A METHOD FOR PRODUCING OLEFINS AND/OR ETHERS OF HIGH OCTANE NUMBER

Abstract: A wide olefinic C₂ to C₁₀ stream is restructured over a special zeolite catalyst to form primarily C₄ to C₇ olefins, the C₄ to C₇ isoolefins are reacted with methanol over an acid catal­ yst to form high octane ethers, and unreacted olefins and methanol separated from the ether product are recycled to the olefin restructuring operation.

Description: Conversion of olefins to MTBE and TAME There are several unit processes in a petroleum refinery which produce, by design or inherently, a mixture of gaseous and liquid olefins, for example C2 plus olefins and particularly a mixture of C2 to ClO olefins. These olefinic products may comprise some paraffinic components mixed therewith. The prior art is replete with processes for converting such olefinic products before and after separation of paraffinic components from olefinic components. For example, components of these olefinic materials may be subjected to alkylation, polymerization, oligomerization, dimerization and aromatization. U.S. Patent 3,760,002 discloses the aromatization of feedstocks comprising C2 to C4 paraffins and olefins with a crystalline zeolite having the characteristics of ZSM-5 crystalline zeolite. U.S. Patent 3,756,942 discloses the conversion of feedstock boiling in the range of C5 hydrocarbons up to about 2500F (1210C) over a ZSM-5 crystalline zeolite to form aromatics. U.S. Patent 3,960,978 discloses the conversion of C2 to C5 olefins, alone or in admixture with paraffins, into an olefinic gasoline by passage over a ZSM-5 crystalline zeolite of controlled acidity. In this patented process, the crystalline zeolite alpha (CC) value is maintained within the range of 0.1 to about 120, the hydrocarbon partial pressure is within the range of 0.5 to 40 atmospheres using a temperature within the range of 500"F (2600C) to 9000F (4820C) to produce oligomers of the olefin feed and comprising Cg product material. The present invention is concerned with producing high octane ethers TAME and MTBE for admixture with gasoline from a mixture of olefins and particularly a mixture of C2 to ClO olefins under particularly selected conditions in the presence of catalyst suitable for the purpose. The novel processing combination of the present invention departs significantly from the prior art and initially involves a particular restructuring or rearrangement of the wide olefin composition stream (C2 to C10 olefins) available as charge to provide high yields of tertiary C4 and C5 olefin components. Conversion of the C2 to C1O olefin charge involves a combination of operations including cracking, polymerization or dimerization and modification of the olefin feed chain length to provide a product composition other than multiples of carbon atomchain growth of the individual olefins in the feed such as is normally obtained by polymerization and/or dimerization. For lack of better identification, applicants refer to the reactions encountered in the initial olefin restructuring operation as one of olefination. The restructuring of the broad carbon chain olefin charge stream according to this invention produces a mixture of C4 to C7 olefins, preferentially with the major portion being C4 and C5 olefins comprising a high percentage of tertiary olefins such as isobutylene and isoamylenes and less than 15% by weight of Cg and higher boiling olefins. The initial olefin conversion or olefination step is therefore carried out under conditions to particularly produce high yields of isobutylene and tertiary isopentenes, which materials are thereafter converted to desired C4 and C5 high octane methyl ethers. It is known that isobutylene may be reacted with methanol over an acidic catalyst to produce methyl tertiary butyl ether (MTBE) and isoamylenes may be reacted with methanol over an acidic catalyst to produce tertiary amyl methyl ether (TAME). The catalyst employed is preferably an ion exchange resin in the hydrogen form. Substantially any acidic catalyst may be employed with varying degrees of success. That is, acidic solid catalyst may be used such as sulfonic resins, phosphoric acid modified kieselguhr, silica alumina and acid zeolites. In the olefination restructuring operation of this invention, the mixture of C2 to C10 olefins is converted in the presence of a diluent material such as hydrogen or nitrogen and in the amount sufficient to reduce the partial pressure of the olefinic feed below atmospheric pressure and preferably to a pressure of at least about 4 psia (0.27 atm) and as low as about 1 psia (0.07 atm). The olefin feed of reduced pressure is contacted at a temperature within the range of 4000F (2040C) to 6000F (3160C) with an acid crystalline zeolite of the class of crystalline zeolites represented by ZSM-5 and characterized by having a silica to alumina ratio of at least 12 and a pore opening of at least 5 Angstroms. This special class of zeolite is capable of sorbing paraffins having a single methyl branch as well as normal paraffins and is identified as having a constraint index within the range of 1 to 12. The olefin restructuring operation of the present invention is preferably effected at a temperature within the range of 4500F (2320C) to 5500F (2880C) and an olefin pressure within the range of 1 (0.07 atm) to 7 psia (.48 atm). A WHSV (weight hourly space velocity) of the olefin feed is maintained within the range of 0.2 to 5. The olefin partial pressure is more particularly maintained less than 0.5 atmosphere and preferably less than about 0.3 atmosphere. The acid crystalline zeolite olefin restructuring catalyst may be combined with a binder, for example, to form an extrudate which is used more preferably at a temperature within the range of 5000F (2600C) to 5500F (2880C) for conversion to high yields of isobutylene and tertiary isopentenes. The crystalline aluminosilicates herein referred to, also known as zeolites, constitute an unusual class of natural and synthetic minerals. They are characterized by having a rigid crystalline framework structure composed of an assembly of silicon and aluminum atoms, each surrounded by a tetrahedron of shared oxygen atoms, and a precisely defined pore structure. Exchangeable cations are present in the pores. The catalysts referred to herein utilize members of a special class of zeolites exhibiting some unusual properties. These zeolites can induce profound transformations of aliphatic hydrocarbons to aromatic hydrocarbons in commercially desirable yields and are generally highly effective in alkylation, isomerization, disproportionation and other reactions involving aromatic hydrocarbons. Although they may have unusually low alumina contents, i.e. high silica to alumina ratios, they are very active even with silica to alumina ratios exceeding 30. This activity is surprising, since catalytic activity of zeolites is generally attributed to framework aluminum atoms and cations associated with these aluminum atoms. These zeolites retain their crystallinity for long periods in spite of the presence of steam even at high temperatures which induce irreversible collapse of the crystal framework of other zeolites, e.g. of the.X and A type. Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temperatures to restore activity. In many environments the zeolites of this class exhibit very low coke forming capability, conducive to very long times on stream between burning regenerations. An important characteristic of the crystal structure of this class of zeolites is that it provides constrained access to, and egress from, the intracrysta-lline free space by virtue of having a pore dimension greater than about 5 Angstroms and pore windows of about a size such as would be provided by l0-membered rings of oxygen atoms. It is to be understood, of course, that these rings are those formed by the regular disposition of the tetrahedra making up the anionic framework of the crystalline aluminosilicate, the oxygen atoms themselves being bonded to the silicon or aluminum atoms at the centers of the tetrahedra. Briefly, the preferred zeolites useful this invention possess, in combination: a silica to alumina ratio of at least about 12; and a structure providing constrained access to the crystalline free space. The silica to alumina ratio referred to may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels. Although zeolites with a silica to alumina ratio of at least 12 are useful, it is preferred to use zeolites having higher ratios of at least about 30. Such zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e., they exhibit "hydrophobic" properties. It is believed that this hydrophobic character is advantageous in the present invention. The zeolites useful as catalysts in this invention freely sorb normal hexane and have a pore dimension greater than about 5 Angstroms. In addition, their structure must provide constrained access to some larger molecules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings, then access by molecules of larger cross-section than normal hexane is substantially excluded and the zeolite is not of the desired type. Zeolites with windows of lO-membered rings are preferred, although excessive puckering or pore blockage may render these zeolites substantially ineffective. Zeolites with windows of 12-membered rings do not generally appear to offer sufficient constraint to produce the advantageous conversions desired in the instant invention, although structures can be conceived, due to pore blockage or other cause, that may be operative. Rather than attempt to judge from crystal structure whether or not a zeolite possesses the necessary constrained access, a simple determination of the "constraint index" may be made by continuously passing a mixture of equal weight of normal hexane and 3-methylpentane over a small sample, approximately 1 gram or less, of zeolite at atmospheric pressure according to the following procedure. A sample of the zeolites, in the form of pellets or extrudate, is crushed to a particle size about that of coarse sand and mounted in a glass tube. Prior to testing, the zeolite is treated with a stream of air. at 1000F (5380C) for at least 15 minutes. The zeolite is then flushed with helium and the temperature adjusted between 5500F (2880C) and 9500F (5100C) to give an overall conversion between 10% and 60%. The mixture of hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 volume of liquid hydrocarbon per volume of catalyst per hour) over the zeolite with a helium dilution to give a helium to total hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchanged for each of the two hydrocarbons. The "constraint index is calculated as follows: Constraint = log 10 (fraction of n-hexane remaining) Index log 10 (fraction of 3-methylpentane remaining) The constraint index approximates the ratio of the cracking rate constants for the two hydrocarbons. Catalysts suitable for the present invention are those which employ a zeolite having a constraint index from 1.0 to 12.0. Constraint index (C.I.) values for some typical zeolites, including some not within the scope of this invention, are: CAS C.I. ZSM-5 8.3 Erionite 38 ZSM-ll 8.7 ZSM-35 6.0 TMA Offretite 3.7 ZSM-38 2.0 ZSM-12 2. Beta 0.6 ZSM-4 0.5 Acid Mordenite 0.5 REY 0.4 Amorphous Silica-Alumina 0.6 The above-described constraint index is an important, and even critical, definition of those zeolites which are useful to catalyze the instant process. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby have different constraint indexes. Constraint index seems to vary somewhat with severity of operation (conversion). Therefore, it will be appreciated that it may be possible to so select test conditions to establish multiple constraint indexes for a particular given zeolite which may be both inside and outside the above defined range of 1 to 12. Thus, it should be understood that the parameter and property "Constraint Index" as such value is used herein is an inclusive rather than an exclusive value. That is, a zeolite when tested by any combination of conditions within the testing definition set forth hereinabove to have a constraint index of 1 to 12 is intended to be included in the instant catalyst definition regardless that the same identical zeolite tested under other defined conditions may give a constraint index value outside of 1 to 12. The class of zeolites defined herein is exemplified by ZSM-5, ZSM-ll, ZSM-12, ZSM-35 and ZSM-38, and other similar materials. Recently issued U.S. Patent 3,702,886, describing and claiming ZSM-5, is incorporated herein by reference. ZSM-ll is more particularly described in U.S. Patent 3,709,979, the entire contents of which are incorporated herein by reference. ZSM-12 is more particularly described in U.S. Patent 3,832,449, the entire contents of which are incorporated herein by reference. The subject of ZSM-35 is described in U.S. Application Serial No. 528,061 filed November 29, 1974. The subject of ZSM-38 is described in U.S. Application Serial No. 528,060 filed November 29, 1974. The specific zeolites described, when prepared in the presence of organic cations, are substantially catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 10000F (5380C) for 1 hour, for example, followed by base exchange with ammonium salts followed by calcination at 10000F (5380C) in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of this special type zeolite; however, the presence of these cations does appear to favor the formation of this special type of zeolites. More generally, it is desirable to activate this type zeolite by base exchange with ammonium salts followed by calcination in air at about 10000F (5380C) for from about 15 minutes to about 24 hours. Natural zeolites may sometimes be converted to this type zeolite by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination, alone or in combinations. Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite and clinoptilolite. The preferred crystalline aluminosilicates are ZSM-5, ZSM-1l, ZSM-12, ZSM-35 and ZSM-38, with ZSM-5 particularly preferred. The zeolites used as catalysts in this invention may be in the hydrogen form or they may be base exchanged or impregnated to contain ammonium or a metal cation complement. It is desirable to calcine the zeolite after base exchange. The metal cations that may be present include any of the cations of the metals of Groups I through VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to substantially eliminate the activity of the zeolite for the catalysis being emplOyed in the instant invention. For example, a completely sodium exchanged H-ZSM-5 appears to be largely inactive for shape selective conversions required in the present invention. In a preferred aspect of this invention, the zeolites useful as catalysts herein are selected as those having a crystal framework density, in the dry hydrogen form, of not substantially below about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired. Therefore, the preferred catalysts of this invention are those comprising zeolite having a constraint index as defined above of about 1 to 12, a silica to alumina ratio of at least about 12 and a dried crystal density of not substantially less than about 1.6 grams per cubic centimeter. The dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite Structure by W.M. Meier. This paper, the entire contents of which are incorporated herein by reference, is included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London, 1968. When the crystal structure is unknown, the crystal framework density may be determined by classical pycnometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. It is possible that the unusual sustained activity and stability of this class of zeolites are associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density of course must be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, seems to be important as the locus of catalytic activity. Crystal framework densities of some typical zeolites, including some which are not within the purview of this invention., are: Void Framework Zeolite Volume Density Ferrierite 0.28 cc/cc 1.76 g/cc Mordenite .28 1.7 ZSM-5, -11 .29 1.79 Dachiardite .32 1.72 L .32 1.61 Clinoptilolite .34. 1.71 Laumontite .34 1.77 ZSM-4 (Omega) .38 1.65 Heulandite .39 1.69 P .41 1.57 Offretite .40 1.55 Levynite .40 1.54 Erionite .35 1.51 Gmelinite .44 1.46 Chabazite .47 1.45 A .5 1.3 Y .48 1.27 An intimate mixture of heterogeneous catalysts may be prepared in various ways. The two components may be separately prepared in the form of catalyst particles such as pellets or extrudates, for example, and simply mixed in the required proportions. The particle size of the individual component particles may be quite small, for example from about 20 to 150 microns, when intended for use in fluid bed operation; or they may be as large as up to about 1/2 inch (1.25 cm.) for fixed bed operation. Or, the two components may be mixed as powders and formed into pellets or extrudate, each pellet containing both components in substantially the required proportions. Binders such as alumina, zirconia, silica, titania, magnesia, etc., may be present. Base exchange of the crystalline aluminosilicate component may be used in some selected cases to effect the introduction of part or all of a metal component. Other means for forming the intimate mixture may be used, such as: precipitation of the metal component in the presence of the acidic crystalline aluminosilicate; or electroless deposition of metal on the zeolite; or deposition of metal from the vapor phase. Various combinations of the above preparative methods will be obvious to those skilled in the art of catalyst preparation. It should be cautioned, however, to avoid techniques likely to reduce the crystallinity of the acidic crystalline aluminosilicate. Figure 1 is a graph showing the effect of olefin feed partial pressure on product composition. Figure 2 is a graph showing the liquid product boiling point and the C5 plus octane rating obtained when converting propylene. Figure 3 is a graph showing a comparison between observed and calculated octane of olefination product + a light reformate. Figure 4 is a diagrammatic sketch of the processing arrangement of the present invention. A distillation of the liquid products obtained from propylene olefination alone at 14 psia (0.95 atm) and propylene diluted with nitrogen ratio (1.10) to reduce the propylene to 1.3 psia (0.09 atm.) shows in Table 1 below a substantial shift in composition and thus boiling points. The same components are present, but shifted substantially in concentration to a lower carbon number product, as shown in the table below: : Table 1 Component Breakdown of C5+ C3 = Alone 10/1 N2C3 = n-C5 0.3 0.2 i-C5 1.3 0.6 C5= 16.9 36.8 Cyclo C5 0.1 n-C6 0.4 0.2 i-C6 1.5 0.7 c6= 15.2 22.9 Cyclo C6 .1 n-C7 0.3 0.1 i-C7 1.5 0.6 C7= 17.2 20.3 DiMe-N5 - 0.1 n-C8 0.2 0.1 Iso-C8-P+O+N5+N6 14.9 10.4 n-C9 0.7 0.1 Iso-C9-P+O-N5+N6 12.9 5.1 n-C10 0.3 Iso-C10-P+0+N5+N6 7.8 1.5 Unknown 8.4 0.3 100.01 100.0 The low pressure olefination operation of this invention provides a larger proportion of shorter chain olefin components of improved quality as represented.by octane number and lower total product end point than obtained when processing the olefin feed under the higher pressure condition. In order to obtain a better understanding of the low pressure operat-ion of this invention, three different olefin charge materials were contacted under particularly selected operating conditions. That is, to better understand the conversion potential of components of a broad olefin charge, propylene, a pentene mixture and l-hexene were separately converted as herein defined. In the following examples, the three separate feeds were admixed with hydrogen in a 10/1 H2/HC ratio for contact at atmospheric pressure and a temperature of about 5300F(277"C) with an acidic ZSM-5 crystalline zeolite catalyst. A weight hourly space velocity (WHSV) in the range of 0.5-0.9 was employed. The results obtained are provided in Table 2 below. Table 2 Carbon Number Distribution Atmospheric Pressure, 10/1 H2/HC 5300F (2770C), 0.5-0.9 WHSV Example 1 2 3 Pentene Charge Propylene Mixture l-Hexane Product Cl+C2 Wt.% ( 0.1 z < 0.1 0.1 C3 9.5 19.1 8.9 Cq 26.7 20.0 20.0 C5 29.3 26.4 22.4 C6 13.,3 15.1 16.0 C7 11.1 11.2 10.3 C8 5.7 7.0 8.0 Cg 2. 9 5. 3 6. 4 C10+ 1.5 4.9 7.5 It will be observed upon examination of the data of Table 2 that the three separate feeds vary considerably in carbon number but each produces close to equilibrium conversion mixtures rich in C4 and C5 olefins. Some C6 and C7 olefins are also produced, with C5 carbon compounds predominating. The C5 product mixture from each feed was separately examined. It was found that about 80% of the C5 olefins are tertiary olefins as summarized below in Table 3. Table 3 C5 Olefin Distribution Example 1 2 3 Equilibrium Charge Propylene Pentenes 1-Hexene Values Product Product Product C5 Analysis Charge (a) C5 Analysis C5 Analysis C5=1 2 < 1.0% 2 2 2 2MlC4= 16 8.0% 18 18 20 3MlC4= 2 < 1.0% 2 2 2 T2C5= 10 1.0% 11 12 9 C2C5= 25 < 1.0% 5 5 7 2M2C4= 65 88.0% 62 61 60 (a) Contains also 1% butenes and 2% i-C5. Although the C4 olefin distribution of Table 2 was not determined, it is reasonable to expect isomer formation and the isomers to be at equilibrium, which is 6% l-butene, 37% 2-butenes, and 57% isobutene. This assumption is predictable in view of the work of F.D. Rossini, "The Science of Petroleum", Vol.V, Part I, pp. 153-181, Oxford University Press, 1950. Under the conditions of operation herein defined, substantially any material inert to the olefination reactions desired to be promoted may be employed as the diluent material mixed with the olefin charge. Some diluents suitable for the process include nitrogen, carbon monoxide, carbon dioxide, helium, paraffins (component of the charge) and hydrogen. In the combination process of this invention, an olefinic charge material available from any source and economically recovered or a light olefinic naphtha product of thermal or catalytic cracking is contacted with the acidic form of the crystalline zeolite catalyst herein identified at a temperature in the range of from about 4000F (2040C) to about 6000F (316"C), preferably from about 4500F (2320C) to about 5500F (2880C), at a pressure less than atmospheric pressure, olefin pressure preferably 4 psia (0.27 atm.) or less, and an olefin feed at a weight hourly space velocity in the range of 0.2 to 5 for a fixed catalyst bed or the equivalent contact time if a fluidized catalyst system is used. The catalyst may be used as a fixed bed of catalyst, a moving catalyst or a fluidized catalyst system may be used. The olefination product stream comprising a-mixture of olefinic hydrocarbons predominantly C4 to C7 olefins and primarily C4 to C5 olefins comprising olefin isomers with minor amounts of lower and higher boiling components, and very little; if any, aromatics are'recovered as a productof the acidic zeolite catalyst olefination step. All or only a portion of the zeolite catalyst conversion product such as the C4 and C5 olefin product above identified is then converted in the presence of methanol and a solid acidic catalyst to form high octane ether products as herein discussed. Some examples pertinent to the olefin producing step of the invention are provided below. Example 4 - Hydrogen/Propylene Mixtures The results obtained by passing propylene alone and mixed with 1, 5 and 10 volumes of hydrogen over acid.H-ZSM-5 extrudate (35% alumina binder) are provided in Table 4. (Propylene partial pressures of 1.0, 0.5, 0.2 and 0.1 atmosphere; psia's 14.7, 7.4, 2.5, 1.3, respectively, were obtained with this hydrogen dilution.) Example 5 - Nitrogen/Propylene Mixtures Table 5 presents the results obtained by mixing 5 and lp volumes of nitrogen with propylene (propylene partial pressures 0.2 and 0.1 atmosphere, psia's 2.5 and 1.3). Example 6 - Propane/Propylene Mixtures Table 6 presents the results obtained by mixing 0.7, 5 and 10 volumes of propane with propylene (propylene partial pressures 0.6, 0.2, and 0.1 atmosphere, psia's 8.6, 2.5 and 1.3, respectively). Example 7 - Nitrogen/Propane/Propylene/Butylene Mixtures Table 7 presents the results obtained with the above mixtures providing olefin partial pressures of 0.2, 0.1 and 0.07 atmosphere (2.9, 1.5 and 0.0 psia, respectively). The effect of olefin partial pressure on yields using data from the above four examples is shown in Figure 1. A marked shift to lighter carbon number product occurs at olefin pressures of below about 3 psia (0.2 atm.). The result is a lower boiling range and a higher octane number product (Figure 2). Table 4 Hydrogen / Propylene Mixtures 10/1/0.7 Mole Ratio, H2/C3= 0/1 1/1 5/1 10/1 (H2/C3=/C3) Total Pressure, psig 14.7 14.7 14.7 14.7 165 (12 atm.) Olefin Partial Pressure, (2 atm.) (2 atm.) (2 atm.) (2 atm.) psia 14.7 7.4 2.5 1.3 14.1 Atmosopheres 1.0 0.5 0.2 0.1 0.1 Temperature, F, Average 524 529 521 529 499 (273 C) (276 C) (272 C) (276 C) (259 C) Maximum 529 540 526 533 502 276 C) (282 C) (274 C) (278 C) (261 C) WHSV (Olefin) 0.56 0.59 0.48 062 0.34 Olefin Conversion wt.% 99 98 95 93 97 Catalyst Age, Days 9 18 4 17 3 Yields, wt.% (Propane free) C1 + C2 - 0.1 0.2 - 0.1 C3 's, Total 2.0 3.1 7.8 8.1 2.6 C3= 1.0 2.3 5.4 7.1 2.6 C3 1.0 0.8 2.4 1.0 C4's Total 8.6 18.2 24.4 27.9 16.2 i-C4 1.0 1.2 3.5 1.1 2.0 C4= 7.3 16.7 20.1 26.7 12.0 n-C4 0.3 0.3 0.8 0.1 1.6 Table 4 (Cont'd) C5's Total 19.0 25.8 26.7 29.7 21.7 i-C5 1.5 1.5 2.8 0.8 1.3 C5= 17.1 24.0 23.0 28.6 19.0 n-C5 0.4 0.3 0.9 0.3 1.4 C6 70.4 50.8 40.9 34.3 59.4 100.0 100.0 100.0 100.0 100.0 C6+Composition, wt.% P 13 11 17 5 10 O 87 89 81 95 89 N < 1 < 1 < 1 < 1 < 1 A < 1 < 1 < 1 < 1 < 1 Liquid Product 90% B.P., F, (Sim. Dist.) 373 343 301 250 363 Liquid Product O.N., R+0 93.4 94.3 95.0 98.4 93.8 C5+O.N., R+0 93.0 94.1 94.6 98.4 93.7 Specific Gravity 0.7255 0.7142 0.7051 0.7030 0.7210 Table 5 Nidrogen / Propylene Mixtures Mole Ratio, N2/C3= 0/1 5/1 10/1 Total Pressure, psia 14.7(1 atm.) 14.7(1 atm.) 14.7(1 atm.) Olefin Partial Pressure,psia 14.7 2.5 1.3 Atmosopheres 1.0 0.2 0.1 Temperature, F, Average 524 522 523 526 452 410 (273 C) (272 C) (273 C) (274 C) (233 C) (210 C) Maximum 528 527 527 528 477 412 (273 C) (275 C) (275 C) (276 C) (247 C) (211 C) WHSV (Olefin) 0.56 0.56 0.65 0.88 0.64 0.63 Olefin Conversion, wt.% 99 95 91 89 82 14 Catalyst Age, Days 8 7 15 9 5 6 Yield, wt.% C1+C2 - - - - - C3's Total 2.0 6.2 9.3 12.2 18.8 87.1 = C3= 1.0 5.2 8.7 11.5 18.2 86.4 C3 1.0 1.0 0.6 0.7 0.6 0.7 C4's Total 8.6 19.8 29.2 27.2 20.7 1.3 i-C4 1.0 2.2 1.0 0.9 0.6 C4= 7.3 17.2 28.1 26.2 19.9 1.3 n-C4 0.3 0.4 0.1 0.1 - - Table 5 (Cont'd) C5's Total 19.0 27.1 29.1 33.0 21.2 1.8 i-C5 1.5 2.0 0.5 0.5 0.2 0.1 C5= 17.1 24.5 27.5 32.4 21.0 1.7 n-C5 0.4 0.6 0.1 0.1 - C6 70.4 46.9 33.4 27.6 39.3 10.0 100.0 100.0 100.0 100.0 100.0 100.0 C6+Composition, wt.% P 13 15 4 5 7 O 87 85 96 95 93 N < 1 < 1 < 1 < 1 < 1 A < 1 < 1 < 1 < 1 < 1 Liquid Product 90% B.P., F, (Sim. Dist.) 373 292 239 - 291 340 Liquid Product O.N., R+0 93.4 98.2 98.5 99.9 93.8 C5+O.N., R+0 93.0 98.0 98.3 99.6 93.6 Specific Gravity 0.7255 0.7080 0.7042 0.6958 0.7145 0.7332 Table 6 Propane/Propylene Mixtures Mole Ratio, C3/C3= 0.1 0.71/1 5/1 10/1 Total Pressure, psia 14.7 14.7 14.7 14.7 (1 atm.) (1 atm.) (1 atm.) (1 atm.) Olefin Partial Pressure, psia 14.7 8.6 2.5 1.3 Atmospheres 1.0 0.6 0.2 0.1 Temperature, F, Average 524 516 520 520 (273 C) (269 C) (271 C) (271 C) Maximum 528 519 526 523 (276 C) (271 C) (274 C) (273 C) WHVS (Olefin) 0.56 0.80 0.44 0.50 Olefin Coonversion, wt.% 99 97 94 94 Catalyst Age,Days 8 14 10 9 Yields, wt.% (Propane (Propane Free) Free) C1+C2 - 0.1 0.6 C3's, Total 2.0 6.6 5.6 6.1 C3= 1.0 2.9 5.6 6.1 C3 1.0 3.7 - C4's Total 8.6 13.7 17.1 34.0 i-C4 1.0 1.0 3.0 8.2 C4= 7.3 12.7 14.0 25.7 n-C4 0.3 - 0.1 0.1 Table 6 (Cont'd) C5's Total 19.0 16.9 21.3 21.3 i-C5 1.5 0.7 2.3 1.4 C5= 17.1 16.2 18.7 25.4 n-C5 0.4 - 0.3 0.2 C6+ 70.4 62.7 55.4 32.9 100.0 100.0 100.0 100.0 C6+Composition, wt.% P 13 9 16 7 O 87 90 83 93 N < 1 < 1 < 1 < 1 A < 1 < 1 < 1 < 1 Liquid Product 90% B.P., F (Sim. Dist.) 373 (189 C) 368 (187 C) 369 (187 C) Liquid Product O.N., R+0 93.4 93.5 93.6 96.7 C5+O.N., R+0 93.0 93.9 93.6 96.6 Specific Gravity 0.7255 0.7287 0.7176 0.7035 Table 7 Nitrogen/Propane/Propylene/Butylene Mixtures Ratio, N2/C3/C3=/C4= 0/6.6/1/0.7 8.5/6.6/1/0.7 17/6.6/1/0.7 Total Pressure, psia 14.7 (1 atm.) 14.7 (1 atm.) 14.7 (1 atm.) Olefin Partial Pressure, psia 2.9 1.5 1.0 Atmospheres 0.2 0.1 0.07 Temperature, F, Average 521 (272 C) 522(272 C) 521(272 C) Maximum 525 (274 C) 530(277 C) 529(276 C) WHSV (Olefin) 0.40 0.46 0.44 Olefin Conversion, wt%, C3= 93 90 88 C4= 50 31 29 Total 76 67 65 Catalyst Age, Days 11 12 12.5 Yields, wt.% (Propane Free) C1+2 - - C3's Total 4.4 6.2 7.5 C3= 4.4 6.2 7.5 C3 - - C4's Total 23.1 30.0 30.5 i-C4 3.5 2.9 2.7 C4= 19.5 26.6 27.7 n-C4 0.1 0.5 0.1 Table 7 (Cont'd) C5's Total 24.9 30.3 30.2 i-C5 2.2 2.8 2.0 C5= 22.4 27.3 28.1 n-C5 0.3 0.2 0.1 C6= 47.6 33.5 31.8 100.0 100.0 100.0 C6+Composition, wt.% P 14 9 9 O 86 90 91 N < 1 < 1 < 1 A < 1 < 1 < 1 Liquid Product 90% B.P., F (Sim. Dist.) 333 (167 C) - Liquid Product O.N., R+0 94.9 96.8 97.1 C5+O.N., R+0 94.9 96.7 97.0 Specific Gravity 0.7119 0.7005 0.7000 The effect of controlling olefin feed partial pressure on product yields is provided by the data of the above tables and descriptively shown by Figure 1. A marked shift to lighter carbon number product is observed to occur at olefin pressures below about 4 psia (0.27 atm). The result is a low boiling range product of relatively high octane number, as shown by the plot of data forming Figure 2. It is observed that butenes increase with propylene as the feed, but with a mixed C3-C4 oleo in feed, some butylene also olefinates without loss of product quality. Yields of C4's, C51s and C6 plus product change only slightly as the olefin partial pressure is decreased from 14 psia (0.95 atom) to about 4 psia (0.27 atm). However, between 3 (0.2 atm) and 1 (0.07 atm) psia, C4 's and C5's rise relatively sharply at the expense of C6 plus material. Whether hydrogen, nitrogen or propane is used as a diluent does not appear to be critical. A loss in C5 plus yield due to an increase of C41s with propylene as the charge can be offset by including butylenes in the olefin charge. In Figure 2 are plotted liquid product 90% boiling points and C5 plus R+0 octane numbers v. olefin partial pressure. It will be observed that beginning about 4 psia (0.27 atm) and more particularly about 3 psia (0.2 atm.) olefin partial pressure, the curve representing the 90% boiling point drops more rapidly and the C5 plus octane number product curve increases rather sharply beginning at 4 psia (0.27 atm.) from about 94 to 97, with and without butylene in the charge. In Table 8 and Figure 3 are presented the results of data obtained using a stable liquid (stable at operating conditions) as a diluent for the olefination conversion operation. In this example, the stable liquid is a C6 to 2000F reformate product which contains 60-808 paraffins and the remaining material comprises benzene and toluene. A part of these aromatics may be alkylated by the olefin, but that doesn't affect their properties as a diluent. Therefore, paraffins, aromatics, and naphthenes can be considered stable liquid diluents under the particular olefination conditions. Note that the carbon number distribution of olefinic product is similar for the nitrogen and reformate diluents. Figure 3 illustrates the remarkably high octane values obtained by the combination of the light olefination component with light reformate. For example, a 50/50 blend of light reformate octane value of about 76 R+0 and olefination product provides a product mixture of 92 (R+0) octane number. Table 8 Diluent NONE N2 Reformate C6-200 F Diluent/C3=, mole - 10/1 3/1 1.5/1 Temp. Max., F 530(277 C) 530(277 C) 540(282 C) 540(282 C) Olefin Pressure, Atm. 1 0.1 0.25 0.4 Olefin Conversion, wt.% 99 91 96 93 Yields wt.% Total Charge C1+C2+Propane < 1 < 1 < 1 < 1 C4 9 29 3 5 C5+ 90 63 96 93 R+0, C5+ 93 98 84(See 87 Fig.3) Sim. Dist.,90% OH at F 375(191 C) 240(116 C) 230(110 C) 245(118 C) Olefin Distribution in C5+ C5= 17 37 19 22 C6= 15 23 24 22 C7= 17 20 25 20 C8= 15 10 10 9 C9+ 21 7 4 3 The olefination product of the crystalline zeolite restructuring operation above identified and specifically discussed is upgraded to an even higher octane product by reacting olefin isomers therein particularly comprising isobutylene and isoamylene with methanol to form ether products thereof and particularly methyl tertiary butyl ether (MTBE) and tertiary amyl methyl ether (TAME). The reaction of methanol with isobutylene and isoamylenes at moderate conditions with a resin catalyst is known technology as provided by R.W. Reynolds et al. The Oil and Gas Journal, June 16, 1975, and S. Pecci and T. Floris, Hydrocarbon Processing, Dec. 1977. An article entitled "MTBE and TAME a good octane boosting combo" by J.D. Chase et al, The Oil and Gas Journal, April 9, 1979, pages 149-152, discusses the technology. The processing combination of the present invention embodies the known technology of forming high octane ethers by reacting methanol with either isobutylene or isoamylene in the presence of solid acidic catalysts in combination with the olefination technology and processing combination of the present invention. The drawing, Figure 4, is a diagrammatic sketch in elevation of the processing combination of this invention comprising the formation of an olefinic product such as C4 and C5 tertiary isoolefins and the conversion thereof to higher octane ethers. Referring now to the drawing, Figure 4, by way of example, an olefin feed comprising C10 and lower boiling olefins such as provided by thermal and catalytic naphthas and/or other combination olefin refining product streams are charged to the process by conduit 2 and thence to reactor 4. A diluent material considered generally inert to the process is charged by conduit 6. In reactor 4, tha olefins are rearranged as by olefination reactions as herein described at a temperature below 6000F (3160C) and more usually the temperature is below about 5500F (2880C). The reaction is effected at olefin subatmospheric pressure by contact with an acid ZSM-5 crystalline zeolite to provide a product rich in C4 and C5 olefins and comprising isobutylene and isoamylene. The product of the zeolite catalyst operation in reactor 4 is withdrawn for further treatment as herein discussed. In one embodiment, it is contemplated charging the total effluent of olefination reactor 4 in contact with a solid acidic catalyst for reaction with an alcohol to form high octane ethers. In another embodiment, the zeolite catalyst olefination effluent is separated in a zone not shown to recover primarily C4 and C5 boiling components and particularly olefin isomers thereof from other olefins and particularly from C6 and higher boiling components. The separated C6 and higher boiling components are recycled to the zeolite catalyst olefination conversion reactor stage 4 by means not shown for further conversion therein to desired isoolefins. Whichever embodiment is relied upon, the product of Qlefination reactor 4, comprising C4 and C5 olefins, is passed by conduit 8 to ether forming reactor 10. A lower alcohol, preferably methanol, is also charged to ether forming reactor 16 by conduit 12. In the ether forming reactor, the charged methanol and olefins comprising isobutylene and tertiary isoamylenes are reacted in the presence of a solid acidic catalyst to form TAME and MTBE. In a particular operation, a commercially available sulfonic acid resin catalyst may be employed. The product of reactor 10 and comprising high octane ethers, unreacted olefins and methanol are passed by conduit 14 to a separation zone 16. Separation zone 16 is maintained at a desired pressure, normally atmospheric pressure, and a temperature within the range of 80 (270C) to 1250F (520C), depending on the separation desired. In one arrangement, C5 and lower boiling unreacted olefins along with unreacted methanol are separated and withdrawn by conduit 18 for recycle to the olefination reactor 4. In reactor 4, the unconverted methanol and olefins recycled are converted and/or restructured to form desired olefin product. On the other hand, it may be desirable to retain in the separation effected in separator 16 the C5 + unreacted olefins with the formed high octane ether product. In this separation and recovery arrangement, the unreacted C5+ olefins may also be separated from the high octane ethers and thereafter blended in pool gasoline. Thus, depending on the separating temperature and pressure conditions relied upon, the high octane ether product (TAME and MTBE) separated in zone 16 either with or without C5 plus olefins is withdrawn by conduit 20 as a primary product of the combination process. On the other hand, the separation may be made to recover C6 plus uneacted olefins with the ether product rather than the C5 plus unreacted olefins Therefore either a C4 or a C5 minus product of ether formation may be separated and recycled to olefination zone 4. MTBE and TAME are known to be high octane ethers. The above referred to article by J.D. Chase et al, Oil and Gas Journal, April 9, 1979, clearly identifies the advantages one can achieve by using these materials to alter gasoline octane. Thus it is clear that, where a shortage of isobutylene and isoamylene exists and low octane olefins abound, the processing combination of the present invention contributes measurably to reducing the problems associated with low octane gasoline product. The octane blending number of MTBE when 10% is added to a base fuel R+0 = 91 is about 120. For a base fuel with a motor rating (M+0) of 83 octane the blending value of MTBE at the 10% level is about 103. On the other hand, for an (R+0) of 95 octane fuel the blending value of 10% MTBE is about 114, and for an (M+O) of 84 octane the 10% blending value is about 100. Having thus generally described the method and concepts of the present invention and presented specific examples in support thereof, it is to be understood that no undue restrictions are to be imposed by reason thereof except as defined by the following claims.

Claims: WHAT WE CLAIM IS: 1. A method for producing gasoline boiling range high octane products from a mixture of olefins comprising up to C10 olefins which comprises, contacting a mixed olefin feed with an acid crystalline zeolite catalyst characterized by a pore opening of at least 5 Angstroms, a silica to alumina ratio of at least 12 and a constraint index within the range of 1 to 12 at an olefin pressure below 0.5 atmosphere and a temperature selected from within the range of 4000F (2040C) to 6000F (3160C), and recovering an olefinic product enriched with C4 and C5 olefins comprising olefin isomers. 2. The method of Claim 1 wherein the olefin feed is contacted with said crystalline zeolite at a temperature within the range of 5000F (2600C) to 5000F (2880C) at an olefin pressure not above 0.3 atmosphere and sufficient to obtain 95% conversion to a higher octane product comprising less than 2% aromatics. 3. The method of Claim 1 wherein a diluent material substantially inert to the restructuring of the olefins charged is employed with said olefin feed to maintain the partial pressure of the olefin feed below 0.5 atmosphere. 4. The method of Claim 1 wherein the olefin feed comprises a mixture of C2 to C10 carbon compounds. 5. The method of Claim 1 wherein the olefin feed is mixed with one or more of hydrogen, propane and nitrogen. 6. The method of Claim 1 wherein the olefinic product comprises isobutylene and isopentenes which materials are reacted with an alcohol by.contact with an acidic catalyst to form high octane ethers. 7. A method for producing high octane ether products comprising tertiary amyl methyl ether and methyl tertiary butyl ether from a C2 to C10 olefin feed mixture which comprises, reacting the C2 to C10 olefin feed under temperature and pressure conditions in the presence of an acid zeolite catalyst providing a pore opening of at least 5 Angstroms, a silica-alumina ratio of at least 12 and a constraint index within the range of 1 to 12 to form an olefin product richer in C4 and C5 olefins and comprising olefin isomers of isobutylene and isopentenes, reacting at least the olefin isomers with a lower alcohol in the presence of an acid catalyst under temperature and pressure conditions promoting the formation of the high octane ethers above identified, separating the formed ethers from unreacted C4 minus olefins and alcohol and recovering the separated ethers, and recycling the separated C4 minus olefins and alcohol for contact with the zeolite catalyst above identified. 8. The method of Claim 7 wherein C5 plus olefins are recovered with the ether product. 9. The method of Claim 7 wherein olefins boiling below C6 olefins are separated from the ether product and recycled to the zeolite catalyst conversion step. 10. The method of Claim 7 wherein the formation of ethers from C4 and C5 olefin isomers is accomplished with methanol and an acidic resin catalyst. 11. The method of Claim 7 wherein the olefin product of the zeolite catalyst conversion operation is separated to recover particularly C4 to C7 olefins which are thereafter reacted with methanol in the presence of a solid acidic catalyst to form the ether products desired and unreacted olefins are separated from the ether product to provide separate streams thereof for use in blending to form desired gasoline product. 12. A method for producing high octane ethers and olefins from a mixture of C2 to C10 olefins which comprises, converting the C2 to C10 olefins in the presence of a special zeolite catalyst by olefination thereof to a product enriched in C4 to C7 olefins, reacting the C4 to C7 olefins thus produced with methanol and in the presence of an acid catalyst to form ethers of isobutylene and isopentenes, separating the ether product and C6 plus olefins from unreacted C5 minus olefins and methanol, and recycling the C5 minus olefins with methanol to the special zeolite catalyst olefination operation, said special zeolite catalyst comprising a crystalline zeolite characterized by a pore opening of at least 5 Anstroms, a silica to alumina ratio of at least 12 and a constraint index within the range of 1 to 12.

Inventors: GARWOOD, WILLIAM EVERETT, SCHOENNAGEL, HANS-JUERGEN
Applicants: MOBIL OIL CORPORATION
Application year: 1980
Main classification: C07C41
IPC codes: C07C6, C10G35, B01J29, C07C67, C10L1, C07C41, C07C43