pa) 21.1 The surface area of the zeolite product of this example was measured to be 471 m2/gram. EXAMPLE 8 Two grams of zeolite ZSM-45 product of Example 2 were dried by heating for 1 hour in air flowing at 10 cc/hour at 5380C. The zeolite was mixed with an equal volume of quartz chips (both 14/25 mesh) and the mixture placed in a quartz microreactor equipped with a thermocouple. The reactor was then flushed with air at 10 cc/minute for 105 minutes at 5380C. The air flow was replaced with helium flow at 10 cc/minute while the reactor temperature was reduced to about 3710C. Feedstock composed of 30 wt. % methanol and 70 wt. % water was then passed into the reactor at 3.4 cc/hour for 2 hours at atmospheric pressure. The weight hourly space velocity was 2.8 her 1 and the temperature was maintained at about 371oC. Product collected from the reactor was analyzed for chemical composition. Conversion of methanol was indicated to be 87 wt. %. The product hydrocarbon content comprised 39 wt. % ethylene and 16 wt. S C5 + components. EXAMPLE 9 Two grams of zeolite ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in the microreactor, air flushed and helium flushed as in Example 8. With the reactor temperature maintained at about 3710C and the pressure at atmospheric, feedstock comprising 30 wt. % methanol and 7Q wt. % water was passed into the reactor at a WHSV of 2.4 her 1. The molar ratio of water/methanol in the feedstock was 4/1. Product was collected and analyzed. Conversion of methanol proved to be 46 wt. %. Product hydrocarDon content comprised 44 wt. % ethylene and nil C5 components. EXAMPLE 10 In this example, two grams of zeolite ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in tne microreactor, air and helium flushed as in Example 9. With the reactor maintained at from about 3710C to about 3790C and the pressure at atmospheric, feedstock of 100% methanol was passed into the reactor -1 at a WHSV of 2.4 hr 1. Product was collected and analyzed, showing 79.7 wt. % conversion of methanol to product hydrocarbons comprising: Component Wt. % Ethylene 16.91 Propylene 39.46 Isobutane 11.68 Butylene 22.55 C5 Hydrocarbons 9.40 EXAMPLE 11 A ZSM-45 sample, prepared in the general manner described in Examples 1 and 2, is used in its ammonium exchanged form to convert methanol to hydrocarbons in the general manner of Examples 8, 9 and 10. The ZSM-45 used in such conversion has a silica/alumina ratio of about 26 and the following sorption capacity and alkali metal content: Cyclohexane, wt. %: 3.5 n-Hexane, wt. %: 11.2 H20, wt. %: 18.0 Residual Na, wt. %: 0.28 Residual K, wt. B: 0.1 In such a procedure, 2 grams of zeolite (no binder) and 4 grams of quartz chips, both of 14/20 mesh size, are mixed and packed into a stainless steel microreactor, equipped with thermocouple. Methanol is fed to the reactor under hydrogen pressure under varying reaction conditions for a period of up to 177 hours. Pressure during the run is maintained at 963 kPa (125 psi.) A WHSV for methanol of 0.4 is used. Data points are taken at various times during the run. The total reactor effluent is analyzed, on line, by gas chromatography. Methanol conversion is calculated based on nydrocarbon formation only. Selectivities (wt. %) to hydrocarbon product are calculated on "coke free" basis. A catalyst aging rate defined as the amount of change in percent methanol conversion to hydrocarbon per hour is also computed. Reaction conditions, as well as methanol conversion results for this run, are set forth in Table 5. TABLE 5 Methanol Conversion to Light Olefins Over Zeolite ZSM-45 Run No. 1 2 3 4 5 6 7 Time on Stream, hours 1-22 22-29 29-49 49-55 55-70 70-95 95-177 Temperature, OC 350-372 391 400 400 402 402 402 H2/MeOH molar ratio 10 10 10 4 4 1.5 Percent Conversion 22 76 96 95 98 82 61 Product Selectivity (wt.%) C2H4 35.8 58.2 , 57.2 54.8 49.9 51.4 46.2 C3H6 21.8 16.1 15.2 21.0 23.0 28.0 28.7 C2H4-C4H8 64.6 75.4 73.2 77.3 75.0 81.8 78.2 CH4-C3H8 29.4 23.8 26.3 22.3 24.3 17.4 20.3 Aging Rate, Percent - 0 0 0.34 0 0.63 0.24 Per Hour The Table 5 data indicate that for a molar ratio of H2/MeOH of 10 and at 4000C, methanol conversion results of about 95% can be achieved. Selectivities to ethylene and total light olefins are greater than 55% and 75%, respectively, under these conditions. When the molar ratio of H2/MeOH was lowered to 1 (Run No. 7), the catalyst maintains its activity and selectivities for more than 80 hours. During this period, the ethylene selectivity ranges from 40-50%. Total light olefin selectivity is greater than 75S. The aging rate for methanol conversion under this condition is only 0.24% per hour. Such results clearly show the effectiveness of Zeolite ZSM-45 under hydrogen pressure in promoting the selective conversion of methanol to a hydrocarbon product enriched in light olefins.

Claims: CLAIMS: 1. A process for converting an organic reactant feed comprising the organic reactants methanol, methyl zither or mixtures thereof to a C2-C4 olefin-containing nydrocarbon reaction product, said process comprising contacting said organic reactant feed in a reaction zone under methanol or methyl ether conversion reaction conditions with a zeolite-based catalyst composition comprising a synthetic porous crystalline zeolite designated ZSM-45, said zeolite naving the formula, on an anhydrous basis and in terms of mole ratio of oxides: M2,nO:A1203: x SiO2 wnerein x is greater than 8, wherein M is an organic or metallic cation or is a comoination of organic and metallic cations and wherein n is the valence of each respective cation present, and having an X-ray powder diffraction pattern containing the following significant lines: Interplanar D-Spacing (A) Relative Intensity, I/Io 8.02 + 0.14 Strong-Very Strong 5.07 + 0.09 Medium-Strong 4.21 + 0.08 Medium-Strong 4.01 + 0.07 Strong-Very Strong 3.78 + 0.07 Medium-Strong 3.11 + 0.06 Medium-Strong 2.751 + 0.05 Medium Strong said contacting of organic reactant feed with said catalyst occurring in the presence of a gaseous diluent selected from water, hydrogen-containing gas, nitrogen, helium, carbon monoxide, carton dioxide and mixtures of said diluents. 2. A process according to Claim 1 wherein, in the catalyst composition, the ZSM-45 zeolite component, in its as-syntnesized form, has a composition on an anhydrous basis and in terms of moles of oxides per mole of alumina, expressed by the formula: (0.8-1.8)R20:(0.3-0.3)Na20:tO.0-0.5)K20:A1203:xSiO2 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl) trialkylammonium compound where alKyl is composed of one or two carbon atoms and x is greater than 8, said ZSM-45 zeolite being further characterized by an X-ray diffraction pattern exnioiting values substantially as set forth in Taole 1 of the specification. 3. A process according to Claim 1 or Claim 2 wherein, in the formula for the zeolite, x is from greater than 8 to 100. 4. A process according to Claim 2 or Claim 3 wherein, in the formula for the zeolite, R is an organic cation derived from choline chloride. 5. A process according to any of Claims 2 to 4 wherein said catalyst composition comprises the product of thermal treatment of the as-synthesized zeolite ZSM-45. 6. A process according to any of Claims 1 to 5 wherein said catalyst comprises zeolite ZSM-45 naving its original cations replaced, at least in part, with a cation or a mixture of cations selected from hydrogen, ammonium, rare earth metals, and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of tne Periodic Table of the Elements. 7. A process according to any of Claims 1 to 6 wherein the gaseous diluent is co-fed to the reaction zone with the organic reactants using a weight hourly space velocity for the diluant of from 0.003 to 20 at a molar ratio of gaseous diluent to organic reactants of from 0.05:1 to 40:1. 8. A process according to any of Claims 1 to 7 wherein the gaseous diluent is selected from hydrogen, water and combinations of hydrogen and water. 9. A process according to any of Claims 1 to 8 wherein a water diluent is co-fed to the reaction zone oy utilizing an organic reactant feed comprising a methanol-water mixture. 10. A process according to any of Claims 1 to 9 wherein said conversion reaction conditions include a temperature from about 275or to about 6000C, a pressure from 104 Pa to 3 x 106 Pa and a weight hourly space velocity of organic components of said feedstocK from about 0.1 her 1 to about 30 her 1 11. A process according to any of Claims 1 to 10 wnerein said catalyst composition additionally comprises a binder for said ZSM,45 zeolite. 12. A process according to any of Claims 1 to 11 wherein the zeolite ZSM-45 component of said catalyst composition has a cyclohexane sorption capacity of 2.2 to 7.0 weight percent at 2666.44 Pa.

Inventors: MAY-SOM WU, MARGARET, ROSINSKI, EDWARD JOSEPH, RUBIN, MAE KOENIG
Applicants: MOBIL OIL CORPORATION
Application year: 1983
Main classification: C07C1
IPC codes: B01J29, C07C1