MX2009000566A - Hydrocracking catalyst containing beta and y zeolites, and process for its use to make distillate. - Google Patents

Abstract

Increased selectivity of middle distillate and/or increased catalyst activity are obtained in a hydrocracking process by the use of a catalyst containing a beta zeolite and a Y zeolite having a unit cell size of from 24.25 to 24.32 angstrom. The catalyst may also contain an additional Y zeolite having a unit cell size of from 24.33 to 24.38 angstrom.

Description

HYDRODISINTEGRATION CATALYST CONTAINING BETA ZEOLITES AND ZEOLITES AND, AND PROCESS FOR USING IN THE PRODUCTION OF DISTILLATES FIELD OF THE INVENTION The present invention relates to catalyst compositions and their use in hydrocarbon conversion processes, particularly hydrodisintegration. More specifically, the present invention relates to a catalyst composition comprising a Y zeolite and a beta zeolite as active components of disintegration. The present invention relates specifically to a hydrodisintegration process that produces middle distillates. BACKGROUND OF THE INVENTION Petroleum refiners often produce desirable products such as turbosine, diesel and other liquid hydrocarbons known as middle distillates, as well as lower boiling liquids such as naphtha and gasoline, by hydrodisintegrating a hydrocarbon feedstock derived from crude oil. . Hydrodisintegration also has other beneficial results, such as removing sulfur and nitrogen from the feed through hydrotreating. The feed charges that are most frequently subject to hydrodisintegration are diesel and heavy gas oil recovered from crude oil by distillation.

Hydrodisintegration is generally carried out by contacting, in a suitable reactor vessel, diesel fuel or other hydrocarbon feedstocks with a suitable hydrodisintegration catalyst under appropriate conditions, including an elevated temperature and high pressure, and the presence of hydrogen, to produce an overall product of lower average boiling point that contains a distribution of desired hydrocarbon products by the refiner. Although the operating conditions in a hydrodisintegration reactor have some influence on the product yield, the hydrodisintegration catalyst is a major factor in determining these yields. The hydrodisintegration catalysts are subject to an initial classification based on the nature of the predominant decay component of the catalyst. This classification divides the hydrodisintegration catalysts into those based on an amorphous disintegration component such as silica-alumina, and those based on a zeolitic disintegration component such as zeolite beta or Y. Hydrodegradation catalysts are also subject to classification based on the product predominantly desired to be obtained from these, where the two main products are naphtha and "distilled", a term that in the technique of refining by hydrodisintegration refers to distillate oil derived from fractions whose boiling range is higher than that of naphtha. Distillate typically includes products recovered in a refinery, such as kerosene and diesel. Currently, the distillate is in great demand. For this reason, refiners have focused on hydrodisintegration catalysts that selectively produce a fraction of distillate. The three main catalytic properties with which the operation of a hydrodisintegration catalyst is evaluated to produce a distillate are activity, selectivity, and stability. The activity can be determined by comparing the temperatures at which various catalysts must be used, under otherwise constant hydrodisintegration conditions with the same feed load, to produce a given percentage, typically 65 percent, of products that boam in the range desired, that is, less than 371 ° C for the distillate. The lower the temperature required for a given catalyst, the more active the catalyst is in relation to a catalyst that requires a higher temperature. The selectivity of the hydrodisintegration catalysts can be determined during the activity test described above, and measured as a percentage of the fraction of the product that boils over the range of the desired distillate, ie from 149 to 371 ° C. Stability is a measure of the degree to which a catalyst maintains its activity for a prolonged period, when treating a hydrocarbon feedstock given the conditions of the activity test. Stability is usually measured in terms of the change in temperature required per day to maintain a given conversion of 65 percent, or different. Although the disintegration catalysts for producing distillates are known and used in commercial environments, there is always a demand for new hydrodisintegration catalysts of selectivity higher than a given activity, or an activity greater than a given selectivity for producing distillates. SUMMARY OF THE INVENTION It has been discovered that hydrodisintegration catalysts containing a Y zeolite with a unit cell size or dimension a0 between 24.33 and 24.38 angstroms (hereinafter referred to as zeolite YI) and containing a beta zeolite, preferably with a molar ratio of silica versus alumina (Si02 versus A1203) less than 30, and an SF6 adsorption capacity of at least 28 weight percent (hereinafter referred to as% weight), have significantly improved the selectivity to a given activity , or have significantly improved the activity at a given selectivity, compared to other commercially available hydrodisintegration catalysts in the Currently to be used in hydrodisintegration processes to produce distillates. The catalyst also contains a metallic hydrogenation component such as nickel, cobalt, tungsten, molybdenum or any combination thereof. The catalyst contains from 0.1 to 2% by weight of zeolite beta based on the combined weight of the zeolite beta, the zeolite YI, and the support based on the dry weight, and the catalyst has a weight ratio of the zeolite YI against beta zeolite from 1 to 10 based on dry weight. The zeolite Y I has a general molar ratio of silica versus alumina of between 5.0 and 11.0. In one embodiment, the catalyst contains an additional Y zeolite with a larger unit cell size than that of the additional zeolite. It is thought that a hydrodisintegration catalyst containing this beta zeolite and this Y zeolite is new in the art. Under typical hydrodisintegration conditions, including elevated temperature and pressure and the presence of hydrogen, these catalysts are highly effective in converting diesel and other hydrocarbon feed charges to products of lower average boiling point and lower average molecular weight. In one embodiment, the product contains a relatively large proportion of components that boil in the range of distillates, which is defined herein as being between 149 and 371 ° C.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of the selectivity of the distillate versus the relative activity of the catalyst for various hydrodisintegration catalysts. Fig. 2 is a graph of the ratio of the selectivity of heavy distillates against the selectivity of light distillates, versus the relative activity of the catalyst for various hydrodisintegration catalysts. INFORMATION DISCLOSURE Y and beta zeolites have been proposed in combination as components of various catalysts, including hydrodisintegration catalysts. For example, U.S. Pat. 5,275,720, 5,279,726 and 5,350,501 disclose hydrodisintegration processes using a catalyst comprising a beta zeolite and a Y zeolite. 5,350,501 describes a hydrodisintegration process using a catalyst comprising, among other components, a zeolite beta and a zeolite Y with a unit cell size between 24.25 and 24.35 angstroms, and a water vapor sorption capacity at a partial pressure of Water vapor of 4.6 and 25 ° C lower than 8.0 percent of the weight of the zeolite. The application US-A1-2004 / 0152587 describes a hydrodisintegration catalyst comprising a vehicle comprising a zeolite with the faujasite structure with a unit cell size in the range of 24.10 to 24.40 angstroms, a ratio of silica to alumina of more than 12, and a surface area of at least 850 m2 / g, and the catalyst can contain a second zeolite as zeolite beta, zeolite ZSM-5 or a zeolite Y with a different unit cell size. Two different Y zeolites have been proposed in combination as components of several different catalysts, including hydrodisintegration catalysts, as described in U.S. Pat. 4,661,239 and 4,925,546. DETAILED DESCRIPTION OF THE INVENTION The process and composition disclosed herein can be used to convert a feedstock containing organic compounds into products, particularly by acid catalysis, such as hydro-disintegrating organic compounds, especially hydrocarbons, into a lower boiling product. medium and lower average molecular weight. The composition, which can be a catalyst or catalyst support, comprises a zeolite beta and a zeolite Y I. The composition may also comprise a refractory inorganic oxide. When used as a hydrodisintegration catalyst, the composition contains a beta zeolite, a Y-zeolite, a refractory inorganic oxide, and a hydrogenation component. The process and composition of hydrodisintegration disclosed herein focuses on using a catalyst containing a particular beta zeolite and a particular Y zeolite. Optionally, the composition may contain an additional Y zeolite. The zeolite beta preferably has a relatively low molar ratio of silica to alumina and a relatively high SF6 adsorption capacity. Zeolite Y I has a unit cell size between 24.25 and 24.32 angstroms. If present, the additional zeolite has a larger unit cell size than the Y zeolite. It has been found that distinct performance results occur when this zeolite beta and these Y zeolites are incorporated in hydrodisintegration catalysts in this way. In comparison with catalysts containing one or two Y zeolites, the selectivity of products that boil in the range of distillates is greater than a given activity, or the activity is greater than a given product selectivity that bubbles in the range of the distillates. Beta zeolite is well known in the art, as a component of hydrodisintegration catalysts. The zeolite is described in U.S. Pat. No. 3,308,069 and the reissue in the USA. No. 28341, which are hereby incorporated by reference in their entirety. The beta zeolite used in the process and composition disclosed herein has a molar ratio of silica to alumina of less than 30 in one embodiment, less than 25 in another modality, more than 9 and less than 30 in another modality, more than 9 and less than 25 in another modality, more than 20 and less than 30 in another modality, or more than 15 and less than 25 in another modality plus. As used herein, and unless otherwise indicated, the molar ratio of silica to alumina (SiO2 to AI2O3) of a zeolite is the molar ratio determined on the basis of the total or general amount of aluminum and silica (structural and non-structural) present in the zeolite, and to which it is sometimes referred to as the general molar ratio of silica to alumina (SiO2 against A1203). Beta zeolite is generally synthesized from a reaction mixture containing a template agent. The use of template agents to synthesize zeolite beta is well known in the art. For example, U.S. Pat. No. 3, 308,069 and its re-issue in the USA. No. 28341 describe the use of tetraethylammonium hydroxide, and U.S. Pat. No. 5, 139,759, which is incorporated in its entirety by reference, describes the use of the tetraethylammonium ion of the corresponding tetraethylammonium halide. Another conventional method for preparing beta zeolite is described in the book entitled Verified Synthesis of Zeolitic Materials, by H. Robson (editor) and KP Lillerud (XRD standards), second revised edition, ISBN 0-444-50703-5, Elsevier, 2001 It is thought that The choice of a particular template agent is not of critical importance for the success of the process that is revealed in the present. In one embodiment, the zeolite beta is calcined in air at a temperature of between 500 and 700 ° C for a sufficient time to remove the template agent from the beta zeolite. The calcination to remove the template agent can be carried out before or after combining the beta zeolite with the support or the hydrogenation component. Although it is thought that the template agent could be removed at calcination temperatures of more than 700 ° C), too high calcination temperatures could significantly decrease the SF6 adsorption capacity of the beta zeolite. For this reason, it is thought that calcination temperatures of more than 750 ° C should be avoided to remove the template agent when preparing the beta zeolite for use in the process disclosed herein. For the process disclosed herein it is critical that the SF6 adsorption capacity of the zeolite beta be at least 28% by weight. While it is known that steaming a zeolite like beta produces changes in the crystalline structure of zeolite, the capabilities of current analytical technology have not made it possible to accurately monitor or characterize these changes in terms of the most important structural details of the zeolite. Instead, measurements of various physical properties of the zeolite, as a surface area, to indicate the changes occurred and the degree of these changes. For example, it is thought that a reduction in the ability of the zeolite to adsorb sulfur hexafluoride (SF6) after being steam treated is caused by a reduction in the crystallinity of the zeolite or in the size or accessibility of the micropores of the zeolite. zeolite However, what may be undesirable is an indirect correlation of the changes in the zeolite, since the adsorption capacity of SF6 in the catalyst used in the process and composition disclosed herein is relatively high. In the embodiments of the process and composition disclosed herein, the SF6 adsorption capacity of the zeolite beta, steam treated or not, should be at least 28% by weight. Accordingly, the beta zeolite of the process and composition disclosed herein can be characterized in terms of SF6 adsorption. There is a recognized technique for the characterization of microporous materials such as zeolites. It is similar to other measurements of adsorption capacity, such as water capacity, in the sense that it uses weight differences to measure the amount of SF6 adsorbed by a sample that has been pretreated to be essentially free of adsorbate. In this test SF6 is used since its size and shape prevents its entry into pores with diameters less than 6 angstroms. Therefore, it can be used as a measurement of pore entries and shrinkage of pore diameters. This, in turn, is a measurement of the effect of the steam treatment on the zeolite. In a simplistic description of this measurement method, preferably the sample is first vacuum pre-dried at 300 ° C for one hour, then heated at atmospheric pressure in air at 650 ° C for two hours, and finally weighed. Then it is exposed to SF6 for one hour, keeping the sample at a temperature of 20 ° C. The vapor pressure of SF6 produced by liquid SF6 at 400 torr (53.3 kPa) is maintained. The sample is then reweighed to measure the amount of SF6 adsorbed. You can suspend the sample on a scale during these steps, to facilitate them. In any mass production process involving techniques such as heating and steam treatment there is the possibility that some particles are subjected to different levels of treatment. For example, particles at the bottom of a stack that moves through a rotary kiln may not be subject to the same atmosphere or temperature as the particles that cover the top of the stack. It is necessary to consider this factor during production, as well as during the analysis and testing of the finished product. Therefore, it is recommended to perform any test measurement of the material in a composite sample representative of the entire quantity of the product finished, to avoid confusion with measurements made with individual particles or with a non-representative sample. For example, an adsorption capacity measurement is performed on a representative composite sample. Although the process and composition disclosed herein may utilize a beta zeolite not subject to steam treatment, the process and composition disclosed herein may also utilize a beta zeolite that has been subjected to steam treatment, as long as the treatment is relatively mild compared to the steam treatment of zeolite beta that is described in the literature. Under the appropriate conditions and for the appropriate time, the steam treatment of zeolite beta can produce a catalyst that can be used in the process and composition disclosed herein. The hydrothermal treatment of zeolites for use in hydrodisintegration catalysts is a relatively imprecise tool. For any given zeolite, the steam treatment decreases the acidity of the zeolite. When the steam-treated zeolite is used as the hydrodisintegration catalyst, the apparent result is that it increases the general yield of the distillates, but the activity of the catalyst decreases. This apparent balance between performance and activity has meant that getting high Activity means not steaming zeolite beta, although at the expense of lower product yield. This apparent balance between performance and activity should be considered, and is a limit to the improvement that appears to be obtained by steam treatment of zeolite beta. When the steam-treated zeolite beta is used in the catalysts disclosed herein, the improvement in activity relative to the catalysts containing only Y zeolite would seem limited, while the increase in yield with respect to such catalysts would appear to be improved. If the zeolite beta is steamed, it can be effectively carried out in different ways, and the method that is used is often influenced and sometimes dictated by the type and capacity of the available equipment. The steam treatment can be carried out by keeping the beta zeolite as a fixed mass, or by confining the beta zeolite in a container or by stirring it while it is confined in a rotary kiln. The most important factors are a uniform treatment of all the zeolite beta particles under appropriate conditions of time, temperature and vapor concentration. For example, zeolite beta should not be placed under conditions where there is a significant difference in the amount of vapor contacting the surface and the interior of the zeolite beta mass. Beta zeolite can be steam treated in an atmosphere with live steam passing through the equipment, providing low vapor concentration. This could be described as a vapor concentration of a positive amount of less than 50 mol%. Steam concentrations can vary from 1 to 20 mol%, or from 5 to 10 mol%, with small-scale laboratory operations extending to higher concentrations. The steam treatment may be carried out for a positive period less than or equal to 1 or 2 hours, or for 1 to 2 hours at a temperature less than or equal to 600 ° C at atmospheric pressure and with a positive vapor content less than or equal to 5 % molar. The steam treatment can be carried out for a positive period less than or equal to 2 hours at a temperature less than or equal to 650 ° C at atmospheric pressure and with a positive vapor content less than or equal to 10 mol%. The content of the steam is based on the weight of the vapors that contact the beta zeolite. Steam treatment at temperatures above 650 ° C appears to produce a beta zeolite which is not useful in the process disclosed herein, since the SF6 adsorption capacity of the resulting zeolite beta is too low. Temperatures of less than 650 ° C may be used, and the temperature of the steam treatment may be 600 to 650 ° C, or less than 600 ° C. It is taught in the art that there is usually an interaction between the time and temperature of the steam treatment, where an increase in temperature reduces the time required. However, if the steam treatment, it seems that a lapse of between ½ to 2 hours or 1 to 1½ hours can be used to obtain good results. The method for carrying out steam treatment on a commercial scale can be with a rotary kiln to which steam is injected at a rate that maintains an atmosphere of 10 mol% vapor. An exemplary steam treatment on a laboratory scale is to put the zeolite in a 6.4 cm quartz tube in an oven. A controller slowly increases the oven temperature. When the temperature of the zeolite reaches 150 ° C, steam, generated by deionized water contained in a flask, is allowed to enter the bottom of the quartz tube, and then pass upwards. Another gas can be passed to the tube to obtain the desired vapor content. The flask can be refilled as necessary. In the exemplary process, the time elapsed between closing the steam passage and the zeolite reaching 600 ° C is one hour. At the end of the period set for the steam, the temperature in the oven is reduced, setting the controller back to 20 ° C. The oven is allowed to cool to 400 ° C (about 2 hours), and the flow of steam to the quartz tube is stopped. The sample is removed at 100 ° C, and placed in a laboratory oven maintained overnight at 110 ° C, with an air purge. The beta zeolite of the process and composition disclosed herein is not treated with an acid solution for perform the dealuminization. In this regard, it is noted that essentially all the synthesized beta zeolite is exposed to an acid to reduce the concentration of alkali metal (ie sodium), but not during the synthesis. This step in the production process of the zeolite beta is not considered part of the treatment of the zeolite beta produced as described herein. In one embodiment, during the treatment and catalyst manufacturing processes, zeolite beta is exposed to an acid only during incidental production activities, such as peptization during formation or during metal impregnation. In another embodiment, the beta zeolite is not washed with acid after steam treatment to remove aluminum "debris" from the pores. A Y zeolite with a unit cell size between 24.25 and 24.32 angstroms is also included in the process and composition disclosed herein. This zeolite Y is sometimes referred to herein as "zeolite Y I", in order to distinguish this Y zeolite from an optional additional Y zeolite with a different unit cell size, and which will be described later. The zeolite Y I preferably has a unit cell size between 24.26 and 24.30 angstroms. The zeolite Y I can have a general molar ratio of silica versus alumina of between 5.0 and 12.0 in one mode, from 5.0 to 11.0 in another mode, and from 5.0 to 10.0 in another mode more mode. The process and composition disclosed herein requires a Y zeolite. Optionally, and in addition to the zeolite Y I, the disclosed process and composition may include an additional Y zeolite, which is sometimes referred to herein as "zeolite Y II". The zeolite Y II has a unit cell size different from the unit cell size of the Y zeolite. The unit cell size of the Y zeolite II is preferably at least 0.04 angstroms greater than the unit cell size of the Y zeolite I The unit cell size of zeolite Y II is more preferably from 24.33 to 24.38 angstroms, and even more preferably from 24.34 to 24.36 angstroms. Zeolite Y II can have a general mole ratio of silica versus alumina of between 5.0 and 12.0 in one embodiment, 5.0 to 11.0 in another embodiment, and 5.0 to 10.0 in another embodiment. The option of adding zeolite Y II during the production process allows catalyst producers the flexibility to manufacture products that meet the requirements of each hydrodisintegration unit operator. The presence of zeolite Y II in the catalyst changes the properties of the catalyst without the need to change how the zeolite Y I itself is prepared, or the amount of zeolite Y I used in the catalyst. However, in certain instances, adding zeolite Y II decreases the need for Y1 zeolite, which is a further advantage when the relative cost of Y1 zeolite production is high, or when sufficient quantities of Y zeolite are not available. Operators of hydrodisintegration units, especially those producing distillates, can use catalysts containing both zeolite YI and zeolite Y II as a way to meet their particular and sometimes one-of-a-kind needs for the activity and selectivity of the hydrodisintegration catalyst. As the term "Y zeolite" is used herein, it encompasses all crystalline zeolites with the powder X-ray diffraction pattern described in U.S. Pat. No. 3,130,007, or a Y zeolite modified with a powder X-ray diffraction pattern similar to that of U.S. Pat. No. 3,130, 007 although with the separations "d" slightly displaced due to, and as will be understood by those skilled in the art, cation exchanges, calcinations, etc., which are generally necessary to convert the Y zeolite to a catalytically active form and stable. The zeolites Y I and Y II are Y zeolites modified in comparison to the Y zeolite disclosed in U.S. Pat. No. 3, 130, 007. As used herein, the term "unit cell size" means the unit cell size determined by powder X-ray diffraction.

The Y zeolites used in the process and composition disclosed herein are large pore zeolites with an effective pore size of more than 7.0 angstroms. Since some of the pores of the Y zeolites are relatively large, the Y zeolites allow the molecules a relatively free access to their internal structure. The pores of the Y zeolites allow the passage inside them of benzene molecules and larger molecules, as well as the passage from their interior of reaction products. A group of Y zeolites that can be used in the process and composition disclosed herein as zeolites Y I, zeolites Y II, or both, includes zeolites sometimes designated as ultra-stable or ultra-hydrophobic zeolites. In essence, the composition and properties of this group of Y zeolites are prepared by a four-step process. First, a Y-zeolite in the form of an alkali metal (usually sodium) and with a typical unit cell size of 24.65 angstroms exchanges cations with ammonia ions. The ammonia exchange step typically reduces the sodium content of the initial sodium Y zeolite, from a value of more than 8% by weight, usually from 10 to 13% by weight, calculated as Na20, to a value in the range of 0.6 to 5% of the weight, calculated as Na20. Methods for carrying out ion exchange are well known in the art.

Second, the zeolite Y of the first step is allowed to calcinate in the presence of water vapor. For example, zeolite Y is calcined in the presence of at least 1.4 kPa (absolute) (hereinafter kPa (a)), at least 6.9 kPa (a), or at least 69 kPa (a) of water vapor, in three modalities. In two other embodiments, zeolite Y is calcined in an atmosphere consisting essentially of steam. Y zeolite is calcined to produce a unit cell size in the range of 24.40 to 24.64 angstroms. Third, the Y zeolite of the second step returns to make an exchange with ammonia. The second ammonia exchange further reduces the sodium content to less than 0.5% by weight, usually less than 0.3% by weight, calculated as Na20. Fourth, the Y zeolite of the third step receives yet another treatment to produce Y zeolite with a unit cell size of 24.25 to 24.32 angstroms, or preferably 24.26 to 24.30 angstroms in the case of the Y zeolite. In the case of the zeolite And II, the treatment produces a Y zeolite with a unit cell size of 24.33 to 24.38 angstroms, or preferably 24.34 to 24.36 angstroms. The Y zeolite resulting from the fourth step has a general silica to alumina molar ratio of 5.0 to 12.0 in one embodiment, 5.0 to 11.0 in another embodiment, and 5.0 to 10.0 in another embodiment. The treatment of the fourth step can comprising any of the well-known techniques for dealuminizing zeolites in general, and ultra-stable Y zeolite in particular, to produce the desired unit cell size and the molar ratio of silica to general alumina. The fourth treatment step may change the unit cell size or the structural molar ratio of silica to alumina, with or without change in the molar ratio of silica to alumina. Generally, the dealuminization of zeolite is obtained by chemical methods such as treatments with acids, for example, HC1, with volatile halides, for example, SiCl4, or with chelating agents such as ethylenediaminetetraacetic acid (EDTA). Another common technique is a hydrothermal treatment of the zeolite in pure steam or in air / steam mixtures, preferably as calcining in the presence of sufficient water vapor (for example, in an atmosphere consisting essentially of steam, and more preferably consisting of steam ), to produce the desired unit cell size and the general molar ratio of silica to alumina. The method of preparing zeolites Y used in the process and composition disclosed herein is similar to the process for zeolites Y disclosed in U.S. Pat. No. 5,350,501. However, particular conditions are selected in the fourth step of the aforementioned treatment, in order to produce ranges critical unit cell sizes for zeolite Y I, and optionally for zeolite Y II. U.S. Pat. No. 5,350,501, which is incorporated herein by reference in its entirety, discloses a fourth step involving calcining the zeolite resulting from the third treatment step in the presence of sufficient water vapor (in an atmosphere consisting essentially of steam or consisting of in steam) to produce a unit cell size of less than 24.40, and more preferably no more than 24.35 angstroms, and with a relatively low water vapor sorption capacity. The Y zeolite produced by the four-step process in U.S. Pat. No. 5,350,501 is a Y UHP zeolite, an ultrahydrophobic Y zeolite as defined in U.S. Pat. No. 5, 350, 501. U.S. Pat. No. 5,350,501 defines a "Y-UHP" zeolite as zeolitic aluminosilicates having, among other properties, a unit cell size or dimension of less than 24.45 angstroms, and a water vapor sorption capacity at 25 ° C and a value p / po of 0.10 less than 10.00 percent of the weight. The zeolite Y UHP in U.S. Pat. No. 5,350,501 is LZ-10. Another group of Y zeolites that can be used in the process and composition disclosed herein as zeolite YI, zeolite Y II, or both, can be prepared by dealuminizing a Y zeolite with a general molar ratio of silica versus alumina less than 5, and describes in detail in US patents Nos. 4,503,023, 4,597,956 and 4,735,928, which are hereby incorporated by reference in their entirety. U.S. Pat. No. 4,503,023 discloses another method for dealuminizing a Y zeolite which involves contacting the Y zeolite with an aqueous solution of a fluorosilicate salt using proportions, temperatures, and controlled pH conditions that prevent the extraction of aluminum without silica replacement. U.S. Pat. No. 4,503,023 specifies that the fluorosilicate salt is used as the aluminum extractant and also as the external source of the silica which is inserted into the structure of the zeolite Y instead of the extracted aluminum. The salts have the general formula: (A) 2 / bSiF6 Where A is a metallic or non-metallic cation other than H + and with valence "b". The cations represented by "A" are alkylammonia, NH 4 +, g ++, Li +, Na +, K +, Ba ++, Cd ++, Cu ++, H +, Ca ++, Cs +, Fe ++, Co ++, Pb ++, n ++, Rb +, Ag +, Sr ++, Ti + and Zn ++. A preferred member of this group is known as LZ-210, a zeolitic aluminosilicate molecular filter commercially available from UOP LLC, Des Plaines, Illinois, USA. The zeolites LZ-210 and the other zeolites of this group are conveniently prepared from an initial material of zeolite Y. The zeolite LZ-210 has a molar ratio general of silica versus alumina from 5.0 to 12.0 in one modality, from 5.0 to 11.0 in another modality, and from 5.0 to 10.0 in another modality. The unit cell size may preferably be from 24.25 to 24.32 angstroms or more, and preferably from 24.26 to 24.30 angstroms in the case of the Y zeolite I. In the case of the Y II zeolite, the unit cell size may be 24.33. at 24.38 angstroms, or preferably from 24.34 to 24.36 angstroms. The LZ-210 class of zeolites used in the process and composition disclosed herein has a composition expressed in terms of molar ratios of oxides as in the following formula: (0.85-ll) M2 / nO: A1203: xSi02 Where "M" is a cation with valence "n", and "x" has a value of 5.0 to 12.0. In general, LZ-210 zeolites can be prepared by dealuminizing Y-type zeolites using an aqueous solution of a fluorosilicate salt, preferably a solution of ammonia hexafluorosilicate. The dealuminization can be obtained by placing a Y zeolite, usually but not necessarily a Y zeolite exchanged with ammonia, in an aqueous reaction medium as an aqueous solution of ammonium acetate, and slowly adding a solution of ammonia fluorosilicate. After proceeding with the reaction, a zeolite is produced with a general molar ratio of silica versus increased alumina. The magnitude the increase depends at least in part on the amount of fluorosilicate solution contacted with the zeolite, and on the allowed reaction time. Normally, a reaction time of between 10 and 24 hours is enough to achieve equilibrium. The resulting solid product, which can be separated from the aqueous reaction medium by conventional filtration techniques, is a form of zeolite LZ-210. In some cases, this product can be steam roasted by methods well known in the art. For example, the product can be contacted with steam at a partial pressure of at least 1.4 kPa (a) for a period of between ¼ to 3 hours at a temperature between 482 and 816 ° C, in order to provide a greater crystalline stability. In some cases, the steam calcining product can be subjected to an ammonia exchange by methods well known in the art. For example, the product can be mixed with water, after which an ammonium salt is added to this slime. Typically, the resulting mixture is heated for a few hours, filtered and rinsed with water. Methods of steam treatment and ammonia exchange of zeolite LZ-210 are described in U.S. Pat. Nos. 4,503,023, 4,735,928 and 5,275,720. The optional Y zeolite I prepared by the preparation methods discussed above and used in the process and composition disclosed herein have an essential X-ray powder diffraction pattern of zeolite Y, and a unit cell size or dimension a0 of preferably 24.25 to 24.32 angstroms, and more preferably 24.26 to 24.30 angstroms. The zeolite Y II prepared by the preparation methods discussed above and used in the process and composition disclosed herein have an essential X-ray powder diffraction pattern of zeolite Y, and a unit cell size or a0 dimension of 24.33 a 24.38 angstroms, preferably from 24.34 to 24.36 angstroms. The zeolite Y I, the zeolite Y II, or both, can have a general molar ratio of silica to alumina of 5.0 to 12.0 in one embodiment, 5.0 to 11.0 in another embodiment, and 5.0 to 10.0 in another embodiment. The zeolite Y I or the zeolite Y II can have a surface area (BET) of at least 500 m2 / g, less than 800 m2 / g, frequently less than 700 m2 / g, and typically from 500 to 650 m2 / g. Another method to increase the stability or acidity of the zeolites Y is by exchanging the Y zeolite with polyvalent metal cations, such as cations containing rare earths, magnesium or calcium cations, or a combination of ammonia ions and polyvalent metal cations, thus reducing the sodium content until they are like the values described above after the first or second step of exchange with ammonia. Methods for carrying out ion exchange are well known in the art. The catalyst used in the process disclosed herein is to be used primarily as a replacement catalyst in commercially available hydrodisintegration units. Accordingly, its size and shape is preferably similar to those of conventional commercial catalysts. Preferably it is produced in the form of a cylindrical extrudate with a diameter of 0.8 to 3.2 mm. However, the catalyst can be produced in any other desired form, such as a sphere or granule. The extrudate may have other forms besides the cylindrical one, such as the well-known trilobal form or another form having advantages in terms of less diffusional distance or pressure drop. Commercial hydrodisintegration catalysts contain various non-zeolitic materials. This is due to several reasons, such as particle resistance, cost, porosity and performance. Therefore, the other components of the catalyst make positive contributions to the catalyst in general, even if it is not as active components of disintegration. These other components are designated in the present "support". Some traditional support components, such as silica-alumina, usually make some contribution to the catalyst's disintegration capacity. In embodiments of the process and composition disclosed herein, the catalyst has a relatively low content of beta zeolite. The catalyst contains a positive amount of less than 2% by weight, preferably from 0.1 to 2% by weight, and more preferably from 0.5 to 0.8% by weight of zeolite beta based on the combined weight of the zeolite beta, the zeolite YI. , the zeolite Y II (if any), and the support, all these based on dry weight. As used herein, dry weight is considered as the weight after heating a substance in dry air at 500 ° C for 6 hours. The catalyst has a weight ratio of zeolite Y I against beta zeolite of between 1 and 10, preferably from 2.3 to 5.9, based on dry weight. When the optional Y zeolite II is present, the catalyst has a weight ratio of zeolite Y I against zeolite Y II of between 1.5 and 6.5, preferably 2.3 to 4.7 based on the dry weight. When zeolite Y II is present, the catalyst contains a positive amount of at most 5% of the weight, preferably a positive amount of when more 4.3% of the weight, and more preferably a positive amount of when more 4.1% of the weight, of the zeolite YI and zeolite Y II based on the combined weight of zeolite beta, zeolite YI, zeolite Y II and the support, all these based on weight dry. The rest of the catalyst particles in addition to the zeolitic material can be composed primarily of conventional hydro-disintegration materials such as alumina or silica-alumina. The presence of silica-alumina helps to achieve the desired performance characteristics for the catalyst. In one embodiment, the catalyst contains at least 25% of the alumina weight and at least 25% of the silica-alumina weight, both based on the combined weight of the zeolites and the support, all based on dry weight. In another embodiment, the silica-alumina content of the catalyst is greater than 40% by weight, and the alumina content of the catalyst is greater than 20% by weight, both based on the combined weight of the zeolites and the support, all This is based on dry weight. However, it is thought that alumina functions only as a binder, and that it is not an active component of disintegration. The catalyst support may contain more than 50% of the weight of silica-alumina or more than 50% of the weight of alumina, based on the dry weight of the support. In one embodiment approximately equal amounts of silica-alumina and alumina are used. Other inorganic refractory materials that can be used as support in addition to silica-alumina and alumina include, for example, silica, zirconia, titania, boria, and zirconia-alumina. These support materials can be used aloneor in any combination. In addition to Y zeolite, beta zeolite and other support materials, the present catalyst contains a metallic hydrogenation component. The hydrogenation component is preferably provided as one or more basic metals uniformly distributed in the catalyst particle. The hydrogenation component is one or more elements of groups 6, 9, and 10 of the periodic table. Noble metals such as platinum and palladium can be applied, although the best results have been obtained with a combination of two basic metals. Specifically, nickel or cobalt is used together with tungsten or molybdenum, respectively. The preferred composition of the metallic hydrogenation component is nickel and molybdenum or nickel and tungsten. The amount of nickel or cobalt is preferably 2 to 8% of the weight of the finished catalyst. The amount of tungsten or molybdenum is preferably from 8 to 22% of the weight of the finished catalyst. The total amount of metallic hydrogenation component is from 10 to 30% of the weight of the finished catalyst. The catalyst of the present process can be formulated using conventional techniques in the industry. This can be summarized, with great generalization, as mixing the zeolite beta and the zeolite Y with the other components of inorganic oxide and a liquid such as water or mild acid to form an extrudable mass, followed by extrusion by a die plate of multiple perforations. The extrudate is collected and preferably calcined at a high temperature to harden the extrudate. The extruded particles are then screened to obtain a uniform size, and the hydrogenation components are added by immersion impregnation, or the well-known incipient humidification technique. If the catalyst contains two metals in the hydrogenation component, these may be added in sequence or simultaneously. The catalyst particles can be calcined between metal addition steps, and again after the metals have been added. In another embodiment, it may be convenient or preferable to combine the refractory and porous inorganic oxide, the zeolite beta and the zeolite Y, and compounds containing the metals, then grinding the already combined materials, extruding the ground material, and finally calcining the extruded material. . The milling is carried out with a metal source, such as ammonia heptamolybdate or ammonia metatungstate and another source of another metal, such as nickel nitrate or cobalt nitrate, where both source compounds are generally introduced to the combined materials in the form of solution harassing or a salt. Similarly, other metals can be introduced in dissolved aqueous form, or as salt. You can also enter non-metallic elements, ie phosphorus, incorporating a soluble component such as phosphoric acids into the aqueous solution. Other methods of preparation are described in U.S. Pat. Nos. 5,279,726 and 5,350,501, which are hereby incorporated by reference in their entirety. The catalysts prepared by the methods discussed above contain the hydrogenation metals in the oxide form. The oxide form is generally converted to sulfide form for hydrodisintegration. This can be achieved by any of the known sulfation techniques, including pre-sulfating ex situ prior to loading the catalyst into the hydrodisintegration reactor, pre-sulfating after loading the catalyst into the hydrodisintegration reactor and before using it at an elevated temperature, and sulfation in situ, that is, using the catalyst in oxidized form to hydrodisintegrate a hydrocarbon feedstock containing sulfur compounds under hydrodisintegration conditions, including elevated temperature and pressure, and the presence of hydrogen. The hydrodisintegration process disclosed herein will be operated within the general range of conditions that are currently used commercially in hydrodisintegration processes. In many instances, the operating conditions are specific to the refinery or unit processor. That is, they are dictated to a large extent by the construction and limitations of the existing hydrodisintegration unit (which can not usually be modified without significant expenditures) the composition of the food and the desired products. The inlet temperature of the catalyst bed should be from 232 to 454 ° C, and the inlet pressure should be from 5,171 to 24,132 kPa (g), and typically from 6,895 kPa (g) to 24,132 kPa (g). The feed stream is mixed with enough hydrogen to produce a volumetric flow rate of hydrogen per unit of feed volume from 168 to 1,684 normal liters / liters measured at 0 ° C, and 101.3 kPa (a) measured at 15.6 ° C and 101.3 kPa (a), and passed to one or more reactors containing fixed beds of catalyst. The hydrogen will be derived primarily from a stream of recycle gas that can pass through purification facilities to remove acid gases, although this is not necessary. The hydrogen-rich gas mixed with the feed and, in one embodiment, any recycle hydrocarbon, will usually contain at least 75 mole percent hydrogen. For hydrodisintegration to produce distillates, the feed rate in terms of VELH will normally be within the broad range of 0.3 to 3.0 hr "1. As used herein, VELH means hourly liquid space velocity, which is defined as the volumetric flow rate of liquid per hour divided by the volume of the catalyst, where the volume of liquid and the volume of catalyst are in the same volumetric units. The typical feed to the process disclosed herein is a mixture of various different hydrocarbons and co-boiling compounds recovered by fractional distillation of a crude oil. Normally it will contain components with a boiling point above the maximum boiling range of 149 to 371 ° C to produce distillates. Frequently it will have a range of boiling points of more than 340 ° C, and that in one mode it is less than 482 ° C, in another mode it is less than 540 ° C, and in a third mode it is less than 565 ° C. This petroleum derivative feed may be a mixture of streams produced in a refinery, such as atmospheric gas oil, coke gas oil, distillation gas oil, deasphalted gas oil, vacuum gas oil and FCC recycle oil. A typical gas oil comprises components that boil in the range of 166 to 566 ° C. Alternatively, the feed to the process disclosed herein may be a single fraction, such as heavy vacuum gas oil. A typical heavy gas oil fraction has a significant proportion of component hydrocarbons, usually at least 80 percent of the weight, boiling at between 371 and 566 ° C. Mixtures of hydrocarbons Synthetics, such as those recovered from tar or coal, can also be processed with the present process. The feed can be subjected to hydrotreatment, or treated by extraction with solvents before passing to the present process to remove large amounts of sulfur, nitrogen or other contaminants such as asphaltenes. It is considered that the present process will convert a large portion of the feed to more volatile hydrocarbons as hydrocarbons in the boiling range of distillates. Typical conversion ratios vary from 50 to 100 percent of the volume (hereinafter referred to as% -vol), depending largely on the feed composition. The conversion ratio is between 60 and 90% -vol in one modality of the process revealed in the present, from 70 to 90% -vol in another modality, from 80 to 90% -vol in another modality more, and from 65 to 75% -vol in another modality more. The process effluent will contain a wide variety of hydrocarbons, from methane to essentially intact feed hydrocarbons, above the boiling range of any desired product. The process effluent typically passes from a reactor containing a catalyst, and is usually separated by methods known to one of ordinary skill in the art, including phase separation or distillation, to produce a product with any desired final boiling point. TheHydrocarbons that boil above the final boiling point of any desired product are designated unconverted products, even if their boiling point has been reduced to some extent in the process. The majority of the unconverted hydrocarbons are recycled to the reaction zone with a small percentage, that is to say, 5% of the weight is removed as a carry-over stream. To produce distillates, at least 30% by weight, and preferably at least 50% by weight, of the effluent bursts at less than 371 ° C. The process and composition disclosed herein may be used in what is designated in the one-stage or two-stage process flow technique, with or without prior hydrotreating. These terms are used as defined and illustrated in the book entitled Hydrocracking Science and Technology, by J. Scherzer and AJ. Gruia, ISBN 0-8247-9760-4, Marcel Dekker Inc., New York, USA, 1996. In a two-stage process, the present catalyst can be used in the first or second stage. The catalyst may be preceded by a hydrotreating catalyst in a separate reactor, or charged to the same reactor as that of the hydrotreating catalyst, or a different hydrodisintegration catalyst. An upstream hydrotreating catalyst can be used as a feed pre-treatment step, or for hydrotreating unconverted recycled materials. The catalyst can be used of hydrotreating for the specific purpose of hydrotreating polynuclear aromatic compounds (APN) to promote their conversion into subsequent hydrodisintegration catalyst beds. The present catalyst can also be used in combination with a different second catalyst, such as a catalyst based on zeolite Y or with mainly amorphous disintegration components.

In some embodiments of the process disclosed herein, the catalyst is used with a feed or in a configuration such that the feed that passes through the catalyst is a raw mixture, or is similar to a raw feed. The sulfur content of crude oil, and therefore the feed to this process, varies greatly, depending on its source. As used herein, "crude stream" refers to a feed that has not been hydrotreated, or that still contains organic sulfur compounds that produce a sulfur level of more than 1,000 parts per million by weight, or that it still contains organic nitrogen compounds that produce a nitrogen level of more than 100 parts per million of the weight (0.01% by weight). In other embodiments of the process disclosed herein, the catalyst is used with a feed that has been hydrotreated. Those who know the technique of processing hydrocarbons know and can practice hydrotreating a crude mixture to produce a hydrotreated feed to be charged to the process disclosed herein. Although the sulfur level of the hydrotreated feed may be 500 to 1,000 parts per million of the weight, the sulfur level of the hydrotreated stream is less than 500 parts per million of the weight in one embodiment of the process disclosed herein, and from 5 to 500 parts per million of the weight in another modality. The nitrogen level of the hydrotreated stream is less than 100 parts per million of the weight in one embodiment, and 1 to 100 parts per million of the weight in another embodiment. All references in the present to the groups of elements of the periodic table are to the "New notation" IUPAC in the periodic table of elements in the fourth linings of the book entitled CRC Handbook of Chemistry and Physics, ISBN 0-8493-0480 -6, CRC Press, Boca Raton, Florida, USA, 80th Edition, 1999-2000. All references in the present to surface area are single point surface areas at a partial pressure nitrogen p / po of 0.03, determined by the BET method (Brunauer-Emmett-Teller), using the nitrogen adsorption technique described in ASTM D4365-95, Standard test method for determining volumes of micropores and zeolite areas of a catalyst, and in the article by S. Brunauer et al., J. Am. Chem. Soc, 60 (2), 309-319 (1938). All references present at boiling points are the boiling points determined by ASTM D2887, Standard Test Method for Distributions of Boiling Ranges of Petroleum Fraction by Gas Chromatography. ASTM methods are available from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, Pennsylvania, USA The following examples are provided for illustrative purposes, and not to limit the process and composition defined in the claims. EXAMPLE 1 Sample 1 A modified Y zeolite was prepared by steam treatment of a Y zeolite exchanged with ammonia marketed by UOP LLC (Des Plaines, Illinois, USA), and designated in the literature as Y-84, with a content of sodium of less than 0.2% of the weight calculated as Na20. The resulting modified Y zeolite is designated in the present "Sample 1", and had a general mole ratio of silica versus alumina (Si02 versus AI2O3) of 5.0 versus 5.5, a unit cell size of 24.28 angstroms, and a surface area of 540 to 640 m2 / g. Sample 1, which is an example of zeolite Y I, is designated in the Table as Yl. Sample 2 A modified Y zeolite was prepared in a manner similar to that described for Sample 1, except that the steam treatment conditions were different. The resulting modified Y zeolite is designated herein as Sample 2, and had a general mole ratio of silica to alumina (Si02 to AI2O3) of 5.0 to 5.5, a unit cell size of 24.35 angstroms, and a surface area of 630. at 730 m2 / g. Sample 2, which is an example of zeolite Y II, is designated in the Table as Y2. EXAMPLE 2 Eight catalysts (AH) were prepared by mixing in a grinder Sample 1 if present, Sample 2 if present, a zeolite beta with a general molar ratio of silica against alumina (Si02 versus? 1203) of 23.8, and a capacity of SF6 adsorption of 29% by weight, and containing the template used during its synthesis, if present, amorphous silica-alumina, and boehmite alumina Catapal ™ C peptized in HN03 in a grinder. The amorphous silica-alumina was silica-alumina CCIC with a nominal composition of 75% by weight of silica and 25% by weight of alumina, or silica-alumina Siral 40, with a nominal composition of 40% by weight of silica and 60% of the weight of alumina. The silica-alumina CCIC is available from Catalysts & Chemicals Industries Co. Ltd. (CCIC), and Catapal C alumina and silica-alumina Siral 40 are available from Sasol Germany GmbH. The quantities of these are described in the Table components based on the dry weight in each final catalyst. The resulting mixture was extruded into cylindrical particles of 1.6 mm in diameter and 3.2 to 12.7 mm in length. The dried extrudates were dried at 104 ° C for a minimum of 4 hours, and then calcined at temperatures of more than 550 ° C for a minimum of 90 minutes. For the AF and H catalysts, sufficient nickel nitrate was added to supply 4% by weight of nickel (calculated as Ni) in the final catalyst, and enough ammonia metatungstate to supply 14% by weight of tungsten (calculated as W). ) in the final catalyst, to the calcined extrudates until reaching incipient humidity, while for the catalyst G the corresponding amounts were 5% of the weight of nickel and 17.5% of the weight of tungsten. The extrudates were dried to have free flow, and then oxidized by calcination at 500 ° C for a minimum of 90 minutes. Catalyst I is a conventional hydrodisintegration catalyst that contains on average 5.5% of the weight of nickel and 17.5% of the weight of tungsten. It is thought that the differences in nickel and tungsten content do not produce a significant effect on the hydrodisintegration activity and selectivity results described in these examples. EXAMPLE 3 Each of the nine was pre-sulfurized previously described catalysts, passing a gas stream consisting of 10% -vol of H2S and the balance of H2 through a bed of catalyst at a temperature of initially 149 ° C, which rose slowly to 413 ° C, which was maintained for 6 hours. The activities and hydrodisintegration selectivities (ie, product yields) of the nine catalysts were compared in simulated first stage tests. Specifically, the nine catalysts were tested separately to hydrodisintegrate an arabic vacuum gas oil feed (VGO) with a specific gravity of 0.877 to 15.6 ° C (API gravity of 30.05 °), an initial boiling point of 107 ° C, a boiling point of 5% by weight of 195 ° C, a final boiling point of 550 ° C, and a boiling point of 50% by weight of 24 ° C, with 13% of the weight bulging at less than 288 ° C , and 26% of the weight bullendo at less than 371 ° C. Each catalyst was tested in a simulated first-stage operation by passing the feed load through a laboratory-sized reactor to a VELH of 1.5 hr-1, a total pressure of 13,786 kPa (g), and a volumetric hydrogen feed rate per unit of feed volume of 1,684 Itr normal / Itr measured at 0 ° C and 101.3 kPa (a) (10,000 SCFB measured at 15.6 ° C and 101.3 kPa (a)). Sufficient di-tert-disulfide was added to the feed.

Butyl to supply 2.1% of the weight of sulfur, and thereby simulate an atmosphere with hydrogen sulfide, as it exists in commercial first-stage hydrodisintegration reactors. In addition, sufficient cyclohexylamine was added to the feed to supply 780 parts per million of the weight of nitrogen, and thereby simulate an ammoniacal atmosphere, such as exists in commercial first stage hydrodisintegration reactors. For the hydrodisintegration tests to produce distillates, the temperature conditions were adjusted as necessary to maintain a 65% net weight conversion to materials with a boiling point lower than 371 ° C, during the course of 100 hours. The net conversion is the effluent that boils at less than 371 ° C as a percentage of the feed, minus the percentage of the feed that boils at less than 371 ° C. At the end of the 100 hours, a record was made of the temperature required to maintain the conversion of 65% of the net weight, and the relative activities and selectivities of each catalyst were calculated. These data are summarized in the Table. The selectivity values for each catalyst were total distillates (ie, 149 to 371 ° C), light distillates (ie, 149 to 288 ° C), and heavy distillates (ie, 288 to 371 ° C). The relative activity value for each catalyst was entered as the difference between the required temperature to the catalyst to maintain the conversion of 65% of the net weight and a reference temperature that was equal for the nine catalysts. The lower the relative activity value, the more active the catalyst would be.

TABLE NA = Not applicable Figure 1 is a graph of section 149 at 371 ° C of the distillate selectivity of AI catalysts plotted against the relative activity of the catalyst, expressed in terms of reactor temperature higher than the reference temperature required to obtain a conversion of the catalyst. % of the net weight of VGO to the cut of total distillates. Catalysts A-F (squares) show more selectivity of total distillates at a given relative activity than Catalysts G-I (diamonds). Figure 2 is a graph of the weight ratio of the cut selectivity of the heavy distillates against the cut selectivity of the light distillates versus the relative activity. The catalysts A-F (square) have a selectivity of heavy distillates significantly higher compared to the light distillates, in comparison with the catalysts G-I (diamonds).

Claims (10)

1. CLAIMS 1. A composition of matter comprising a catalyst comprising a hydrogenation component, a beta zeolite with a general molar ratio of silica versus alumina less than 30, and an SF6 adsorption capacity of at least 28% by weight, a zeolite Y with a unit cell size of 24.25 to 24.32 angstroms (zeolite YI), and a support, where zeolite YI has a general molar ratio of silica versus alumina of 5.0 to 11.0, where the catalyst contains 0.1 to 2% of the weight of beta zeolite based on the combined weight of zeolite beta, zeolite YI and support based on dry weight, and where the catalyst has a weight ratio of zeolite YI against beta zeolite from 1 to 10 based on the dry weight.
2. 2. The composition of claim 1, wherein the zeolite Y I has a surface area of less than 800 m2 / g.
3. The composition of claim 1, wherein the hydrogenation component is selected from the group consisting of molybdenum, tungsten, nickel, cobalt, and the oxides and sulfides thereof.
4. The composition of claim 1, wherein the unit cell size of zeolite YI is a first unit cell size, and the catalyst comprises an additional Y zeolite (zeolite Y II) having a second unit cell size of 24.33 at 24.38 angstroms and it's at least 0.04 angstroms greater than the first unit cell size.
5. The process of claim 1, wherein the zeolite Y I has a unit cell size between 24.26 and 24.30 angstroms.
6. The composition of claim 1, wherein the weight ratio of zeolite Y I against zeolite beta is between 2.3 and 5.9 based on dry weight.
7. The composition of claim 1, wherein the zeolite Y I is prepared by a process comprising the steps of: a) partially exchanging ammonia ions in a sodium Y zeolite; b) calcining the zeolite resulting from step (a) in the presence of water vapor; c) exchanging ammonia ions in the zeolite resulting from step (b); and d) calcining the zeolite resulting from step (c) in the presence of water vapor.
8. The composition of claim 1, wherein the Y zeolite I is prepared by a process comprising the steps of: a) partially exchanging ammonia ions in a sodium Y zeolite; b) calcining the zeolite resulting from step (a) in the presence of water vapor; c) contacting the zeolite resulting from step (b) with a fluorosilicate salt in the form of an aqueous solution; and d) calcining the zeolite resulting from step (c) in the presence of water vapor.
9. 9. The composition of claim 1, wherein zeolite Y I is prepared by a process comprising the steps of: a) contacting a sodium Y zeolite with a fluorosilicate salt in the form of an aqueous solution; and b) calcining the zeolite resulting from step (a) in the presence of water vapor.
10. 10. A process for hydrodisintegrating a hydrocarbon feedstock, comprising contacting the feedstock at a temperature of 232 to 454 ° C, and at a pressure of 5.171 to 24.132 kPa (g) in the presence of hydrogen, with the catalyst composition of any of the preceding claims.