PROCESS FOR THE CATALYTIC CRACKING OF A HYDROCARBON FEEDSTOCK

Abstract: Process for the catalytic cracking of a hydro­ carbon feedstock, comprising contacting the feedstock with a catalyst composition comprising a zeolite I having a pore diameter larger than 0.7 nm and a zeolite II having a pore diameter smaller than 0.7 nm, which composition further comprises at least one dehydrogenating metal or metal component, under catalytic cracking conditions.

Description: The present invention relates to a process for the catalytic cracking of a hydrocarbon feedstock by contacting the feedstock with a suitable catalyst composition at catalytic cracking conditions. Catalytic cracking is a refining process which is applied commercially on a large scale. In this process heavy hydrocarbon fractions are converted into lighter and less viscous products. The conversion or cracking takes mainly place in the vapour phase in the presence of a catalyst. The feedstock is so converted into e.g. gasoline. Part of the feedstock is converted into gas consisting of four or less carbon atoms per molecule. The gas partly consists of olefins and partly of saturated hydrocarbons. During the cracking reactions some heavy material, known as coke, is deposited onto the catalyst. This reduces its catalytic activity and regeneration is desired. Regeneration is accomplished by burning off the coke and then the catalyst activity is restored. Therefore three steps can be distinguished in the process, viz. a cracking step in which the hydrocarbons are converted into lighter products, a stripping step to remove hydrocarbons adsorbed on the catalyst and a regeneration step to burn off coke from the catalyst. The regenerated catalyst is then reused in the cracking step. As catalysts for catalytic cracking, zeolites in an amorphous matrix have been found to be very effective. In particular zeolites having relatively large pores, i.e. having pore diameters larger that 0.7 nm, are very suitable. From EP-B-0,131,986 catalyst compositions are known comprising a zeolite I with large pores and a zeolite II, being a ZSM-5-type zeolite, with a pore diameter of smaller than 0.7 nm. Similar catalyst compositions are also known from DE-A-2,149,218. In GB-A-1 486 927 a method for the cracking of hydrocarbons is described wherein a hydrocarbonaceous feedstock is contacted with a two-zeolite catalyst composition consisting of a type-Y zeolite and a commercial mordenite, identified as Zeolon H. In "Molecular Sieve Catalysts", P. Michiels and O.C.E. De Herdt, EPO Applied technology series-volume 9, at page 40 it is indicated that mordenite zeolites generally used have an effective pore diameter of about 6 to 10 Å. Further, it has been indicated that the mordenite Zeolon H is called a "large pore" mordenite. Accordingly mordenite Zeolon H may be classed rather as a zeolite having a pore diameter above 7 Å, instead of a zeolite having a pore diameter below 7 Å. Thus, both zeolite catalyst components in GB-A-1 486 927 comprise essentially a zeolite having a pore diameter larger than 0.7 nm. Moreover, GB-A-1 486 927 is totally silent about a very light feedstock component is to be converted together with a heavy feedstock component. In EP-A-0 021 787 a cracking process is disclosed wherein use is made of a catalyst composition containing a ZSM-5 component and a Zeolite Y component. The catalyst can further be provided with a trace amount of a metal such as platinum to promote combustion of carbon monoxide to the dioxide in the regenerator. Hydrocarbonaceous feedstocks comprising light hydrocarbons, such as a gaseous stream of C₂-C₅ hydrocarbons, as a feedstock component is not mentioned at all, let alone suggested as possible feedstock components. In GB-A-1 058 189 a catalytic cracking process is described wherein an oil is contacted with an aluminosilicate having a pore size less than 7 Angstrom units and a cracking catalyst of generalized competence. GB-A-1 058 189 is totally silent about C₂-C₅ hydrocarbons feedstock components. As stated hereinbefore, part of the feedstock that has been cracked has been converted into a gaseous fraction. Part of this gaseous fraction is saturated and has a relatively low intrinsic value. It would therefore be advantageous if one could amend the process and/or catalyst such that hardly any saturated gaseous compound will be formed. Surprisingly, it has now been found that the yield of saturated gaseous components is reduced if the catalyst composition further contains a dehydrogenating metal or metal component. Accordingly, the invention provides a process for the catalytic cracking of a hydrocarbon feedstock, comprising contacting the feedstock with a catalyst composition comprising a zeolite I having a pore diameter larger than 0.7 nm and a zeolite II having a pore diameter smaller than 0.7 nm, which composition further comprises at least one dehydrogenating metal or metal component, under catalytic cracking conditions whereby the feedstock comprises hydrocarbons having a boiling point of at least 330 °C and hydrocarbons having from 2 to 5 carbon atoms. The surprising nature of the present invention is illustrated by US-A-4,100,218, which describes a process for the preparation of LPG (saturated C₃₋₄-hydrocarbons) and gasoline starting from an olefinic stream, using a zeolitic catalyst having a pore diameter of less than 0.7 nm, which catalyst may contain a metal component, e.g. a dehydrogenating Group 8 metal. Since it was known that zeolites, hereinabove indicated as zeolite II, have activity to promote the conversion of olefins to saturated gaseous hydrocarbons, it is surprising that according to the present invention olefinic gaseous hydrocarbons are formed. The dehydrogenating metal or metal component is present on the zeolitic catalyst composition. It is possible to distribute the dehydrogenating metal (component) over both zeolites. In the latter case the dehydrogenating activity is effected on the complete feedstock. It is believed that when the dehydrogenating metal (component) is present only on the zeolite II, the dehydrogenating activity is effected only on those molecules which can enter the pores of the zeolite II. Basically that means that only linear and/or relatively small molecules will be subjected to the dehydrogenating activity of the metal. Since one of the objects of the invention is to convert linear and/or relatively small molecules including C₆-C₈ cyclic groups, e.g. naphthenes into small olefins or aromatics, the case in which only zeolite II comprises a dehydrogenating metal is preferred. The amount of the dehydrogenating metal or metal component may vary within wide ranges. Very small amounts, i.e. in the ppm range, show a dehydrogenating activity which is too low for commercial practice. Therefore, the amount of dehydrogenating metal (component) is preferably from 0.5 to 20 %wt, calculated as metal and based on zeolite II. The dehydrogenating metal that can be used can be selected from many metals. Suitable metals include those of Group 2b, in particular zinc, and of Group 3a, in particular gallium. It is however preferred to select a Group 8 and/or a Group 6b metal or metal component. More preferably, the metal is selected from the group consisting of platinum, palladium, nickel, cobalt, molybdenum, tungsten and mixtures thereof. When one of the noble metals is used, e.g. platinum or palladium, the Group 8 metal is preferably present in the metallic form. When a non-noble metal is employed, e.g. nickel and/or cobalt and/or molybdenum and/or tungsten, the dehydrogenating metal is preferably used in its oxidic, sulphidic or metallic form. The weight percentage of zeolite I to the sum of zeolites I and II may vary. Suitably the percentage amounts from 0.1 to 30 %wt, more preferably, the weight percentage of zeolite I to the sum of zeolites I and II ranges from 1 to 10 %wt. The catalyst composition used in the present process comprises two zeolites. In one embodiment of the present invention the catalyst composition includes a physical mixture of at least two cracking components, one comprising a zeolite I and another comprising a zeolite II. In this embodiment the composition comprises a mixture of catalyst particles that contain only one of both zeolites. It will be clear to the man skilled in the art that the catalyst particles may further comprise a matrix material, such as an refractory oxide, e.g. silica, alumina, silica-alumina, magnesia, thoria, titania and zirconia. In another embodiment of the present invention, which is preferred, the catalyst composition comprises an intimate mixture of the zeolites I and II in a porous matrix material. That implies that a catalyst particle contains both zeolites. Zeolite I has a pore diameter greater than 0.7 nm. The pore diameters of suitable zeolites I can be as large as 1.2 nm. Suitable zeolites I include the faujasite-type zeolites and zeolite L. Faujasite-type zeolites, including zeolites X and Y, are preferred; in particular zeolite Y is preferred. The zeolite can be in its acidic form, i.e. the form in which the zeolite hardly contains any alkali metal ions. It is also possible to load the zeolite with a dehydrogenating metal as described hereinabove. Preferably the zeolite I comprises rare earth metals. The latter metals may have been incorporated onto the zeolite by any conventional method. In particular ion-exchange is a very suitable method. The zeolite II has a pore diameter smaller than 0.7 nm. The pore diameter can be as low as 0.4 nm. Suitable zeolites II include crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TASO), boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates. Examples of zeolites II that may be used in the process of the invention and that have a pore diameter of 0.4 to 0.7 nm, include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,500,651, TASO-45, described in EP-A-229,295, boron silicates, described in e.g. US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-23, and ZSM-38. Preferably the zeolite is selected from the group consisting of crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof. Suitable examples of crystalline metal silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or chromium silicates as described in e.g. GB-B-2,110,559. The pore diameters of these silicates are in the range of 0.5-0.6 nm. The zeolite II is preferably not in its acidic form. This can be accomplished by having the dehydrogenating metal (components) occupy the potentially acidic sites. It is also possible to allow the zeolite II to be in its alkali metal form. By avoiding the presence of a great number of acidic sites on zeolite II the risk of overcracking of relatively small molecules is reduced. The preparation of the catalyst composition used in the process according to the present invention can be done by any conventional method, such as ion-exchange, (co)precipitation, impregnation, (co)mulling etc. A suitable method is to prepare a zeolite II containing a dehydrogenating metal component via one or more conventional methods and incorporating this loaded zeolite together with a matrix material and a zeolite II into catalyst particles. The process is carried out under catalytic cracking conditions. This implies that the process is advantageously carried out in the absence of added hydrogen. Preferably the process is carried out in an upwardly or downwardly moving catalyst bed. Suitably the process is carried out in the manner of conventional Thermofor Catalytic Cracking (TCC) or Fluidised Catalytic Cracking (FCC) processes. The process conditions are preferably a temperature of 400 to 650 °C, in particular 450 to 600 °C, a pressure of 1 to 10 bar, in particular 1 to 7.5 bar, a weight hourly space velocity of 1 to 250 kg/kg.h, in particular 5 to 150 kg/kg.h and a catalyst composition/feedstock weight ratio of 1 to 25, in particular 1.5 to 20. The feedstock that can be used in the present process includes conventional catalytic cracking feedstocks, such as (vacuum) gas oils, deasphalted residual oils, and long or short residues, provided that they comprise hydrocarbons having a boiling point of at least 330 °C. An advantage of the present invention resides in the inclusion in the feedstock of additional hydrocarbons having from 2 to 5 carbon atoms. These small molecules will be dehydrogenated to yield valuable olefins. The feedstock may consist of a mixture of gaseous (C₂₋₅) hydrocarbons, naphtha, kerosine, gasoil, vacuum distillates and vacuum residual fractions. Preferably, the feedstock consists of a mixture of a conventional catalytic cracking feedstock as defined hereinabove and a gaseous stream of C₂₋₅ hydrocarbons. The amount of hydrocarbons with 2 to 5 carbon atoms in the feedstock is preferably from 1 to 20 %wt, based on the weight of the hydrocarbons with a boiling point of at least 330 °C and the hydrocarbons having from 2 to 5 carbon atoms. The hydrocarbons having 2 to 5 carbon atoms in the molecule may accrue from a variety of sources. Suitable sources include straight run LPG, gaseous products from hydrotreatment and/or hydrocracking processes, waste streams from alkylation processes or catalytic dewaxing processes and the like. The hydrocarbons with 2 to 5 carbon atoms preferably comprise an LPG fraction, i.e. propane and/or butanes. Preferably, the hydrocarbons having 2 to 5 carbon atoms in the molecule at least partly originate from a recycle stream obtained in the present process. In the present process olefins are formed, nut an amount of saturated compounds remain unconverted. After separation of the unconverted hydrocarbons these are conveniently recycled to the present process.

Claims: 1. Process for the catalytic cracking of a hydrocarbon feedstock, comprising contacting the feedstock with a catalyst composition comprising a zeolite I having a pore diameter larger than 0.7 nm and a zeolite II having a pore diameter smaller than 0.7 nm, which composition further comprises at least one dehydrogenating metal or metal component, under catalytic cracking conditions, whereby the feedstock comprises hydrocarbons having a boiling point of at least 330 °C and a stream of hydrocarbons having from 2 to 5 carbon atoms. 2. Process according to claim 1, in which the amount of hydrocarbons with 2 to 5 carbon atoms in the feed is from 1 to 20 %wt, based on the weight of hydrocarbons with a boiling point of at least 330 °C and the hydrocarbons with 2 to 5 carbon atoms. 3. Process according to claim 1 or 2, in which the hydrocarbons having 2 to 5 carbon atoms in the molecule at least partly originate from a recycle stream obtained in the present process. 4. Process according to any one of claims 1 to 3, in which hydrocarbons with 2 to 5 carbon atoms include an LPG fraction. 5. Process according to any one of claims 1-4, in which only zeolite II comprises the dehydrogenating metal or metal component. 6. Process according to any one of claims 1-5, in which in the catalyst composition the amount of dehydrogenating metal or metal component is from 0.5 to 20 %wt, based on zeolite II. 7. Process according to any one of claims 1 to 6, in which the dehydrogenating metal has been selected from a Group 6b and/or a Group 8 metal. 8. Process according to claim 7, in which the metal has been selected from the group consisting of platinum, palladium, nickel, cobalt, iron, tungsten, molybdenum and mixtures thereof. 9. Process according to any one of claims 1 to 8, in which in the catalyst composition the weight percentage of zeolite I to the sum zeolites I and II ranges from 0.1 to 30 %wt. 10. Process according to any one of claims 1 to 9, in which the catalyst composition includes a physical mixture of catalyst particles containing zeolite I and catalyst particles containing zeolite II. 11. Process according to any one of claims 1 to 10, in which the catalyst composition comprises an intimate mixture of the zeolites I and II in a porous matrix. 12. Process according to any one of claims 1 to 11, in which zeolite I in the catalyst composition includes a faujasite-type zeolite. 13. Process according to claim 12, in which the faujasite is a zeolite Y. 14. Process according to claim 12 or 13, in which the faujasite contains rare earth metals. 15. Process according to any one of claims 1 to 14, in which the zeolite II is selected from crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof. 16. Process according to any one of claims 1 to 14, in which zeolite II is substantially in its alkali metal form. 17. Process according to any one of claims 1 to 16, which is carried out in the absence of added hydrogen. 18. Process according to any one of claims 1 to 17, which is carried out in an upwardly or downwardly moving catalyst bed. 19. Process according to any one of claims 1 to 18, which is carried out at a temperature of 400 to 650 °C, a pressure of 1 to 10 bar, a space velocity of 1 to 250 kg/kg.h and a catalyst composition/feedstock weight ratio of 1 to 25.

Inventors: BISWASS, JAYDEEP, MAXWELL, IAN ERNEST
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1989
Main classification: C10G11
IPC codes: B01J29, C10G11