DEMETALLATION OF HYDROCARBON FEEDSTOCKS WITH A SYNTHETIC MESOPOROUS CRYSTALLINE MATERIAL

Abstract: There is provided a process for demetallizing hydrocarbon feedstocks, such as resids or shale oil. The process uses a catalyst comprising at least one hydrogenation metal, such as nickel and molybdenum, and an ultra-large pore oxide material. This ultra-large pore oxide material may have uniformly large pores, e.g., having a size of 40 nm in diameter.

Description: DEMETALIATION OF HYDROCARBON FEEDSTOCKS WITH A SYNTHETIC MESOPOROUS CRYSTAT.T.TWTϋ MATERIAL This invention relates to a process for demetallizing hydrocarbon feedstocks, such as resids or shale oil, using a novel ultra-large pore oxide material as a catalyst component. Heavy oils, petroleum residua, and bitumen derived from tar sand or oil shales contain asphaltenes and trace metals (nickel, vanadium, etc) , which are poisonous to the catalysts used in refining processes. Consequently, demetallation and asphaltene conversion are two important reactions for the upgrading of those heavy hydrocarbons. Asphaltenes and metal-containing molecules are bulky and therefore not readily accessible to the surface of conventional zeolite pores. Ultra-large pore materials with pore openings as large as 4 nm (40 Angstroms) would be attractive for the metal removal and asphaltene conversion. Retorted shale oil contains trace metals, such as arsenic, iron, and nickel, which can cause permanent deactivation of the down-stream upgrading catalysts. In addition, shale oil is highly olefinic and rich in nitrogen-containing compounds. Olefins, without saturation, can result in a rapid temperature rise in the down-stream upgrading processes. Olefins can also facilitate bed-plugging due to coke formation at elevated temperature. Consequently, it is desirable to maximize catalytic activities for metal removal, olefin saturation, and heteroatom removal. The present invention provides a process for demetallizing a hydrocarbon feedstock, which process SUBSTITUTE SHEET co prises contacting the hydrocarbon feedstock with a catalyst under sufficient demetallation conditions, the catalyst comprising at least one hydrogenation metal and an inorganic, porous crystalline phase material having, after calcination, a hexagonal arrangement of uniformly-sized pores having diameters of at least 1.3 nm (13 Angstrom Units) and exhibiting a hexagonal electron diffraction pattern that can be indexed with a d_ 00 value greater than 1.8 nm (18 Angstrom Units). The present invention also provides a process for demetallizing a hydrocarbon feedstock, the process comprising contacting the hydrocarbon feedstock with a catalyst under sufficient demetallation conditions, the catalyst comprising at least one hydrogenation metal and an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 1.8 nm (18 Angstrom Units) with a relative intensity of 100 and a benzene adsorption capacity of greater than 15 grams benzene per 100 grams of the material at 6.7 kPa (50 Torr) and 25°C. The crystalline mesoporous oxide material described herein may be an inorganic, porous material having a pore size of at least 1.3 nm (13 Angstroms). More particularly, this pore size may be within the range of from 1.3 nm (13 Angstroms) to 20 nm (200 Angstroms) . Certain of these novel crystalline compositions may exhibit a hexagonal electron diffraction pattern that can be indexed with a d 100 value greater than 1.8 nm (18 Angstroms), and a benzene adsorption capacity of greater than 15 grams benzene/100 grams crystal at 6.7 kPa (50 Torr) and 25°C. Certain of these mesoporous oxide materials may have a hexagonal arrangement of uniformly sized pores. As demonstrated hereinafter, the inorganic, non-layered mesoporous crystalline material described herein may have the following composition: M n/q (W a X Y c Z d V wherein is a divalent element, such as a divalent first row transition metal, e.g. manganese, cobalt and iron, and/or magnesium, preferably cobalt; X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum; Y is a tetravalent element such as silicon and/or germanium, preferably silicon; Z is a pentavalent element, such as phosphorus; M is one or more ions, such as, for example, ammonium, Group IA, IIA and VIIB ions, usually hydrogen, sodium and/or fluoride ions; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; a, b, c, and d are mole fractions of , X, Y and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d) = 1. A preferred embodiment of the above crystalline material is when (a+b+c) is greater than d, and h = 2. A further embodiment is when a and d = 0, and h - 2. In the as-synthesized form, this material may have a composition, on an anhydrous basis, expressed empirically as follows: wherein R is the total organic material not included in M as an ion, and r is the coefficient for R, i.e. the number of moles or mole fraction of R. The M and R components are associated with the material as a result of their presence during crystallization, and are easily removed or, in the case of M, replaced by post-crystallization methods hereinafter more particularly described. To the extent desired, the original M, e.g. sodium or chloride, ions of the as-synthesized material described herein can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other ions. Examples of such replacing ions include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof. Particular examples of such ions are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. Replacing ions include hydrogen, rare earth metals and metals of Groups IA (e.g. K) , IIA (e.g. Ca) , VIIA (e.g. Mn) , VIIIA (e.g. Ni),IB (e.g. Cu) , IIB (e.g. Zn) , IIIB (e.g. In), IVB (e.g. Sn) , and VIIB (e.g. F) of the Periodic Table of the Elements (Sargent-Welch Scientific Co. Cat. No. S-18806, 1979) and mixtures thereof. The crystalline (i.e. meant here as having sufficient order to provide a diffraction pattern such as, for example, by X-ray, electron or neutron diffraction, following calcination with at least one peak) mesoporous material described herein may be characterized by its heretofore unknown structure, including extremely large pore windows, and high sorption capacity. The term "mesoporous" is used here to indicate crystals having pores within the range of from 1.3 to 20 nm (13 Angstroms to 200 Angstroms). The materials described herein may have uniform pores within the range of from 1.3 to 20 nm (13 Angstroms to 200 Angstroms), more usually from 1.5 to 10 nm (15 Angstroms to 100 Angstroms) . For the purposes of this disclosure, a working definition of "porous" is a material that adsorbs at least 1 gram of a small molecule, such as Ar, N 2 , n-hexane or cyclohexane, per 100 grams of the solid. The mesoporous oxide material described herein can be distinguished from other porous inorganic solids by the regularity of its large open pores, whose pore size is greater than that of zeolites, but whose regular arrangement and uniformity of size (pore size distribution within a jingle phase of, for example, + 25%, usually + 15% or less of the average pore size of that phase) resemble those of zeolites. Certain forms of this material appear to have a hexagonal arrangement of large open channels that can be synthesized with open internal diameters from 1.3 nm to 20 nm (13 Angstroms to 200 Angstroms) . These forms are referred to herein as hexagonal forms. The term "hexagonal" is intendfe_ to encompass not only materials that exhibit mathematically perfect hexagonal symmetry within the limits of experimental measurement, but also those with significant observable deviations from that ideal state. A working definition as applied to the microstructure of the hexagonal form of the present mesoporous material would be that most channels in the material would be surrounded by six nearest neighbor channels at roughly the same distance. Defects and imperfections may cause significant numbers of channels to violate this criterion to varying degrees, depending on the quality of the material's preparation. Samples which exhibit as much as + 25% random deviation from the average repeat distance between adjacent channels still clearly give recognizable images of the hexagonal form of the present ultra-large pore materials. Comparable variations are also observed in the d_ 00 values from the electron diffraction patterns. To illustrate the nature of the mesoporous material described herein, samples of these materials may be studied by transmission electron microscopy (TEM) . TEM is a technique used to reveal the microscopic structure of materials, including crystalline materials. In order to illuminate the microstructure of materials by TEH, samples must be thin enough for an electron beam to pass through them, generally 50-100 nm (500-1000 Angstrom Units) or so thick. The crystal morphology of the present materials usually requires that they be prepared for study by ultramicrotomy. While time consuming, this technique of sample preparation is quite familiar to those skilled in the art of electron microscopy. The materials may be embedded in a resin, e.g., a commercially available low viscosity acrylic resin L.R. WHITE (hard) , which is then cured at 80 β C for 1-1/2 hours. Thin sections of the block may be cut on an ultramicrotome using a diamond knife and sections in the thickness range 50-100 nm (500-1000 Angstrom Units) may be collected on fine mesh electron microscope support grids. An LKB model microtome with a 45 β C diamond knife edge may be used; the support grids may be 400 mesh copper grids. After evaporation of a thin carbon coating on the sample to prevent charging in the microscope (light c ,*ay color on a white sheet of paper next to the sample in the evaporator) , the samples are ready for examination in the TEM. High resolution TEM micrographs show projections of structure along the direction that the sample is viewed. For this reason, it is necessary to have a sample in specific orientations to see certain details of the microstructure of the material. For crystalline materials, these orientations are most easily chosen by observing the electron diffraction pattern (EDP) that is produced simultaneously with the electron microscope image. Such EDP's are readily produced on modern TEM instruments using, e.g., the selected area field limiting aperture technique familiar to those skilled in the art of electron microscopy. When an EDP with the desired arrangement of diffraction spots is observed, the corresponding image of the crystal giving that EDP will reveal details of the microstructure along the direction of projection indicated by the EDP. In this way, different projections of a crystal's structure can be observed and identified using TEM. In order to observe the salient features of the hexagonal form of the present mesoporous material, it is necessary to view the material in an orientation wherein the corresponding EDP gives a hexagonal arrangement of diffraction spots from a single individual crystal. If multiple crystals re present within the field limiting aperture, overlε _?ing diffraction patterns will occur that can be quite difficult to interpret. The number of ffraction spots observed depends to a degree upon tϊ. regularity of the crystalline arrangement in the material, among other things. At the very least, however, the inner ring of bright spots should be observed to obtain a good image. Individual crystals can be manipulated by specimen tilt adjustments on the TEM until this orientation is achieved. More often, it is easier to take advantage of the fact that the specimen contains many randomly oriented crystals and to simply search through the sample until a crystal giving the desired EDP (and hence orientation) is located. Microtomed samples of materials may be examined by the techniques described above in a JEOL 200 CX transmission electron microscope operated at 200,000 volts with an effective 2 Angstrom objective aperture in place. The instrument has a point-to-point resolution of 0.45 nm (4.5 Angstroms). Other experimental arrangements familiar to one skilled in the art of high resolution (phase contrast) TEM could be used to produce equivalent images provided care is taken to keep the objective lens on the underfocus (weak lens) side of the minimum contrast lens current setting. The application of the above-mentioned TEM techniques to particular samples is described in Example 23 of the aforementioned U.S. Application Serial No. 625,245, filed December 10, 1990. The most regular preparations of the hexagonal form of the present mesoporous material give an X-ray diffraction pattern with a few distinct maxima in the extreme low angle region. The positions of these peaks approximately fit the positions of the hkO reflections from a hexagonal lattice. The X-ray diffraction pattern, however, is not always a sufficient indicator of the presence of these materials, as the degree of regularity in the m:crostructure and the extent of repetition of the structure within individual particles affect the number of peaks that will be observed. Indeed, preparations with only one distinct peak in the low angle region of the X-ray diffraction pattern have been found to contain substantial amounts of the present material in them. Other techniques to illustrate the microstructure of this material are transmission electron microscopy and electron diffraction. Properly oriented specimens of the hexagonal form of the present material show a hexagonal arrangement of large channels and the corresponding electron diffraction pattern gives an approximately hexagonal arrangement of diffraction maxima. The d 100 spacing of the electron diffraction patterns is the distance between adjacent spots on the hkO projection of the hexagonal lattice and is related to the repeat distance a_ between channels observed in the electron micrographs through _ the formula d- 00 = a Q 73/2. This d. QQ spacing observed in the electron diffraction patterns corresponds to the d-spacing of a low angle peak in the X-ray diffraction pattern of the material. The most highly ordered preparations of the material obtained so far have 20-40 distinct spots observable in the electron diffraction patterns. These patterns can be indexed with the hexagonal hkO subset of unique reflections of 100, 110, 200, 210, etc., and their symmetry-related reflections. In its calcined form, the crystalline mesoporous material described herein may be further characterized by an X-ray diffraction pattern with at least one peak at a position greater than 1.8 nm (18 Angstrom Units) d-spacing (4.909 degrees two-theta for Cu K-alpha radiation) which corresponds to the d 1QQ value of the electron diffraction pattern of the material, and an equilibrium benzene adsorption capacity of greater than 15 grams benzene/100 grams crystal at 50 Torr and 25°C (basis: crystal material having been treated in an attempt to insure no pore blockage by incidental contaminants, if necessary) . The equilibrium benzene adsorption capacity characteristic of this material is measured on the basis of no pore blockage by incidental contaminants. For instance, the sorption test will be conducted on the crystalline material phase having any pore blockage contaminants and water removed by ordinary methods. Water may be removed by dehydration techniques, e.g. thermal treatment. Pore blocking inorganic amorphous materials, e.g. silica, and organics may be removed by contact with acid or base or other chemical agents such that the detrital material will be removed without detrimental effect on the mesoporous crystal described herein. Certain of the calcined crystalline non-layered materials described herein may be characterized by an X-ray diffraction pattern with at least two peaks at positions greater than 1 nm (10 Angstrom Units) d-spacing (8.842 degrees two-theta for Cu K-alpha radiation) , at least one of which is at a position greater than 1.8 nm (18 Angstrom Units) d-spacing, and no peaks at positions less than 1 nm (10 Angstrom Units) d-spacing with relative intensity greater than 20% of the strongest peak. The X-ray diffraction pattern of calcined materials described herein may have no peaks at positions less than 1 nm (10 Angstrom Units) d-spacing with relative intensity greater than 10% of the strongest peak. In any event, at least one peak in the X-ray diffraction pattern will have a d-spacing that corresponds to the . Q0 value of the electron diffraction pattern of the material. The calcined inorganic, non-layered crystalline material described herein may have a pore size of 1.3 nm (13 Angstroms) or greater, as measured by physisorption measurements, hereinafter more particularly set forth. It will be understood that pore size refers to the diameter of pore. The pores of the present hexagonal form of these materials are believed to be essentially cylindrical. The following description provides examples of how physisorption measurements, particularly argon physisorption measurements, may be taken. Examples 22(a) and 22(b) of the aforementioned U.S. Application Serial No. 625,245, filed December 10, 1990, provide demonstrations of these measurements as applied to particular samples. Argon Physisorption For Pore Systems UP to About 6 nm (60 Angstroms) Diameter To determine the pore diameters of products with pores up to 6 nm (60 Angstroms) in diameter, 0.2 gram samples of the products may be placed in glass sample tubes and attached to a physisorption apparatus as described in U.S. Patent No. 4,762,010. The samples may be heated to 300°C for 3 hours in vacuo to remove adsorbed water. Thereafter, the samples may be cooled to 87°K by immersion of the sample tubes in liquid argon. Metered amounts of gaseous argon may then be admitted to the samples in stepwise manner as described in U.S. Patent No. 4,762,010, column 20. From the amount of argon β _βιmπe ββt ad itted to the samples and the amount of argon left in the gas space above the samples, the amount of argon adsorbed can be calculated. For this calculation, the ideal gas law and the calibrated sample volumes may be used. (See also S.J. Gregg et al.. Adsorption. Surface Area and Porosity, 2nd ed. , Academic Press, 1982) . In each instance, a graph of the amount adsorbed versus the relative pressure above the sample, at equilibrium, constitutes the adsorption isotherm. It is common to use relative pressures which are obtained by forming the ratio of the equilibrium pressure and the vapor pressure P of the adsorbate at the temperature where the isotherm is measured. Sufficiently small amounts of argon may be admitted in each step to generate, e.g., 168 data points in the relative pressure range from 0 to 0.6. At least 100 points are required to define the isotherm with sufficient detail. The step (inflection) in the isotherm indicates filling of a pore system. The size of the step indicates the amount adsorbed, whereas the position of the step in terms of P/P Q reflects the size of the pores in which the adsorption takes place. Larger pores are filled at higher ?/?_• In order to better locate the position of the step in the isotherm, the derivative with respect to log (P/P ) is formed. The position of an adsorption peak in terms of log (P/P ) may be converted to the physical pore diameter in Angstroms by using the following formula: log(P/P )= K s 4 s 10 s 4 s 10 d-0.38 3(L-D/2) 3 9(L-D/2) 9 3(D/2) 3 9(D/2) 9 wherein d = • pore diameter in nanometers, K = 32.17, S = 0.2446, L = d + 0.19, and D = 0.57. This formula is derived from the method of Horvath and Kawazoe (G. Horvath et al., J. Chem. En . Japan. 16 (6) 470(1983)). The constants required for the implementation of this formula were determined from a measured isotherm of A1P0.-5 and its known pore size. This method is particularly useful for microporous materials having pores of up to 6 nm (60 Angstroms) in diameter. For materials having a pore size greater than 0.9 nm (9 Angstroms), the plot of log (P/P Q ) vs. the derivative of uptake may reveal more than one peak. More particularly, a peak may be observed at P/P_ = 0.015. This peak reflects adsorption on the walls of the pores and is not otherwise indicative of the size of the pores of a given material. A material with pore size of 3.96 nm (39.6 Angstroms) has a peak occurring at log (P/P ) = -0.4 or P/P = 0.4. A value of P/P Q of 0.03 corresponds to 13 Angstroms pore size. Argon Physisorption For Pore Systems Over 6 nm (About 60 Angstroms) Diameter The above method of Horvath and Kawazoe for determining pore size from physisorption isotherms was SUBSTITUTE SHEET intended to be applied to pore systems of up to 2 nm (20 Angstroms) diameter; but with some care as above detailed, its use can be extended to pores of up to 6 nm (60 Angstroms)1 diameter. In the pore regime above 6 nm (60 Angstroms) diameter, however, the Kelvin equation can be applied. It is usually given as: -2 V In(P/P ) = cos _ r k RT where: = surface tension of sorbate V — molar volume of sorbate _ = contact angle (usually taken for practical reasons to be 0) R = gas constant T = absolute temperature r. = capillary condensate (pore) radius P/P = relative pressure (taken from the physisorption isotherm) The Kelvin equation treats adsorption in pore systems as a capillary condensation phenomenon and relates the pressure at which adsorption takes place to the pore diameter through the surface tension and contact angle of the adsorbate (in this case, argon) . The principles upon which the Kelvin equation are based are valid for pores in the size range 5-10 nm (50 to 1000 Angstroms) diameter. Below this range the equation no longer reflects physical reality, since true capillary condensation cannot occur in smaller pores; above this range the logarithmic nature of the equation precludes obtaining sufficient accuracy for pore size determination. The particular implementation of the Kelvin equation often chosen for measurement of pore size is that reported by Dollimore and Heal (D. Dollimore and G.R. Heal, J. Applied Chem. 14, 108 (1964)). This method corrects for the effects of the surface iayer of adsorbate on the pore wall, of which the Kelvin equation proper does not take account, and thus provides a more accurate measurement of pore diameter. While the method of Dollimore and Heal was derived for use on desorption isotherms, it can be applied equally well to adsorption isotherms by simply inverting the data set. X-ray diffraction data were collected on a Scintag PAD X automated diffraction system employing theta-theta geometry, Cu K-alpha radiation, and an energy dispersive X-ray detector. Use of the energy dispersive X-ray detector eliminated the need for incident or diffracted beam monochromators. Both the incident and diffracted X-ray beams were collimated by double slit incident and diffracted collimation systems. The slit sizes used, starting from the X-ray tube source, were 0.5, 1.0, 0.3 and 0.2 mm, respectively. Different slit systems may produce differing intensities for the peaks. The mesoporous materials described herein that have the largest pore sizes may require more highly collimated incident X-ray beams in order to resolve the low angle peak from the transmitted incident X-ray beam. The diffraction data were recorded by step-scanning at 0.04 degrees of two-theta, where theta is the Bragg angle, and a counting time of 10 seconds for each step. The interplanar spacings, d's, were calculated in Angstrom units (A) , and the relative intensities of the lines, I/Io, where Io is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine. The intensities were uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols vs • = very strong (75-100) , s = strong (50-74) , m = medium (25-49) and w = weak (0-24) . It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines which under certain conditions, such as very high experimental resolution or crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry / without a substantial change in structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, thermal and/or hydrothermal history, and peak width/shape variations due to particle size/shape effects, structural disorder or other factors known to those skilled in the art of X-ray diffraction. The equilibrium benzene adsorption capacity may be determined by contacting the mesoporous material described herein, after dehydration or calcination at, for example, 540°C for at least one hour and other treatment, if necessary, in an attempt to remove any pore blocking contaminants, at 25°C and 50 Torr benzene until equilibrium is reached. The weight of benzene sorbed is then determined as more particularly described hereinafter. When used as a catalyst component, the mesoporous material described herein should be subjected to treatment to remove part or all of any organic constituent. The present composition can also be used as a catalyst component in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium or mixtures thereof where a hydrogenation- dehydrogenation function is to be performed. Such component can be in the composition by way of co-crystallization, exchanged into the composition to the extent a Group IIIB element, e.g. aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in or on to it such as, for example, by, in the case of platinum, treating the material with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. The above crystalline material, especially in its metal, hydrogen and ammonium forms can be beneficially converted to another form by thermal treatment (calcination) . This thermal treatment is generally performed by heating one of these forms at a temperature of at least 400°C for at least 1 minute and generally not longer than 20 hours, preferably from 1 to 10 hours. While subatmospheric pressure can be SUBSTITUTE SHEET employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience, such as in air, nitrogen, ammonia, etc. The thermal treatment can be performed at a temperature up to 750 β C. The thermally treated product is particularly useful in the catalysis of certain hydrocarbon conversion reactions. The crystalline material described herein, when employed either as a catalyst component in an organic compound conversion process may be dehydrated, at least partially. This can be done by heating to a temperature in the range of 200°C to 595°C in an atmosphere such as air, nitrogen, etc. and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the composition in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration. In accordance with a general method of preparation, the present crystalline material can be prepared from a reaction mixture containing sources of, for example, alkali or alkaline earth metal (M) , e.g. sodium or potassium, cation, one or a combination of oxides selected from the group consisting of divalent element W, e.g. cobalt, trivalent element X, e.g. aluminum, tetravalent element Y, e.g. silicon, and pentavalent element Z, e.g. phosphorus, an organic (R) directing agent, hereinafter more particularly described, and a solvent or solvent mixture, especially water, the reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: Reactants Useful Preferred X 2°3 Y0 2 0 to 0.05 0.001 to 0.05 X 2 O 3 /(YO 2 +Z 2 O_) 0.1 to 100 0.1 to 20 X 2 O 3 /(YO 2+ WO + Z 2 O 5 ) 0.1 to 100 0.1 to 20 Solvent/YO 1 to 1500 5 to 1000 OH " /YO 2 0.01 to 10 0.05 to 5 < M 2/e° +R 2/f 0)/ (Y0 2 +W0+Z 2 0_.+X 2 0 3 ) 0.01 to 20 0.05 to 5 M 2/e 0 (YO 2+ WO + Z 2 O 5+ X 2 O 3 ) 0 to 10 0.005 to 5 wherein e and f are the weighted average valences of M and R, respectively. In this general synthesis method, when no Z and/or W oxides are added to the reaction mixture, the pH is critical and must be maintained at from 10 to 14. When Z and/or W oxides are present in the reaction mixture, the pH is not narrowly critical and may vary between 1 and 14 for crystallization of the present invention. The present crystalline material can be prepared by one of the following four particular methods, each with particular limitations. A first particular method involves a reaction mixture having an X-0-/YO- mole ratio of from 0 to 0.5, but a « Al 2 0 3 /SiO_ mole ratio of from 0 to 0.01, a crysT; lization temperature of from 25"C to 250°C, preferably from 50 β C to 175°C, and an organic directing agent, hereinafter more particularly described, or, preferably a combination of that organic directing agent plus an additional organic directing agent, hereinafter more particularly described. This first particular method comprises preparing a reaction mixture containing sources of, for example, alkali or alkaline earth metal (M) , e.g. sodium or potassium, cation if desired, one or a combination of oxides selected from the group consisting of divalent element W, e.g. cobalt, trivalent element X, e.g. aluminum, tetravalent element Y, e.g. silicon, and pentavalent element Z, e.g. phosphorus, an organic (R) directing agent, hereinafter more particularly described, and a solvent or solvent mixture, such as, for example, C.-C- alcohols, C.-C 8 diols and/or water, especially water, the reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: wherein e and f are the weighted average valences of M and R, respectively. In this first particular method, when no Z and/or W oxides are added to the reaction mixture, the pH is important and must be maintained at from 9 to 14. When SUB S TITUTESHEET Z and/or W oxides are present in the reaction mixture, the pH is not narrowly important for synthesis of the present crystalline material. In this, as well as the following methods for synthesis of the present material, the R /f O/(YO +WO+Z 2 0_+X 2 0 3 ) ratio is important. When this ratio is less than 0.01 or greater than 2.0, impurity products tend to be synthesized at the expense of the present material. A second particular method for synthesis of the present crystalline material involves a reaction mixture having an X_0_/Y0- mole ratio of from 0 to 0.5, a crystallization temperature of from 25°C to 250 β C, preferably from 50 β C to 175"C, and two separate organic directing agents, i.e. the organic and additional organic directing agents, hereinafter more particularly described. This second particular method comprises preparing a reaction mixture containing sources of, for example, alkali or alkaline earth metal (M) , e.g. sodium or potassium, cation if desired, one or a combination of oxides selected from the group consisting of divalent element W, e.g. cobalt, trivalent element X, e.g. aluminum, tetravalent element Y, e.g. silicon, and pentavalent element Z, e.g. phosphorus, a combination of organic directing agent and additional organic directing agent (R) , each hereinafter more particularly described, and a solvent or solvent mixture, such as, for example, C.-Cg alcohols, C.-C 8 diols and/or water, especially water, the reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: wherein e and f are the weighted average valences of M and R, respectively. In this second particular method, when no Z and/or W oxides are added to the reaction mixture, the pH is important and must be maintained at from 9 to 14. When Z and/or W oxides are present in the reaction mixture, the pH is not narrowly important for crystallization. A third particular method for synthesis of the present crystalline material is where X comprises aluminum and Y comprises silicon, the crystallization temperature must be from 25 β C to 175 β C, preferably from 50 β C to 150 β C, and an organic directing agent, hereinafter more particularly described, or, preferably a combination of that organic directing agent plus an additional organic agent, hereinafter more particularly described, is used. This third particular method comprises preparing a reaction mixture containing sources of, for example, alkali or alkaline earth metal (M) , e.g. sodium or potassium, cation if desired, one or more sources of aluminum and/or silicon, an organic (R) directing agent, hereinafter more particularly described, and a solvent or solvent mixture, such as, for example C -C β alcohols, C.-Cg diols and/or water, especially water, the reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: wherein e and f are the weighted average valences of M and R, respectively. In this third particular method, the pH is important and must be maintained at from 9 to 14. This method involves the following steps: (1) Mix the organic (R) directing agent with the solvent or solvent mixture such that the mole ratio of solvent/R 2/f O is within the range of from 50 to 800, preferably from 50 to 500. This mixture constitutes the "primary template" for the synthesis method. (2) To the primary template mixture of step (1) add the sources of oxides, e.g. silica and/or alumina such that the ratio of R 2/f O/(Si0 2 +Al_0 3 ) is within the range of from 0.01 to 2.0. SUBSTITUTE SH (3) Agitate the mixture resulting from step (2) at a temperature of from 20 "C to 40°C, preferably for from 5 minutes to 3 hours. (4) Allow the mixture to stand with or without agitation, preferably at a temperature of from 20 β C to 100 β C, and preferably for from 10 minutes to 24 hours. (5) Crystallize the product from step (4) at a temperature of from 50 β C to 175"C, preferably for from 1 hour to 72 hours. Crystallization temperatures higher in the given ranges are most preferred. A fourth particular method for the present synthesis involves the reaction mixture used for the third particular method, but the following specific procedure with tetraethylorthosilicate the source of silicon oxide: (1) Mix the organic (R) directing agent with the solvent or solvent mixture such that the mole ratio of solvent/R 2/f 0 is within the range of from 50 to 800, preferably from 50 to 500. This mixture constitutes the "primary template" for the synthesis method. (2) Mix the primary template mixture of step (1) with tetraethylorthosilicate and a source of aluminum oxide, if desired, such that the R 2/f 0/Si0_ mole ratio is in the range of from 0.5 to 2.0. (3) Agitate the mixture resulting from step (2) for from 10 minutes to 6 hours, preferably from 30 minutes to 2 hours, at a temperature of from 0'C to 25°C, and a pH of less than 12. This step permits hydrolysis/polymerization to take place and the resultant mixture will appear cloudy. (4) Crystallize the product from step (3) at a temperature of from 25°C to 150°C, preferably from 95°C to 110°C, for from 4 to 72 hours, preferably from 16 to 48 hours. In each of the above general and particular methods, batch crystallization of the present crystalline material can be carried out under either static or agitated, e.g. stirred, conditions in a suitable reactor vessel, such as for example, polypropylene jars or Teflon lined or stainless steel autoclaves. Crystallization may also be conducted continuously in suitable equipment. The total useful range of temperatures for crystallization is noted above for each method for a time sufficient for crystallization to occur at the temperature used, e.g. from 5 minutes to 14 days. Thereafter, the crystals are separated from the liquid and recovered. When a source of silicon is used in the synthesis method, an organic silicate, such as, for example, a quaternary ammonium silicate, may be used, at least as part of this source. Non-limiting examples of such a silicate include tetramethylammonium silicate and tetraethylorthosilicate. By adjusting conditions of the synthesis reaction for each method, such as temperature, pH and time of reaction, etc., within the above limits, embodiments of the present non-layered crystalline material with a desired average pore size may be prepared. In particular, changing the pH, the temperature or the reaction time may promote formation of product crystals with different average pore size. Non-limiting examples of various combinations of W, X, Y and Z contemplated for the first and second particular synthesis methods of the present invention include: si including the combinations of W being Mg, or an element selected from the divalent first row transition metals, e.g. Mn, Co and Fe; X being B, Ga or Fe; and Y being Ge. An organic directing agent for use in each of the above general and particular methods for synthesizing the present material from the respective reaction mixtures is an ammonium or phosphonium ion of the formula R.R R.R.Q , i.e: R l R 4 - Q + —R 2 R 3 wherein Q is nitrogen or phosphorus and wherein at least one of R_, R 2 , R 3 and R. is aryl or alkyl of from 6 to 36 carbon atoms, e.g. -C_H 13 , ~ C 10 H 21 , ~ i 6 H 33 and ~C 18 H_ 7 , or combinations thereof, the remainder of R., R 2 , 3 and R. being selected from hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof. The compound from which the above ammonium or phosphonium ion is derived may be, for example, the hydroxide, halide, silicate, or mixtures thereof. In the first and third particular methods above, it is preferred to have an additional organic directing agent and in the second particular method it is required to have a combination of the above organic directing agent and an additional organic directing agent. That additional organic directing agent is the ammonium or phosphonium ion of the above directing agent formula wherein R_, R_, R_ and R. together or separately are selected from the group consisting of hydrogen and alkyl of 1 to 5 carbon atoms and combinations thereof. Any such combination of organic directing agents go to make up "R" and will be in molar ratio of 100/1 to 0.01/1, first above listed organic directing agent/additional organic directing agent. The particular effectiveness of the presently required directing agent, when compared with other such agents known to direct synthesis of one or more other crystal structures, is believed due to its ability to function as a template in the above reaction mixture in the nucleation and growth of the desired ultra-large pore crystals with the limitations discussed above. Non-limiting examples of these directing agents include cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldidodecylammonium. It should be realized that the reaction mixture components can be supplied by more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the new crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions. The crystals prepared by the instant invention can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded. The present compositions are useful as catalyst components for catalyzing the conversion of organic compounds, e.g. oxygenates and hydrocarbons, by acid-catalyzed reactions. The size of the pores is also such that the spatiospecific selectivity with respect to transition state species is minimized in reactions such as cracking (Chen et al., "Shape Selective Catalysis in Industrial Applications", 36 CHEMICAL INDUSTRIES, pgs. 41-61 (1989) to which reference is made for a discussion of the factors affecting shape selectivity) . Diffusional limitations are also minimized as a result of the very large pores in the present materials. For these reasons, the present compositions are especially useful for catalyzing reactions which occur in the presence of acidic sites on the surface of the catalyst and which involve reactants, products or transitional state species which have large molecular sizes, too great for undergoing similar reactions with conventional large pore size solid catalysts, for example, large pore size zeolites such as zeolite X, Y, L, ZSM-4, ZSM-18, and ZSM-20. Thus, the present catalytic compositions will catalyze reactions such as cracking, and hydrocracking, and other conversion reactions using hydrocarbon feeds of varying molecular sizes, but with particular applicability to feeds with large molecular sizes such as highly aromatic hydrocarbons with substituted or unsubstituted polycyclic aromatic components, bulky naphthenic compounds or highly substituted compounds with bulky steric configurations, e.g. molecular sizes of 13 Angstroms or more. The present catalytic compositions are particuarly useful for reactions in which the molecular weight of the feed is reduced to a lower value, i.e. to reactions involving cracking such as cracking or hydrocracking. Cracking may be conducted at a temperature of from 200°C to 800 β C, a pressure of from atmospheric to 790 kPa (100 psig) and contact time of from 0.1 second to 60 minutes. Hydrocracking may be conducted at a temperature of from 150 β C to 550 β C, a pressure of from 790 kPa (100 psig) to 20800 kPa (3000 psig) , and a weight hourly space velocity of from 0.1 hr -1 to 100 hr-l, with a hydrogen/hydrocarbon molar ratio of from 0.1 to 100. The present catalytic compositions are especially useful for reactions using high molecular weight, high boiling or non-distillable feeds, especially residual feeds, i.e. feeds which are essentially non-distillable or feeds which have an initial boiling point (5% point) above 566 β C (1050 β F) . Residual feeds which may be used with the present catalytic compositions include feeds with API gravities below 20, usually below 15 and typically from 5 to 10 with Conradsen Carbon Contents (CCR) of at least 1% by weight and more usually at least 5% or more, e.g. 5-10%. In some resid fractions SUBSTITUTE SHEE the CCR may be as high as 20 weight percent or even higher. The aromatic contents of these feeds will be correspondingly high, as may the contents of heteroatoms such as sulfur and nitrogen, as well as metals. Aromatics content of these feeds will usually be at least 50 weight percent and typically much higher, usually at least 70 or 80 weight percent, with the balance being principally naphthenes and heterocyclics. Typical petroleum refinery feeds of this type include atmospheric and vacuum tower resids, asphalts, aromatic extracts from solvent extraction processes, e.g. phenol or furfural extraction, deasphalted oils, slop oils and residual fractions from various processes such as lube production, coking and the like. High boiling fractions with which the present catalytic compositions may be used include gas oils, such as atmospheric gas oils; vacuum gas oils; cycle oils, especially heavy cycle oil; deasphalted oils; solvent extracts, such as bright stock; heavy gas oils, such as coker heavy gas oils; and the like. The present catalytic materials may also be utilized with feeds of non-petroleum origin, for example, synthetic oils produced by coal liquefaction, Fischer-Tropsch waxes and heavy fractions and other similar materials. Another example of a particular feed is shale oil. The present invention relates to a method for removing metal from a metal-containing hydrocarbon feed by hydrotreating. The feed is contacted with hydrogen in the presence of a hydrotreating catalyst comprising the mesoporous material described herein. The hydrotreating catalyst also includes a hydrogenation component such as one or more metals selected from Group VIA and Group VIII of the Periodic Table. The preferred Group VIII metals include iron, nickel and cobalt, with nickel and cobalt being especially preferred. The preferred Group VIA metals include molybdenum and tungsten. The metals of Group VIII commonly known as the "noble" metals (e.g., palladium and platinum) are more expensive and more readily subject to poisoning than are iron, nickel and cobalt. Thus, the non-noble metals of Groups VIII are preferred to the noble metals thereof as a hydrogenation component. Although noble metals may, in theory, be useful in the present catalyst system, it is currently believed that in the practical applications envisioned, the overall effectiveness of catalyst systems containing non-noble metals will be much greater. It should be understood that the content of the noble metal in percent by weight would be considerably lower than the ranges set forth below for non-noble metals; a range of from 0.1 to 5% by weight has been found to be * suitable for the noble metals. Accordingly, the following description relating to the metals content and, more specifically, the Group VIII metals content of the present catalyst system, is oriented toward the use of non-noble metals from Group VIII. The Group VIA and Group VIII metals content of the present catalyst system may range from 1 to 10% of Group VIII metal and from 2 to 20% of Group VIA metal. A preferred amount of Group VIII metal in elemental form is between 2% and 10%. A preferred amount of Group VIA metal in elemental form is between 5% and 20%. The foregoing amounts of metal components are given in percent by weight of the catalyst on a dry basis. SUBSTIT The metals content, which is defined as including both the Group VIA metal(s) and the Group VIII metal(s), most preferably nickel and molybdenum or cobalt and molybdenum, may range from 10 to 25% by weight, expressed in elemental form, based on total catalyst. The relative proportion of Group VIII metal to Group VIA metal in the catalyst system is not narrowly critical, but Group VIA, e.g., molybdenum, is usually utilized in greater amounts than the Group VIII metal, e.g., nickel. The metals removed from the feed may include such common metal contaminants as nickel, vanadium, iron, copper, zinc and sodium, and are often in the form of large organometallic complexes such as metal porphyrins or asphaltenes. The feedstock employed in the present invention will normally be substantially composed of hydrocarbons boiling above 340 β C and containing a substantial quantity of asphaltic materials. Thus, the chargestock can be one having an initial or 5 percent boiling point somewhat below 340"C provided that a substantial proportion, for example, 70 or 80 percent by volume, of its hydrocarbon components boil above 340 β C. A hydrocarbon stock having a 50 percent boiling point of 480 β C and which contains asphaltic materials, 4 percent by weight sulfur and 50 p.p.m. nickel and vanadium is illustrative of such chargestock. The process of the present invention may be carried out by contacting a metal contaminated feedstock with the above-described hydrotreating catalyst under hydrogen pressure of at least 2860 kPa (400 psig) , temperatures ranging between 315° to 455 β C (600 β to 850 β F) and liquid hourly space velocities between 0.1 and 10 hr " , based on the total complement of catalyst in the system. Preferably these conditions include hydrogen pressures between 7000 to 17000 kPa (1000 to 2500 psig), temperatures between 370" to 440 β C (700 β to 825 β F), and liquid hourly space velocities between 0.2 and 1. 0 hr " . The catalytic hydrotreating may take place in any suitable hydrotreating reactor, preferably a fixed bed downflow (trickle bed) reactor. Other suitable hydrotreaters include moving bed downflow ("bunker") reactors, fluidized bed or ebullated bed reactors and fixed bed upflow reactors. For the upgrading feedstocks such as resids, the present catalysts are quite active for asphaltene conversion and removal of nickel and vanadium, while operating at low overall hydrogen consumptions. Especially for upgrading shale oils, the present catalysts are particularly active for olefin saturation, denitrogenation and removal of iron and nickel. These catalysts are also active for desulfurization and arsenic removal. In view of the high pore volume of the mesoporous catalyst component, a large volume for metals uptake is also available. As in the case of many catalysts, it may be desired to incorporate the new crystal composition with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina, titania and/or zirconia. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new crystal, i.e. combined therewith or present during synthesis of the new crystal, which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated with naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst. Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. In addition to the foregoing materials, the new crystal can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. It may be desirable to provide at least a part of the foregoing matrix materials in colloidal form so as to facilitate extrusion of the bound catalyst components(s) . The relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 weight percent of the composite. In order to more fully illustrate the nature of the invention and the manner of practicing same, the following Examples are presented. In the Examples, whenever sorption data are set forth for comparison of sorptive capacities for water, cyclohexane, benzene and/or n-hexane, they are Equilibrium Adsorption values determined as follows: A weighed sample of the adsorbent, after calcination at 540 β C for at least 1 hour and other treatment, if necessary, to remove any pore blocking contaminants, is contacted with the desired pure adsorbate vapor in an adsorption chamber. The increase in weight of the adsorbent is calculated as the adsorption capacity of the sample in terms of grams/100 grams adsorbent based on adsorbent weight after calcination at 540°C. The present composition exhibits an equilibrium benzene adsorption capacity at 50 nm Hg (50 Torr) and 25°C of greater than 15 grams/100 grams, particularly greater than 17.5 g/100 g and more particularly greater than 20 g/100 g. A preferred way to " do this is to contact the desired pure adsorbate vapor in an adsorption chamber evacuated to less than 1 mm at conditions of 12 Torr of water vapor, 40 Torr of n-hexane or cyclohexane vapor, or 50 Torr of benzene vapor, at 25"C. The pressure is kept constant (within ± 0.5 mm) by addition of adsorbate vapor controlled by a manostat during the adsorption period. As adsorbate is adsorbed by the new crystal, the decrease in pressure causes the manostat to open a valve which admits more adsorbate vapor to the chamber to restore the above control pressures. Sorption is complete when the pressure change is not sufficient to activate the manostat. Another way of doing this for benzene adsorption data is on a suitable thermogravimetric analysis system, such as a computer-controlled 990/951 duPont TGA system. The adsorbent sample is dehydrated (physically sorbed water removed) by heating at, for example, 350°C or 500°C to constant weight in flowing helium. If the sample is in as-synthesized form, e.g. containing organic directing agents, it is calcined at 540 β C in air and held to constant weight instead of the previously described 350 β C or 500"C treatment. Benzene adsorption isotherms are measured at 25"C by blending a benzene saturated helium gas stream with a pure helium gas stream in the proper proportions to obtain the desired benzene partial pressure. The value of the adsorption at 50 Torr of benzene is taken from a plot of the adsorption isotherm. In the Examples, percentages are by weight unless otherwise indicated. Examples 1 to 19 illustrate the preparation of various ultra-large pore catalytic materials useful in the present process. Example 1 One hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution, prepared by contacting a 29 wt.% N,N,N- trimethyl-1-hexadecanaminium chloride solution with a hydroxide-for-halide exchange resin, was combined with 100 grams of an aqueous solution of tetramethylammonium (TMA) silicate (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 μm, was added. The resulting mixture was placed in a polypropylene bottle, which was placed in a steam box at 95°C overnight. The mixture had a composition in terms of moles per mole A1,0 3 : 2.7 moles Na_0 392 moles SiO_ 35.7 moles (CTMA) 2 0 61.7 moles (TMA) 2 0 6231 moles H_0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area 2 2 of 4755 mm //gg aanndd tthhee ffoolllloowwiinngg ιequilibrium adsorption capacities in grams/100 grams: The product of this example may be characterized by X-ray diffractiion as including a very strong relative intensity line at 37.8 + 2.0 A d-spacing, and weak lines at 21.6 + 1.0 and 19.2 + 1.0 A. Transmission electron microscopy (TEM) produced images of a hexagonal arrangement of uniform pores and hexagonal electron diffraction pattern with a d. QQ value of 39 A. Example 2 One hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 100 grams of an aqueous solution of tetramethylammonium (TMA) hydroxide (25%) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 μm, was added. The resulting mixture was placed in a static autoclave at 150"C overnight. The mixture had a composition in terms of moles per mole A1,0 3 : 2.7 moles Na 0 291 moles SiO_ 35.7 moles (CTMA)_0 102 moles (TMA) O 6120 moles H O The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area 2 of 993 m /g and the following equilibrium adsorption capacities in grams/100 grams: H O 7.1 Cyclohexane 47.2 n-Hexane 36.2 Benzene 49.5 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 39.3 + 2.0 A d-spacing, and weak lines at 22.2 + 1.0 and 19.4 + 1.0 A. TEM indicated that the product contained the ultra-large pore material. A portion of the above product was then contacted with 100% steam at 1450°F for two hours. The surface area of the steamed material was measured to be 440 m 2/g, indicating that 45% was retained following severe steaming. Another portion of the calcined product of this example was contacted with 100% steam at 1250°F for two hours. The surface area of this material was measured to be 718 m 2/g, indicating that 72% was retained after steaming at these conditions. Example 3 Water, cetyltrimethylammonium hydroxide solution prepared as in Example 1, aluminum sulfate, HiSil and an aqueous solution of tetrapropylammonium (TPA) bromide (35%) were combined to produce a mixture having a composition in terms of moles per mole A1_0 3 : 0.65 moles Na 2 0 65 moles Si0_ 8.8 moles ( * CTMA)_0 1.22 moles (TPA) 2 0 1336 moles H O The resulting mixture was placed in a polypropylene bottle, which was kept in a steam box at 95°C for 192 hours. The sample was then cooled to room temperature and combined with CTMA hydroxide solution prepared as in Example 1 and TMA hydroxide (25% by weight) in the weight ratio of 3 parts mixture, 1 part CTMA hydroxide and 2 parts TMA hydroxide. The combined mixture was then placed in a polypropylene bottle and kept in a steam box at 95°C overnight. The combined mixture had a composition in terms of moles per- mole A1 2 0 3 : 0.65 moles Na 2 0 65 moles Si0 2 15 moles (CTMA)_0 1.22 moles (TPA) 2 0 35.6 moles (TMA) 2 0 2927 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540"C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area of 10 8855 mm 2 2//gg aanndd tthhee ffoolllloowwiinngg equilibrium adsorption capacities in grams/100 grams: The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 38.2 + 2.0 A d-spacing, and weak lines at 22.2 + 1.0 and 19.4 + 1.0 A. TEM indicated the product contained the ultra-large pore material. Example 4 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 2 grams of Catapal alumina (alpha-alumina monohydrate, 74% alumina) and 100 grams of an aqueous solution of tetramethylammonium (TMA) silicate (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 micron, was added. The resulting mixture was placed in a static autoclave at 150°C for 48 hours. The mixture had a composition in terms of moles per mole A1 2 0 3 : 0.23 moles Na 2 0 33.2 moles Si0 2 6.1 moles (CTMA)_0 5.2 moles (TMA) 2 0 780 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540"C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area of 1043 m /g and the following equilibrium adsorption capacities in grams/100 ' grams: H 2 0 6.3 Cyclohexane > 50 n-Hexane 49.1 Benzene 66.7 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 40.8 + 2.0 A d-spacing, and weak lines at 23.1 + 1.0 and 20.1 + 1.0 A. TEM indicated that the product contained the ultra-large pore material. Example 5 Two-hundred sixty grams of water was combined with 77 grams of phosphoric acid (85%) , 46 grams of Catapal alumina (74% alumina) , and 24 grams of pyrrolidine (Pyr) with stirring. This first mixture was placed in a stirred autoclave and heated to 150 β C for six days. The material was filtered, washed and air-dried. Fifty grams of this product was slurried with 200 grams of water and 200 grams of cetyltrimethylammonium hydroxide solution prepared as in Example 1. Four hundred grams of an aqueous solution of tetraethylammonium silicate (10% silica) was then added to form a second mixture which was placed in a polypropylene bottle and kept in a steam box at 95 β C overnight. The first mixture had a composition in terms of moles per mole 1 2 0 3 : 1.0 moles P Δ_0__> 0.51 moles (Pyr) 2 0 47.2 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540"C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area of 707 m 2/g and the followi.ng equilibri.um adsorpti.on capacities in grams/100 grams: H-0 33.2 Cyclohexane 19.7 n-Hexane 20.1 Benzene 23.3 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 25.4 + 1.5 A d-spacing. TEM indicated the product contained the present ultra-large pore material. Example 6 A solution of 1.35 grams of NaA10 2 (43.5% A1 2 0 3 , 30% Na 2 0) dissolved in 45.2 grams of water was mixed with 17.3 grams of NaOH, 125.3 grams of colloidal silica (40%, Ludox HS-40) and 42.6 grams of 40% aqueous solution of tetraethylammonium (TEA) hydroxide. After stirring overnight, the mixture was heated for 7 days in a steam box (95°C). Following filtration, 151 grams of this solution was mixed with 31 grams of cetyltrimethylammonium hydroxide solution prepared as in Example 1 and stored in the steam box at 95°C for 13 days. The mixture had the following relative molar composition: 0.25 moles A1_0 10 moles Na 2 0 36 moles SiO_ 0.95 moles (CTMA) 2 0 2.5 moles (TEA) 2 0 445 moles H 2 0 The resulting solid product was recovered by filtration and washed with water and ethanol. The product was then calcined at 540 β C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product composition included 0.14 wt.% Na, 68.5 wt.% SiO_ and 5.1 wt.% 1 2 0_, and proved to have a benzene equilibrium adsorption capacity of 58.6 grams/100 grams. The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 31.4 + 1.5 A d-spacing. TEM indicated that the product contained the present ultra-large pore material. Example 7 A mixture of 300 grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 and 41 grams of colloidal silica (40%, Ludox HS-40) was heated in a 600 ml autoclave at 150°C for 48 hours with stirring at 200 rpm. The mixture has a composition in terms of moles per mole Si0 2 : 0.5 mole (CTMA) 2 0 46.5 moles H ? 0 The resulting solid product was recovered by filtration, washed with water, then calcined at 540 " C for 1 hour in nitrogen, followed by 10 hours in air. The calcined product composition included less than 0.01 wt.% Na, 98.7 wt.% Si0 2 and 0.01 wt.% A1 2 0 3 , and proved to have a surface area of 896 m /g. The calcined product had the following equilibrium adsorption capacities in grams/100 grams: H 2 0 8.4 Cyc1ohexane 49.8 n-Hexane 42.3 Benzene 55.7 The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 40.0 + 2.0 A d-spacing and a weak line at 21.2 + 1.0 A. TEM indicated that the product of this example contained at least three separate phases, one of which was the ultra-large pore material. Example 8 A mixture of 150 grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 and 21 grams of colloidal silica (40%, Ludox HS-40) with an initial pH of 12.64 was heated in a 300 cc autoclave at 150°C for 48 hours with stirring at 200 rpm. The mixture had a composition in terms of moles per mole Si0 2 : 0.5 mole (CTMA) 2 0 46.5 moles H_0 The resulting solid product was recovered by filtration, washed with water, then calcined at 540°C for 6 hours in air. The calcined product composition was measured to include 0.01 wt.% Na, 93.2 wt.% SiO and 0.016 wt.% A1 2 0 3 , and proved to have a surface area of 992 m 2/g S and the following equilibrium adsorption capacities in grams/100 grams: H 2 0 4.6 Cyclohexane > 50 n-Hexane > 50 Benzene 62.7 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 43.6 + 2.0 A d-spacing and weak lines at 25.1 ± 1.5 and 21.7 ± 1.0 A. TEM indicated that the product contained the ultra-large pore material. Example 9 Sodium aluminate (4.15g) was added slowly into a solution containing 16g of myristyltrimethylammonium bromide (C-.TMABr) in lOOg of water. Tetramethylammoniu silicate (100g-10% Si0 2 ) , HiSil (25g) and tetramethylammonium hydroxide (14.2g-25% solution) were then added to the mixture. The mixture was crystallized in an autoclave at 120 β C with stirring for 24 hours. The product was filtered, washed and air dried. Elemental analysis showed the product contained 53.3 Wt% Si0 2 , 3.2 Wt% A1-0-, 15.0 Wt% C, 1.88 Wt% N, 0.11 wt% Na and 53.5 wt% ash at 1000°C. The X-ray diffraction pattern of the material after calcination at 540 β C for 1 hour in N 2 and 6 hours in air includes a very strong relative intensity line at 35.3 + 2.0 A d-spacing and weak lines at 20.4 + 1.0 and 17.7 + 1.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material. The washed product, having been exchanged with IN ammonium nitrate solution at room temperature, then 2 calcined, proved to have a surface area of 827 m /g and the following equilibrium adsorption capacities in g/lOOg anhydrous sorbent: H 2 0 30.8 Cyclohexane 33.0 n-Hexane 27.9 Benzene 40.7 Example 10 Sodium aluminate (8.3g) was added slowly into a solution containing 184g of dodecyltrimethylammonium hydroxide (C.-TMAOH, 50%) solution diluted with 480g of water. UltraSil (50g) and an aqueous solution of tetramethylammonium silicate (200g-10% Si0 2 ) and tetramethylammonium hydroxide (26.38g-25% solution) were then added to the mixture. The mixture was crystallized in an autoclave at 100°C with stirring for 24 hours. The product was filtered, washed and air dried. After calcination at 540°C for 1 hour in N 2 and 6 hours in air, the X-ray diffraction pattern includes a very strong relative intensity line at 30.4 ± 1.5 A d-spacing and weak lines at 17.7 + 1.0 and 15.3 + 1.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material. The washed product, having been exchanged with IN ammonium nitrate solution at room temperature, then 2 calcined, proved to have a surface area of 1078 m /g and the following equilibrium adsorption capacities in g/lOOg anhydrous sorbent: Example 11 A solution of 4.9 grams of NaA10 2 (43.5 % A1 2 0 3 , 30% Na0 2 ) in 37.5 grams of water was mixed with 46.3 cc of 40% aqueous tetraethylammonium hydroxide solution and 96 grams of colloidal silica (40%, Ludox HS-40) . The gel was stirred vigorously for 0.5 hour, mixed with an equal volume (150 ml) of cetyltrimethylammonium hydroxide solution prepared as in Example 1 and reacted at 100 β C for 168 hours. The mixture had the following composition in terms of moles per mole A1 2 0_: 1.1 moles Na_0 30.6 moles Si0 2 3.0 moles (TEA) 2 0 3.25 moles (CTMA) 2 0 609 moles H 2 0 The resulting solid product was recovered by filtration, washed with water then calcined at 540 β C for 16 hours in air. The calcined product proved to 2 have a surface area of 1352 m /g and the following equilibrium adsorption capacities in grams/100 grams: H 2 0 23.6 • Cyclohexane >50 n-Hexane 49 Benzene 67.5 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 38.5 + 2.0 A d-spacing and a weak line at 20.3 + 1.0 A. TEM indicated that the product contained the ultra-large pore material. Example 12 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 micron, was added. The resulting mixture was placed in a static autoclave at 150 β C for 24 hours. The mixture had a composition in terms of moles per mole A1 2 0 3 : 1.25 moles Na 2 0 27.8 moles SiO_ 5.1 moles (CTMA) 2 0 4.40 moles (TMA)_0 650 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540 β C for 1 hour in nitrogen, followed by 6 hours in air. TEM indicated that this product contained the ultra-large pore material. The X-ray diffraction pattern of the calcined product of this example can be characterized as including a very strong relative intensity line at 44.2 + 2.0 A d-spacing and weak lines at 25.2 ± 1.5 and 22.0 + 1.0 A. The calcined product proved to have a surface area of 9322 m 2 2//gg aanndd tthhee ffoolllloowwii.nngg <equi.li.bri.um adsorption capacities in grams/100 grams: Example 13 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 micron, was added. The resulting mixture was placed in a steam box at 100 β C for 48 hours. The mixture had a composition in terms of moles per mole A1 2 0 : 1.25 moles Na 2 0 27.8 moles SiO 2, 5.1 moles (CTMA) 2 0 4.4 moles (TMA) 2 0 650 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have the following equilibrium adsorption capacities in grams/100 grams: H 2 0 35.2 Cyclohexane > 50 n-Hexane 40.8 Benzene 53.5 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 39.1 + 2.0 A d-spacing and weak lines at 22.4 + 1.0 and 19.4 ± 1.0 A. TEM indicated that this product contained the ultra-large pore material. Example 14 A mixture of 125 grams of 29% CTMA chloride aqueous solution, 200 grams of water, 3 grams of sodium aluminate (in 50 grams H 2 0) , 65 grams of Ultrasil, amorphous precipitated silica available from PQ Corporation, and 21 grams NaOH (in 50 grams H 2 0) was stirred thoroughly and crystallized at 150°C for 168 hours. The reaction mixture had the following relative molar composition in terms of moles per mole silica: 0.10 moles (CTMA) 2 0 21.89 moles H..0 0.036 moles NaA10 2 0.53 moles NaOH The solid product was isolated by filtration, washed with water, dried for 16 hours at room temperature and calcined at 540 β C for 10 hours in air. The calcined product proved to have a surface area of 2 840 m /g, and the following equilibrium adsorption capacities in grams/100 grams: H 2 θ 15.2 Cyc1ohexane 42.0 n-Hexane 26.5 Benzene 62 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 40.5 + 2.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material. Example 15 To make the primary template mixture for this example, 240 grams of water was added to a 92 gram solution of 50% dodecyltrimethylammonium hydroxide, 36% isopropyl alcohol and 14% water such that the mole ratio of Solvent/R 2/f 0 was 155. The mole ratio of H-O/R 2 f 0 in this mixture was 149 and the IPA/R 2/f O mole ratio was 6. To the primary template mixture was added 4.15" grams of sodium aluminate, 25 grams of HiSil, 100 grams of aqueous tetramethylammonium silicate solution (10% Si0 2 ) and 13.2 grams of 25% aqueous tetramethylammonium hydroxide solution. The mole ratio of R 2/f O/(Si0 2 +Al 2 0 3 ) was 0.28 for the mixture. This mixture was stirred at 25 β C for 1 hour. The resulting mixture was then placed in an autoclave at 100 β C and stirred at 100 rpm for 24 hours. The mixture in the autoclave had the following relative molar composition in terms of moles per mole Si0 2 : 0.05 mole Na 2 0 0.036 mole 1 2 0 3 0.18 mole (C 12 T A) 2 0 0.12 mole (TMA) O 36.0 moles H 2 0 1.0 mole IPA The resulting solid product was recovered by filtration, washed with water and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area 2 of 1223 m /g and the following equilibrium adsorption capacities in grams/100 grams: H 2 0 25.5 Cyclohexane 41.1 n-Hexane 35.1 Benzene 51 The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 30.8 ± 1.5 A d-spacing and weak lines at 17.9 + 1.0 and 15.5 ± 1.0 A. TEM indicated this product to contain the ultra-large pore material. Example 16 A 50.75 gram quantity of decyltrimethylammonium hydroxide (prepared by contacting a ca. 29 wt.% solution of decyltrimethylammonium bromide with a hydroxide-for-halide exchange resin) was combined with 8.75 grams of tetraethylorthosilicate. The mixture was stirred for 1 hour and then transferred to a polypropylene jar which was then placed in a steambox for 24 hours. The mixture had a composition in terms of moles per mole Si0 2 : 0.81 mole (C 10 TM ) 2 0 47.6 moles H 2 0 The resulting solid product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538°C in N 2 /air mixture and then held in air for 8 hours. The calcined product proved to have a surface 2 area of 915 m /g and an equilibrium benzene adsorption capacity of 35 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.34 cc/gram, and a pore size of 15 A. The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 27.5 ± 1.5 A d-spacing and weak lines at 15.8 ± 1.0 and 13.7 + 1.0 A. TEM indicated that the product of this example contained the ultra-large pore material. Example 17 To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaAl0 2 . The mixture was stirred at room temperature until the NaA10 2 was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% Si0 2 ), 10 grams of HiSil, 200 grams of water and 70 grams of 1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 600 cc autoclave and heated at 105 β C for sixty-eight hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole A1 2 0 3 : 1.25 moles Na_0 27.8 moles Si0 2 5.1 moles (CTMA) 2 0 2.24 moles (TMA)_0 2256 moles H 2 0 80.53 moles 1,3,5-trimethylbenzene The resulting product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538 β C in N 2 /air mixture and then held in air for 10 hours. The calcined product proved to have an equilbrium benzene adsorption capacity of >25 grams/100 grams. The X-ray diffraction pattern of the calcined product may be characterized as including a broad, very strong relative intensity line at 102 A d-spacing, but accurate positions of lines in the extreme low angle region of the X-ray diffraction pattern are very difficult to determine with conventional X-ray diffractometers. Furthermore, finer collimating slits were required to resolve a peak at this low 2-theta angle. The slits used in this example, starting at the X-ray tube, were 0.1, 0.3, 0.5 and 0.2 mm, respectively. TEM indicated that the product of this example contained several materials with different d 100 values as observed in their electron diffraction patterns. These materials were found to possess d. QQ values between 85 A d-spacing and 120 A d-spacing. Example 18 To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaA10 2 - The mixture was stirred at room temperature until the NaA10 2 was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% SiO ) , 10 grams of HiSil, 200 grams of water and 120 grams of 1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 600 cc autoclave and heated at 105"C for ninety hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole Al 2 0 3 : 1.25 moles Na 0 27.8 moles Si0 2 5.1 moles (CTMA) 2 0 2.24 moles (TMA) 2 0 2256 moles H 2 0 132.7 moles 1,3,5-trimethylbenzene The resulting product was filtered and washed several times with warm (60-70"C) distilled water and with acetone. The final product was calcined to 538 " C in N 2 /air mixture and then held in air for 10 hours. The calcined product proved to have a surface area of 2 915 m /g and an equilbrium benzene adsorption capacity of >25 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.95 cc/gra , and a pore size centered on 78 A (Dollimore-Heal Method, see Example 22(b)) , but running from 70 to greater than 105 Angstoms. The X-ray diffraction pattern of the calcined product of this example may be characterized as having only enhanced scattered intensity in the very low angle region of the X-ray diffraction, where intensity from the transmitted incident X-ray beam is usually observed. However, TEM indicated that the product contained several materials with different d. QQ values as observed in their electron diffraction patterns. These materials were found to possess de¬ values between 85 A d-spacing and 110 A d-spacing. Example 19 To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaA10 2 . The mixture was stirred at room temperature until the NaA10 2 was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% Si0 2 ) , 10 grams of HiSil, and 18 grams of 1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 300 cc autoclave and heated at 105 β C for four hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole A1 2 0 3 : 1.25 moles Na 2 0 27.8 moles Si0 2 5.1 moles (CTMA) 2 0 2.24 moles (TMA) 2 0 650 moles H 2 0 19.9 moles 1,3,5-trimethylbenzene The resulting product was filtered and washed several times with warm (60-70"C) distilled water and with acetone. The final product was calcined to 538°C in N 2 /air mixture and then held in air for 8 hours. The calcined product proved to have a surface area of 975 m 2/g and an equi4lbri4um benzene adsorption capacity of >40 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.97 cc/gram, and a pore size of 63 A (Dollimore-Heal Method) , with the peak occurring at P/P =0.65. The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 63 + 5 A d-spacing and weak lines at 36.4 + 2.0, 31.3 + 1.5 A and 23.8 + 1.0 A d-spacing. TEM indicated that the product of this example contained the ultra-large pore material. Example 20 Argon Physisorption Determination To determine the pore diameters of the mesoporous products with pores up to 60 A in diameter, 0.2 gram samples of the products of Examples 1 through 17 were placed in glass sample tubes and attached to a physisorption apparatus as described in U.S. Patent No. 4,762,010. The samples were heated to 300 β C for 3 hours in vacuo to remove adsorbed water. Thereafter, the samples were cooled to 87°K by immersion of the sample tubes in liquid argon. Metered amounts of gaseous argon were then admitted to the samples in stepwise manner as described in U.S. Patent No. 4,762,010, column 20. From the amount of argon admitted to the samples and the amount of argon left in the gas space above the samples, the amount of argon adsorbed can be calculated. For this calculation, the ideal gas law and the calibrated sample volumes were used. (See also S.J. Gregg et al. , Adsorption, Surface Area and Porosity. 2nd ed. , Academic Press, 1982) . In each instance, a graph of the amount adsorbed versus the relative pressure above the sample, at equilibrium, constitutes the adsorption isotherm. It is common to use relative pressures which are obtained by forming the ratio of the equilibrium pressure and the vapor pressure P of the adsorbate at the temperature where the isotherm is measured. Sufficiently small amounts of argon were admitted in each step to generate 168 data points in the relative pressure range from 0 to 0.6. At least 100 points are required to define the isotherm with sufficient detail. The step (inflection) in the isotherm, indicates filling of a pore system. The size of the step indicates the amount adsorbed, whereas the position of the step in terms of P/P reflects the size of the pores in which the adsorption takes place. Larger pores are filled at higher P/P_« In order to better locate the position of the step in the isotherm, the derivative with respect to log (P/P ) is formed. The adsorption peak (stated in terms of log (P/P ) ) may be related to the physical pore diameter (A) by the following formula: logfP/P^ K .10 .10 d-0.38 3(L-D/2) 3 9(L-D/2) 9 3(D/2) 3 9(D/2) 9 where d = pore diameter in nanometers, K = 32.17, S = 0.2446, L = d + 0.19, and D = 0.57. This formula is derived from the method of Horvath and Kawazoe (G. Horvath et al., J. Chem. Eng. Japan. 16 SUBS (6) 470(1983)). The constants required for the implementation of this formula were determined from a measured isotherm of A1P0-5 and its known pore size. This method is particularly useful for microporous materials having pores of up to 60 A in diameter. The results of this procedure for the samples from Examples 1 through 17 are tabulated below. The samples from Examples 10, 13 and 15 gave two separate peaks, believed to be the result of two separate ultra-large pore phases in the products. Examle Pore Diameter A The above method of Horvath and Kawazoe for determining pore size from physisorption isotherms was intended to be applied to pore systems of up to 20 A diameter; but with some care as above detailed, its use can be extended to pores of up to 60 A diameter. In the pore regime above 60 A diameter, the Kelvin equation can be applied. It is usually given as: -2 γ V In(P/P ) = cos β r-_RT where: γ = surface tension of sorbate V = molar volume of sorbate Θ = contact angle (usually taken for practical reasons to be 0) R = gas constant T = absolute temperature r. = capillary condensate (pore) radius P/P = relative pressure (taken from the physisorption isotherm) The Kelvin equation treats adsorption in pore systems as a capillary condensation phenomenon and relates the pressure at which adsorption takes place to the pore diameter through the surface tension and contact angle of the adsorbate (in this case, argon) . The principles upon which the Kelvin equation are based are valid for pores in the size range 50 to 1000 Angstrom diameter. Below this range the equation no longer reflects physical reality, since true capillary condensation cannot occur in smaller pores; above this range the logarithmic nature of the equation precludes SUBSTITUTE SHE obtaining sufficient accuracy for pore size determination. The particular implementation of the Kelvin equation often chosen for measurement of pore size is that reported by Dollimore and Heal (D. Dollimore and G.R. Heal, J. Applied Chem. 14, 108 (1964)). This method corrects for the effects of the surface layer of adsorbate on the pore wall, of which the Kelvin equation proper does not take account, and thus provides a more accurate measurement of pore diameter. While the method of Dollimore and Heal was derived for use on desorption isotherms, it can be applied equally well to adsorption isotherms by simply inverting the data set. EXAMPLE 21 48 parts by weight of cetyltrimethylammonium (CTMA) hydroxide solution, prepared by contacting a 29 wt.% N,N,N-trimethyl-l-hexadecanaminium chloride solution with a hydroxide-for-halide exchange resin, was combined with l part by weight of sodium aluminate and 24 parts by weight of an aqueous solution of tetramethylammonium (TMA) silicate (10% silica) with stirring. 6 parts by weight of HiSil, a precipitated hydrated silica containing 6 wt.% free water and 4.5 wt.% bound water of hydration and having an ultimate particle size of 0.02 micron, was added. The resulting mixture was crystallized at 100 β C for 20 hours. The mixture had a composition in terms of moles per mole A1 2 0 3 : 1.46 moles- Na 2 0 27.8 moles Si0 2 5.6 moles (CTMA) O 3.11 moles (TMA) 2 0 723.7 moles H 2 0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540"C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have a surface area 2 of 1200 m /g and the following equilibrium adsorption capacities in grams/100 grams: H 2 0 13.5 Cyclohexane > 50 n-Hexane 43.6 Benzene 71 The product of this Example has an X-ray diffraction pattern including a very strong relative intensity line at 38.4 + 2.0 Angstroms d-spacing, and weak lines at 22.6 + 1.0, 20.0 + 1.0 and 15.2 + 1.0 Angstroms. EXAMPLE 22 35 parts by weight of the material of Example 21 was bound with 65 parts by weight of an alumina binder by a mulling and pelletizing procedure. The pelletized mixture was then calcined, first in nitrogen and then in air, at temperatures up to 538°C (1000°F) under conditions sufficient to substantially remove organic material included in the as-synthesized material from Example 21. Cations in the calcined pellets were then exchanged with ammonium cations by contacting the SUBSTITUTE SHEET pellets with solutions of IN NH.N0 3 maintained at a pH of 8. The twice-exchanged pellets were then dried in air at 121°C (250°F) followed by calcination at 538"C (1000°F) under conditions sufficient to decompose ammonium ions and evolve ammonia, thereby converting the bound material to the hydrogen form. The hydrogen form of the bound material was then impregnated with an ammonium heptamolybdate solution. More particularly, 45.12 ml of an aqueous solution containing 5.08 grams of ammonium heptamolybdate (81.5 wt.% Mo0 3 ) was added to 40 grams of the hydrogen form of the bound material. The resulting wet material was dried at 121 β C (250 β F) and then calcined in air at 538 β C (1000 β F) under conditions sufficient to decompose ammonium heptamolybdate and generate Mo0 3 , thereby producing a molybdenum impregnated material. The molybdenum impregnated bound material was then impregnated with a nickel nitrate solution. More particularly, 48.14 ml of an aqueous solution containing 9.12 grams of Ni(NO ) 2 β 6H 2 0 (21.2 wt.% Ni) was added to the molybdenum impregnated material. The resulting wet material was dried at 121"C (250 β F) and then calcined in air at 538 β C (1000°F) under conditions sufficient to decompose nickel nitrate and generate Nio, thereby producing a nickel and molybdenum impregnated material. The resulting catalyst had the properties shown in Table 1. " Table 1 Catalyst Properties Chemical Composition^ ' . wt% Nickel 4.9 Molybdenum 8.0 Physical properties Real Density, g/ml 2.784 2 Surface Area, M /g 306 ' ' 65 wt % Example 21 material and 35 wt % alumina prior to the metals addition. EXAMPLE 23 The catalyst of Example 22 was tested for upgrading an Arabian Light Atmospheric Resid at 7000 kPa (1000 psig) and a weight hourly space velocity (WHSV)of 0.66. Properties of this resid are given in Table 2. Reactor temperature was varied from 315°C (600°F) to 399 β C (750 β F) to cover a wide range of conversion. The results of this test are given in Table 3. These results indicate that the Example 22 catalyst is quite active for demetallation and asphaltene removal while requiring low hydrogen consumption (as determined by the low hydrogen content of the products) . Table 2 Table 3 Product Properties (ATM Resid, Ϊ900 psig, 0.66 WHSV) Cations in the as-synthesized material of Example 21 were exchanged with ammonium cations by contacting the material with a solution of 1M NH 4.NO-3 at room temperature for one hour. The exchanged material was filtered and rinsed with water. This exchange/filter/ rinse procedure was repeated and the material was then dried at 121"C (250 β F) overnight to form an ammonium exchanged material. 35 parts by weight of this ammonium exchanged material was bound with 65 parts by weight of an alumina binder by an extrusion procedure, thereby producing extrudate in the form of 1.58 mm (1/16-inch) cylinders. The extruded, bound material was dried overnight at 121"C (250°F) . The dried material was then calcined, first in nitrogen and then in air, at temperatures up to 538 β C (1000°F) under conditions sufficient to decompose ammonium ions and to substantially remove organic material, thereby converting the material to the hydrogen form. SUBSTITUTE SHEET The hydrogen form of the bound material was humidified with moist air by placing the material in the path of a stream of air which had been passed through a bubbler at room temperature. The moisture saturated material was then impregnated with a solution containing ammonium heptamolybdate and nickel nitrate. More particularly, 214.8 ml of an aqueous solution containing 25.8 grams of ammonium heptamolybdate (54.3 wt.% Mo, 81.5 wt.% Mo0 3 ) and 27.7 grams of Ni(N0 3 ) β 6H 2 0 (20.2 wt.% Ni) was added to 182 grams of the moisture saturated bound material. The resulting wet material was dried at 121 β C (250°F) and then calcined in air at 538°C (1000 β F) under conditions sufficient to decompose ammonium heptamolybdate and nickel nitrate, generating Mo0 3 and NiO, and thereby producing a molybdenum/nickel impregnated material. The resulting catalyst had the properties shown in Table 4. EXAMPLE 25 The catalyst of Example 24 was evaluated for upgrading Paraho shale oil at relatively mild conditions (2.0 LHSV and 7000 (1000 psig) H 2 ) . Analyses of the retorted Paraho shale oil are given in Table 5. Experimental data are summarized in Table 6. Table 5 10 nm = not measured The results of this evaluation showed that the Example 24 catalyst was quite active for olefin saturation, removal of iron and nickel, and denitrogenation. The catalyst is also active for arsenic removal and desulfurization. The catalyst can dearsenate the shale oil to less than 1.0 ppmw at 371°C (700 β F) . T H T

Claims: CLAIMS : 1. A process for demetallizing a hydrocarbon feedstock, which process comprises contacting the hydrocarbon feedstock with a catalyst under sufficient demetallation conditions, the catalyst comprising at least one hydrogenation metal and an inorganic, porous crystalline phase material having, after calcination, a hexagonal arrangement of uniformly-sized pores having diameters of at least 13 nm and exhibiting a hexagonal electron diffraction pattern that can be indexed with a ^ l oo va 3- ue greater than 18 nm. 2. A process according to Claim 1, wherein the crystalline phase has an X-ray diffraction pattern following calcination with at least one peak whose d-spacing corresponds to the d. QQ value from the electron diffraction pattern. 3. A process according to Claim 1, wherein the crystalline phase exhibits a benzene adsorption capacity of greater than 15 grams benzene per 100 grams at 6.7 kPa (50 Torr) and 25°C. 4. A process according to Claim 1, wherein the crystalline phase has a composition expressed as follows: M n/q (W a X b Y c Z d°h> wherein M is one or more ions; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; W is one or more divalent elements; X is one or more trivalent elements; Y is one or more tetravalent elements; Z is one or more pentavalent elements; a, b, c, and d are mole fractions of W, X, Y, and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d) = 1. 5. A process according to Claim 4, wherein the sum (a+b+c) is greater than d, and h = 2. 6. A process according to Claim 4, wherein W comprises a divalent first row transition metal or magnesium; X comprises aluminum, boron, gallium or iron; Y comprises silicon or germanium; and Z comprises phosphorus. 7. A process according to claim 4, wherein W comprises cobalt, X comprises aluminum, Y comprises silicon and Z comprises phosphorus. 8. A process according to claim 5, wherein W comprises a divalent first row transition metal or magnesium; X comprises aluminum, boron, gallium or iron; Y comprises silicon or germanium; and Z comprises phosphorus. 9. A process according to claim 5, wherein W comprises cobalt, X comprises aluminum, Y comprises silicon and Z comprises phosphorus. 10. A process according to claim 4, wherein a and d are 0 and h = 2. 11. A process according to claim 10, wherein X comprises aluminum, boron, gallium or iron and Y comprises silicon or germanium. 12. A process according to claim 10, wherein X comprises aluminum and Y comprises silicon. 13. A process according to claim 1, wherein the demetallation conditions include a hydrogen pressure of at least 2860 kPa, a temperature between 315°C and 455 β C and a liquid hourly space velocity between 0.1 - l and 10 hr SUBSTITUTE SHEET 14. A process according to claim 1, wherein the feedstock is substantially composed of hydrocarbons boiling at 340 β C. 15. A process according to claim 14, wherein the feedstock is an atmospheric resid. 16. A process according to claim 1, wherein the hydrogenation metal is selected from Group VIA metals and Group VIII metals. 17. A process according to claim 15, wherein the catalyst comprises two hydrogenation metals, and the hydrogenation metals are nickel and molybdenum. 18. A process according to claim 1, wherein the feedstock is shale oil. 19. A process according to claim 18, wherein the catalyst comprises two hydrogenation metals and the hydrogenation metals are nickel and molybdenum.

Inventors: DEGNAN THOMAS FRANCIS JR, DWYER FRANCIS GERARD, KEVILLE KATHLEEN MARIE, KRESGE CHARLES THEODORE, LANDIS MICHAEL EUGENE, LEONOWICZ MICHAEL EDWARD, ROTH WIESLAW JERZY, SHIH STUART SHAN-SAN, VARTULI JAMES CLARKE, DEGNAN, THOMAS, FRANCIS, JR., DWYER, FRANCIS, GERARD, KEVILLE, KATHLEEN, MARIE, KRESGE, CHARLES, THEODORE, LANDIS, MICHAEL, EUGENE, LEONOWICZ, MICHAEL, EDWARD, ROTH, WIESLAW, JERZY, SHIH, STUART, SHAN-SAN, VARTULI, JAMES, CLARKE
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1992
Main classification: C10G45
IPC codes: B01J29, B01J37, C10G45