||November 20, 1979
||December 19, 1977
||Burress; George T. (Somerville, NJ)
||Mobil Oil Corporation (New York, NY)|
|Attorney Or Agent:
||Huggett; Charles A.Barclay; Raymond W.Szatkowski; Thomas S.
||585/322; 585/411; 585/481; 585/486
|Field Of Search:
|U.S Patent Documents:
||2795630; 3646236; 3691247; 3751504; 3756942; 3761389; 3790471
|Foreign Patent Documents:
||Mixtures of C.sub.8 aromatic hydrocarbons are contacted in vapor phase with acid zeolite ZSM-5. The xylene content is thereby isomerized and the ethyl benzene content of the charge is converted in a manner which results in net increase of aromatic rings.
1. In a process for conversion of a mixture of aromatic compounds having eight carbon atoms, said mixture containing ethyl benzene and xylenes, to isomerize xylenes contained in saidmixture and convert at least part of ethyl benzene so contained to xylene or to compounds readily separable by distillation from eight carbon atom aromatics; the improvement which comprises contacting such mixture of eight carbon atom aromatic compoundswith a catalyst which comprises acid zeolite of the ZSM-5 type, acid zeolite ZSM-12 .[.or acid zeolite ZSM-21.]. .Iadd., acid zeolite ZSM-35 or acid zeolite ZSM-38 .Iaddend.in vapor phase and in the absence of added hydrogen at a temperature of about500.degree. F. to about 1,000.degree. F. .Iadd. 2. The process of claim 1 wherein said contacting is effected at a pressure in the range of 0 to about 1000 psig. .Iaddend..Iadd. 3. The process of claim 1 wherein said contacting is effected atatmospheric pressure. .Iaddend..Iadd. 4. The process of claim 1 wherein said contacting is effected at 150 psig. .Iaddend..Iadd. 5. The process of claim 1 wherein said contacting is effected at 200 psig..Iaddend.
||BACKGROUND OF THE INVENTION
Xylenes are found in fractions from coal tar distillate, petroleum reformates and pyrolysis liquids in admixture with other compounds of like boiling point. The aromatic components are readily separated from non-aromatics by solvent extraction. Distillation provides a fraction consisting essentially of C.sub.8 aromatics. As will appear below, o-xylene is separable from other C.sub.8 aromatics by fractional distillation, and p-xylene is separable by fractional crystallization. Present demandis largely for p-xylene and it has become desirable to convert m-xylene, the principal xylene present in the feed stream, to the more desired p-xylene.
Since the announcement of the first commercial installation of Octafining in Japan in June, 1958, this process has been widely installed for the supply of p-xylene. See "Advances in Petroleum Chemistry and Refining" volume 4, page 433(Interscience Publishers, New York 1961). That demand for p-xylene has increased at remarkable rates, particularly because of the demand for terephthalic acid to be used in the manufacture of polyesters.
Typically, p-xylene is derived from mixtures of C.sub.8 aromatics separated from such raw materials as petroleum naphthas, particularly reformates, usually by selective solvent extraction. The C.sub.8 aromatics in such mixtures and theirproperties are:
______________________________________ Density Freezing Boiling Lbs./U.S. Point .degree.F. Point .degree.F. Gal. ______________________________________ Ethyl benzene -139.0 277.1 7.26 P-xylene 55.9 281.0 7.21 M-xylene -54.2 282.4 7.23 O-xylene -13.3 292.0 7.37 ______________________________________
Principal sources at present are catalytically reformed naphthas and pyrolysis distillates. The C.sub.8 aromatic fractions from these sources vary quite widely in composition but will usually be in the range 10 to 32 wt. percent ethyl benzenewith the balance, xylenes, being divided approximately 50 wt. percent meta, and 25 wt. percent each of para and ortho.
In turn, calculated thermodynamic equilibra for the C.sub.8 aromatic isomers at Octafining conditions are:
______________________________________ Temperature 850.degree. F. ______________________________________ Wt. % Ethyl benzene 8.5 Wt. % para xylene 22.0 Wt. % meta xylene 48.0 Wt. % ortho xylene 21.5 TOTAL 100.0 ______________________________________
An increase in temperature of 50.degree. F. will increase the equilibrium concentration of ethyl benzene by about 1 wt. percent, ortho-xylene is not changed and para and meta xylenes are both decreased by about 0.5 wt. percent.
Individual isomer products may be separated from the naturally occurring mixtures by appropriate physical methods. Ethyl benzene may be separated by fractional distillation although this is a costly operation. Ortho xylene may be separated byfractional distillation and is so produced commercially. Para xylene is separated from the mixed isomers by fractional crystallization.
As commercial use of para and ortho xylene has increased there has been interest in isomerizing the other C.sub.8 aromatics toward an equilibrium mix and thus increasing yield of the desired xylenes.
Octafining process operates in conjunction with the product xylene or xylenes separation processes. A virgin C.sub.8 aromatics mixture is fed to such a processing combination in which the residual isomers emerging from the product separationsteps are then charged to the isomerizer unit and the effluent isomerizate C.sub.8 aromatics are recycled to the product separation steps. The composition of isomerizer feed is then a function of the virgin C.sub.8 aromatic feed, the product separationunit performance, and the isomerizer performance.
The isomerizer unit itself is most simply described as a single reactor catalytic reformer. As in reforming, the catalyst contains a small amount of platinum and the reaction is carried out in a hydrogen atmosphere.
Octfiner unit designs recommended by licensors of Octafining usually lie within these specification ranges:
______________________________________ Process Conditions ______________________________________ Reactor Pressure 175 to 225 PSIG Reactor Inlet Temperature Range 830-900.degree. F. Heat of Reaction Nil Liquid Hourly Space Velocity 0.6 to1.6 Vol/Vol/Hr. Number of Reactors, Downflow 1 Catalyst Bed Depth, Feet 11 to 15 Catalyst Density, Lb/Cu. Ft. 38 Recycle Circulation, Mols Hydrogen/Mol Hydrocarbon Feed 7.0 to 14.0 Maximum Catalyst Pressure Drop, PSI 20 ______________________________________
It will be apparent that under recommended design conditions, a considerable volume of hydrogen is introduced with the C.sub.8 aromatics. In order to increase throughput, there is great incentive to reduce hydrogen circulation with consequentincrease in aging rate of the catalyst. Aging of the catalyst occurs through deposition of carbonaceous materials on the catalyst with need to regenerate by burning off the coke when the activity of the catalyst has decreased to an undesirable level. Typically the recommended design operation will be started up at about 850.degree. F. with reaction temperature being increased as needed to maintain desired level of isomerization until reaction temperature reaches about 900.degree. F. At that pointthe isomerizer is taken off stream and regenerated by burning of the coke deposit.
Because of its capability to convert ethyl benzene, Octafining can accept a charge stream which contains that component. Normally, a portion of the ethyl benzene is removed by fractional distillation before the charge is processed. If noattempt is made to reduce ethyl benzene below a few percent by weight, this can be accomplished inexpensively and the ethyl benzene recovered is in usable form as a relatively pure chemical, e.g., for dehydrogenation to styrene.
The Octafiner is in a "loop" which includes means for separation of desired xylenes; p-xylene by crystallization and, possible, o-xylene by distillation. The C.sub.8 stream stripped of desired xylenes returns to the Octafiner where more of thedesired xylenes are generated, for example by isomerization of m-xylene. It will be apparent that ethyl benzene will tend to build up in the loop as other components are removed. The Octafining catalyst has capability for converting ethyl benzene, thuscounteracting that tendency. It, the Octafining catalyst, has the disadvantage that it is a hydrocracking catalyst due to the acid function of its silica/alumina base and its content of hydrogenation/dehydrogenation metal of the platinum group. Inaddition to converting ethyl benzene, this catalyst also causes net loss of xylenes.
Other catalysts have recently been identified as behaving in the same fashion as Octafining catalyst for isomerization of xylenes in C.sub.8 aromatic fractions accompanied by conversion of ethyl benzene. These new catalysts include zeolites ofthe ZSM-5 type, zeolite ZSM-12 .[.and zeolite ZSM-21.]. .Iadd., zeolite ZSM-35 and zeolite ZSM-38.Iaddend.. ZSM-5 type includes zeolite ZSM-5 as described in Argauer and Landolt Pat. No. 3,702,886, dated Nov. 14, 1972 and zeolite ZSM-11 as describedin Chu Pat. No. 3,709,979, dated Jan. 7, 1973 and variants thereon. Zeolite ZSM-12 is described in German Offenlegungsschrift No. 2,213,109. The activity of these catalysts for the stated purpose and of .[.ZSM-21 is.]. .Iadd.zeolites ZSM-35 andZSM-38 (there identified as ZSM-21) are .Iaddend.described and claimed in copending application of R. A. Morrison, Ser. No. 397,039, filed Sept. 13, 1973, the disclosure of which is hereby incorporated by reference.
In general, Octafining catalyst and the zeolite catalysts referred to above behave in about the same manner, except for their aging characteristics; decline of activity with time on stream.
A typical charge to the isomerizing reactor (effluent of crystallizer for separation of p-xylene) may contain 17 wt. percent ethyl benzene, 65 wt. percent m-xylene, 11 wt.% p-xylene and 7 wt. percent o-xylene. The thermodynamic equilibriumvaries slightly with temperature in a system in which o-xylene is separated in the loop by fractional distillation prior to the crystallizer. The objective in the isomerization reactor is to bring the charge as near to theoretical equilibriumconcentrations as may be feasible consistent with reaction times which do not give extensive cracking and disproportionation.
Ethyl benzene reacts through ethyl cyclohexane to dimethyl cyclohexanes which in turn equilibrate to xylenes. Competing reactions are disproportionation of ethyl benzene to benzene and diethyl benzene, hydrocracking of ethyl benzene to ethyleneand benzene and hydrocracking of the alkyl cyclohexanes.
The rate of ethyl benzene approach to equilibrium concentration in a C.sub.8 aromatic mixture is related to effective contact time. Hydrogen partial pressure has a very significant effect on ethyl benzene approach to equilibrium. Temperaturechange within the range of Octafining conditions (830.degree. to 900.degree. F.), has but a very small effect on ethyl benzene approach to equilibrium.
Concurrent loss of ethyl benzene to other molecular weight products relates to percent approach to equilibrium. Products formed from ethyl benzene include C.sub.6 + naphthenes, benzene from cracking, benzene and C.sub.10 aromatics fromdisproportionation, and total loss to other than C.sub.8 molecular weight. C.sub.5 and lighter hydrocarbon by-products are also formed.
The three xylenes isomerize much more selectively than does ethyl benzene, but they do exhibit different rates of isomerization and hence, with different feed composition situations the rates of approach to equilibrium vary considerably.
Loss of xylenes to other molecules weight products varies with contact time. By-products include naphthenes, toluene, C.sub.9 aromatics and C.sub.5 and lighter hydrocracking products.
Ethyl benzene has been found responsible for a relatively rapid decline in catalyst activity of Octafining catalyst and this effect is proportional to its concentration in a C.sub.8 aromatic feed mixture. It has been possible then to relatecatalyst stability (or loss in activity) to feed composition (ethyl benzene content and hydrogen recycle ratio) so that for any C.sub.8 aromatic feed, desired xylene products can be made with a selected suitably long catalyst use cycle.
A more recent development than Octafining is Low Temperature Isomerization (LTI) as described in Wise Pat. No. 3,377,400, dated Apr. 9, 1968. That process is particularly effective when the zeolite catalyst employed is ZSM-4 as described inBowes, et al. U.S. Pat. No. 3,578,723, dated May 11, 1971.
The advantages of LTI rest in its capbility to isomerize xylenes in liquid phase at relatively low temperatures and the lack of necessity for hydrogen pressure in the reactor. The zeolite catalyst, particularly ZSM-4, ages very slowly even withhydrogen or a hydrogenation/dehydrogenation metal component of the catalyst. However, LTI has one disadvantage. It leaves ethyl benzene unchanged.
Because the ethyl benzene content of C.sub.8 aromatic fractions is unchanged in LTI operations as practiced heretofore, such operations incur severe costs in capital investment and in operating expense to dispose of the ethyl benzene in orderthat it shall not build up in the system. Because of the minor difference in boiling point between ethyl benzene and certain of the xylenes, complete removal of ethyl benzene from the charge is prohibitive in cost. The practical way to handle thiscomponent is to provide an additional distillation column in the loop to remove ethyl benzene at substantial cost.
It has now been found that catalysts which are the acid forms of zeolite ZSM-5 type, zeolite ZSM-12 .[.or zeolite ZSM-21.]. .Iadd., zeolite ZSM-35 or zeolite ZSM-38 .Iaddend.provide C.sub.8 aromatic isomerization catalysts which not only arevery active and selective for shifting methyl groups on xylenes, but also convert ethyl benzene in a manner not previously observed for feeds of this type, if the process is conducted in the absence of substantial added hydrogen.
It is, accordingly, a primary object of this invention to isomerize the xylene content of C.sub.8 aromatic fractions, but also to convert the ethyl benzene content thereof in a novel and unexpected fashion.
As will be readily understood, the type of ethyl benzene conversion typical of Octafining (and also observed with metal ZSM-5 in the presence of hydrogen) cannot occur when hydrogen is not supplied to the reactor. It will be recalled that theconversion of ethyl benzene in Octafining proceeds by hydrogenation to ethyl cyclohexane which undergoes rearrangement to dimethyl cyclohexane. Dehydrogenation of that compound yields xylenes.
Despite the fact that the classical (Octafining) type of ethyl benzene conversion is impossible under the conditions characteristic of this invention, the conversion of that compound in the process of the invention does result in enhanced yeildof desired aromatic compounds. While not wishing to be limited by theoretical considerations, it is postulated that the alkyl side chain of ethyl benzene is cracked off the ring by the present catalysts at the conditions employed. This yeilds benzene,a valuable by-product, and ethylene. The increase in number of aromatic rings is believed to occur by way of the reaction described in U.S. Pat. application Ser. No. 153,855, filed June 16, 1971, the disclosure of which is hereby incorporated by thisreference. By whatever mechanism the reaction proceeds, the ethylene will react over HZSM-5 and other zeolites recited above to form benzene and alkyl benzenes, thus generating additional aromatic molecules from the conversion of the ethyl benzene inaddition to the benzene resultant from stripping off the alkyl group. It is perhaps surprising that this reaction will proceed in a system so heavily predominating in aromatic ring compounds which could be thought inhibitory of the reaction.
Theabove objects are attained in a process illustrated in the single FIGURE of drawings which is a diagrammatic representation of apparatus suited to practice of the invention.
A mixture of C.sub.8 aromatics is supplied to the system by line 1, as from solvent extraction of a narrow cut taken by distillation of product of reforming a petroleum naphtha over platinum on alumina catalyst in the presence of hydrogen. Thefeed passes to distillation in ethyl benzene tower 2, from which a portion of the ethyl benzene content is taken overhead by line 3. It is impracticably expensive to attempt removal of substantially all of the ethyl benzene by tower 2. The amountremoved as essentially pure ethyl benzene, suitable for charge to such operations as dehydrogenation to styrene, will depend on exact nature of the charge and demand for different products.
Bottoms from tower 2 are constituted by the xylenes present in the charge and a reduced content of ethyl benzene. This mixture passes by line 4 and is blended with recycle xylenes, derived in a manner presently to be described, from line 5. Theblended stream is admitted to splitter tower 6 from which a heavy end is withdrawn by line 7. In the embodiment shown, that heavy end is constituted by C.sub.9 + aromatics derived from the minor side reaction of transalkylation in the isomerizer. Alternatively, when it is desired to recover o-xylene as a separate product, splitter tower 6 may be operated to include o-xylene in the bottoms which are then passed to distillation for separation of o-xylene from C.sub.9 + aromatics (not shown).
The overhead of splitter tower 6 passes by line 8 to means for separation of p-xylene. In the embodiment illustrated, p-xylene is separated by fractional crystallization in crystallizer 9, involving chilling and filtration of p-xylene crystalsfrom the liquid phase, for example, in the manner described by Machell et al. U.S. Pat. No. 3,662,013, dated May 9, 1972. It will be understood that other systems for p-xylene separation may be used in a plant for practice of this invention, e.g.,selective sorption as described in Cattanach patent No. 3,699,182, dated Oct. 17, 1972. By whatever means separated, high purity p-xylene is withdrawn as product by line 10.
The stream of C.sub.8 aromatics of reduced p-xylene content is withdrawn from crystallizer 9 by line 11, passed through heater 12 and admitted to catalytic isomerizer 13 where it is contacted at reaction conditions with the acid form of ZSM-5type zeolite or zeolite ZSM-12 .[.or zeolite ZSM-21.]. .Iadd., zeolite ZSM-35 or zeolite ZSM-38.Iaddend..
The principal reaction in isomerizer 13 is shifting of methyl groups in xylene molecules toward the equilibrium concentrations of the three xylenes. In addition to xylene isomerization, secondary reactions of transalkylation occur to producebenzene, toluene, polyethyl benzenes and polymethyl benzenes. Important for the purposes of this invention is cracking of the side chain of ethyl benzene to yield benzene and ethylene. At the elevated temperatures contemplated by this invention,ethylene will react in the manner above described to produce aromatic compounds, primarily benzene.
The isomerizate produced in isomerizer 13 is transferred by line 14 through heat exchanger 15 to stripper 16. The light ends of the isomerizate (benzene, toluene and normally gaseous hydrocarbons) are taken overhead by line 17 from stripper 16and the balance passes by line 5 to be blended with fresh feed and recycled in the process.
The catalyst is prepared by converting the zeolite to "acid form" by calcination which converts tetraalkylammonium cations characteristic of these zeolites to protons by decomposition of the substituted ammonium cations. Additional protons andvarious metal cations may be substituted for the sodium cations present in the zeolites as formed by base exchange in conventional manner. It is essential to success in the present process that the zeolite catalyst be at least partially in the acidform, that is, that at least a portion of the cation positions be occupied by protons. Metal cations of various types may occupy the other sites if desired.
Since the process is conducted in the absence of added hydrogen, there is no need for metals of the transition groups such as nickel, platinum, palladium, etc. These metals may be present, but as now understood, the process appears to beunaffected by such cations.
The zeolite crystals are preferably embedded in a bonding material to provide pellets of desired size and resistance to attrition. A suitable binder is alumina. In order to provide a preponderance of the active zeolite, the binder is a minorconstituent of the composite. A particularly preferred catalyst is constituted by pellets of 35 wt. percent alumina and 65 wt. percent of the acid form of type ZSM-5 zeolite, zeolite ZSM-12 .[.or zeolite ZSM-21.]. .Iadd., zeolite ZSM-35 or zeoliteZSM-38.Iaddend..
The isomerization process of this invention is operated in the vapor phase at temperatures of 500.degree. F. to 1,000.degree. F. under pressure below that which will liquefy the charge. Aside from the need to maintain vapor phase conditions,pressure does not seem to be a critical parameter and will be dictated in the usual case by economic and engineering considerations. Pressures may range upwards from atmospheric pressure (0 pounds per square inch, gauge) but will normally be sentsomewhat higher to accommodate the process to relatively small reaction vessels. Excessively high pressures, above about 1,000 p.s.i.g. will be generally undesirable, though fully operative, because of the great strength of reaction vessel wallsrequired at high pressures, making the equipment unnecessarily expensive and requiring expensive compression stages.
Space velocities will vary in the range of 0.5 to 250 unit weights of charge per unit weight of zeolite per hour (weight hourly space velocity, WHSV). In general, temperature and WHSV will be coordinated to provide a desired severity which willprovide an adequate degree of xylene isomerization and ethyl benzene conversion without excessive losses to by-products. Thus, temperatures in the lower part of the temperature range will normally call for low space velocities.
The catalyst employed was 65 wt. percent HZSM-5 (the acid form of ZSM-5 prepared by ammonium exchange and calcining) in 35 wt. percent alumina. The run was conducted at 950.degree. F., atmospheric pressure and 21 WHSV based on zeolite contentonly of the catalyst. The nature of the conversion will be apparent from a tabulation of feed and product compositions:
TABLE I ______________________________________ Feed,wt. % Product, wt. % ______________________________________ Light Ends -- 0.1 Ethyl benzene 25.8 6.2 Benzene 0.0 11.8 Toluene 1.0 4.9 p-xylene 10.2 17.6 m-xylene 53.1 39.3 o-xylene 9.918.9 C.sub.9 + 0.0 1.2 TOTAL XYLENES 73.2 75.8 ______________________________________
It will be seen that under the relatively high severity of this run, major conversion of ethyl benzene is accomplished. The very extensive reaction of ethyl benzene on this acid catalyst, accompanied by isomerization of the xylenes is highlyadvantageous for commercial operations,
Using the same catalyst as that described in Example 1, a run was made at 540.degree. F., pressure of 150 p.s.i.g. and WHSV of 4. The results shown in Table II report conversion after more than 10 hours on stream.
TABLE II ______________________________________ Wt. % of Feed Product, xylene portion wt. % wt. % of product ______________________________________ Ethyl benzene 16.2 15.0 -- Benzene -- 0.4 -- Toluene -- 0.2 -- p-xylene -- 20.2 24.1 m-xylene 61.2 45.1 53.9 o-xylene 22.6 18.4 22.0 C.sub.9 + -- 0.7 -- ______________________________________
This example illustrates effectiveness of zeolites according to the invention which have been treated to incorporate both protons and metal cations. Zeolite ZSM-5 was base exchanged with ammonium and nickel salts, incorporated in alumina to forma composite catalyst containing 65 wt. percent NiHZSM-5 and 35 wt. percent alumina. The composite catalyst analyzed 0.68 wt. percent nickel and 0.05 wt. percent sodium. The composite was formed into one-sixteenth inch extrudate and admixed with tabularalumina (inert) to facilitate operation at high space velocity. The admixture contained 12.5 vol. percent of NiHZSM-5/alumina composite and 87.5 vol. percent of tabular alumina.
The conditions and product yield are set out in Table III.
TABLE III ______________________________________ C.sub.8 Aromatics Isomerization NiHZSM-5 Catalyst Charge, wt. %: 17.2 EB, 10.7 p-xyl, 65.6 m-xyl, 6.5 o-xyl ______________________________________ Temperature, .degree.F. 600 Pressure, PSIG200 WHSV (on zeolite) 2 H.sub.2 /HC 0 Time on Stream, Hrs. 21.4 Material Balance 95.7 Product Distribution wt. % C.sub.1 -- C.sub.2 0.03 C.sub.3 0.1 i-C.sub.4 -- n-C.sub.4 -- i-C.sub.3 -- C.sub.6 H.sub.6 2.1 C.sub.7 (alkyl) -- Toluene 1.6 C.sub.8 (alkyl) -- ______________________________________ -C.sub.8 aromatics on total and on C.sub.9 aromatics Total C.sub.8 Ar ______________________________________ EB 11.2 12.0 m-xylene 44.9 47.9 p-xylene 19.0 20.3 o-xylene 18.5 19.8 C.sub.9Aromatics 2.6 Wt. % Conversion to Non-Aromatics 0.1 Wt. % loss C.sub.8 Aromatics 6.4 ______________________________________
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