EP0548296A4 - - Google Patents

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Publication number
EP0548296A4
EP0548296A4 EP19920904784 EP92904784A EP0548296A4 EP 0548296 A4 EP0548296 A4 EP 0548296A4 EP 19920904784 EP19920904784 EP 19920904784 EP 92904784 A EP92904784 A EP 92904784A EP 0548296 A4 EP0548296 A4 EP 0548296A4
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EP
European Patent Office
Prior art keywords
swollen
pillared
layered
oxide
ray diffraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19920904784
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English (en)
Other versions
EP0548296A1 (en
Inventor
Charles Theodore Kresge
Wieslaw Jerzy Roth
Kenneth Gregory Simmons
James Clarke Vartuli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
Original Assignee
Mobil Oil AS
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Publication date
Priority claimed from US07/811,384 external-priority patent/US5229341A/en
Application filed by Mobil Oil AS filed Critical Mobil Oil AS
Publication of EP0548296A1 publication Critical patent/EP0548296A1/en
Publication of EP0548296A4 publication Critical patent/EP0548296A4/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/049—Pillared clays
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This application relates to method of preparing a pillared, layered oxide material.
  • layered materials which have three-dimensional structures which exhibit their strongest chemical bonding in only two dimensions.
  • the stronger chemical bonds are formed in two-dimensional planes and a three-dimensional solid is formed by stacking such planes on top of each other.
  • the weaker bonds generally arise from interlayer attractions such as Van der Waals forces, electrostatic interactions, and hydrogen bonding.
  • a high degree of lubricity is manifested as the planes slide across each other without encountering the energy barriers that arise with strong interlayer bonding.
  • Graphite is an example of such a material.
  • the silicate layers of a number of clay materials are held together by electrostatic attraction mediated by ions located between the layers.
  • hydrogen bonding interactions can occur directly between complementary sites on adjacent layers, or can be mediated by interlamellar bridging molecules.
  • Laminated materials such as clays may be modified to increase their surface area.
  • the distance between the layers can be increased substantially by absorption of various swelling agents such as water, ethylene glycol, amines and ketones, which enter the interlamellar space and push the layers apart.
  • various swelling agents such as water, ethylene glycol, amines and ketones, which enter the interlamellar space and push the layers apart.
  • the interlamellar spaces of such layered materials tend to collapse when the molecules
  • SUBSTITUTESHEET occupying the space are removed by, for example, exposing the clays to high temperatures. Accordingly, such layered materials having enhanced surface area are not suited for use in chemical processes involving even moderately severe conditions.
  • the extent of interlayer separation can be estimated by using standard techniques such as X-ray diffraction to determine the basal spacing, also known as "repeat distance" or "d-spacing". These values indicate the distance between, for example, the uppermost margin of one layer with the uppermost margin of its adjoining layer. If the layer thickness is known, the interlayer spacing can be determined by subtracting the layer thickness from the basal spacing.
  • Various approaches have been taken to provide layered materials of enhanced interlayer distance having thermal stability. Most techniques rely upon the introduction of an inorganic "pillaring" agent between the layers of a layered material. For example, U.S.
  • Patent 4,216,188 discloses a clay which is cross-linked with metal hydroxide prepared from a highly dilute colloidal solution containing fully separated unit layers and a cross-linking agent comprising a colloidal metal hydroxide solution.
  • U.S. Patent 4,248,739 relates to a stable pillared interlayered clay prepared from a smectite clay reacted with a cationic metal complex of a metal such as aluminum and zirconium. The resulting product exhibits high interlayer separation and thermal stability.
  • U.S. Patent 4,176,090 discloses a clay composition interlayered with polymeric cationic hydroxy metal complexes of metals such as aluminum, zirconium and titanium. Interlayer distances of up to 16A are claimed although only distances restricted to about 9A are exemplified for calcined samples. These distances
  • SUBSTITUTESHEET are essentially unvariable and related to the specific size of the hydroxy metal complex.
  • Silicon-containing materials are believed to be a highly desirable species of intercalating agents owing to their high thermal stability characteristics.
  • U.S. Patent 4,367,163 describes a clay intercalated with silica by impregnating a clay substrate with a silicon-containing reactant such as an ionic silicon complex, e.g., silicon acetylacetonate, or a neutral species such as SiCl..
  • the clay may be swelled prior to or during silicon impregnation with a suitable polar solvent such as methylene chloride, acetone, benzaldehyde, tri- or tetraalkylammonium ions, or dimethylsulfoxide.
  • This method appears to provide only a monolayer of intercalated silica resulting in a product of small spacing between layers, about 2-3 A as determined by X-ray diffraction.
  • U. S. Patent 4,859,648 describes layered oxide products of high thermal stability and surface area which contain interlayer polymeric oxides such as polymeric silica. These products are prepared by ion exchanging a layered metal oxide, such as layered titanium oxide, with organic cation, to spread the layers apart. A compound such as tetraethylorthosilicate, capable of forming a polymeric oxide, is thereafter introduced between the layers. The resulting product is treated to form polymeric oxide, e.g. , by hydrolysis, to produce the layered oxide product. The resulting product may be employed as a catalyst material in the conversion of hydrocarbons.
  • Zeolites both naturally occurring and synthetic, are crystalline oxides, which unlike layered materials, are ordered and strongly bonded in three directions.
  • the structure of zeolites may be described as containing corner-sharing tetrahedra having a
  • SUBSTITUTE SHEET three-dimensional four-connected net with T-atoms at the vertices of the net and O-atoms near the midpoints of the connecting lines. Further characteristics of certain zeolites are described in Collection of Simulated XRD Powder Patterns for Zeolites by Roland von Ballmoos, Butterworth Scientific Limited, 1984.
  • Synthetic zeolites are often prepared from aqueous reaction mixtures comprising sources of appropriate oxides.
  • Organic directing agents may also be included in the reaction mixture for the purpose of influencing the production of a zeolite having the desired structure.
  • SUBSTITUTESHEET upon one another in an orderly fashion. This transformation may occur during the drying of the recovered crystals, even at moderate temperatures, e.g., 110 ⁇ C or greater.
  • the material When the swollen, non-pillared form of the material is calcined, the material may be transformed into product which has disorder in the axis perpendicular to the planes of the layers, due to disordered stacking of the layers upon one another.
  • a method for preparing a pillared, layered crystalline oxide comprising the steps of: (i) forming a zeolite reaction mixture and effecting crystallization of the mixture; (ii) intercepting the crystalline product of step
  • step (i) in, or converting the product to, an intermediate state wherein the product contains a swellable, layered crystalline oxide; (iii) contacting the swellable, layered crystalline oxide of step (ii) with a swelling agent to produce a swollen, layered crystalline oxide;
  • the pillared, layered crystalline oxide, prepared by this method may have an Alpha Value of at least 10, e.g., 50 or greater.
  • S UBSTITUTE SHEET material may be porous, for example, having pore windows formed by at least 8, e.g., 10, oxygen atoms.
  • the pores in the layers may have diameters of at least 5 Angstroms.
  • Figure 1 is an X-ray diffraction pattern of an as-synthesized form of a layered material which may be swollen and pillared;
  • Figure 2 is an X-ray diffraction pattern of a swollen form of the material having the X-ray diffraction pattern shown in Figure 1;
  • Figure 3 is an X-ray diffraction pattern of the pillared form of the layered material having the X-ray diffraction pattern shown in Figure 1;
  • Figure 4 is an X-ray diffraction pattern of the calcined form of the swollen material having the X-ray diffraction pattern shown in Figure 2.
  • a pillared, layered oxide material is prepared by intercepting the synthesis of the zeolite MCM-22 prior to calcination and preferably prior to drying of the crystalline product.
  • MCM-22 is described in U.S. Patent No. 4,954,325 and in its conventional calcined form (that is without being subjected to the swelling and pillaring of the present invention) has an X-ray diffraction pattern as shown in Table 1:
  • SUBSTITUTE SHEET The values in this Table and like tables presented hereinafter were determined by standard techniques.
  • the radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used.
  • the material having the X-ray diffraction pattern of Table 1 is known as MCM-22 and is described in U.S. Patent No. 4,954,325.
  • This material can be prepared from a reaction mixture containing sources of alkali or alkaline earth metal (M) , e.g., sodium or potassium, cation, an oxide of trivalent element X, e.g., aluminum, an oxide of tetravalent element Y, e.g., silicon, an organic (R) directing agent, and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
  • M alkali or alkaline earth metal
  • R organic
  • the source of Y0_ should comprise predominantly solid Y0 2 , for example at least about 30 wt.% solid Y0 2 in order to obtain the desired crystal product.
  • Y0 2 is silica
  • a silica source containing at least about 30 wt.% solid silica e.g., Ultrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated Si0 2 containing about 87 wt.% silica, about 6 wt.% free H 2 0 and about 4.5 wt.% bound H_0 of hydration and having a particle size of about 0.02 micron) favors formation of MCM-22 from the above mixture.
  • Ultrasil a precipitated, spray dried silica containing about 90 wt.% silica
  • HiSil a precipitated hydrated Si0 2 containing about 87 wt.% silica, about 6 wt.% free H 2 0 and about 4.5 wt.% bound H_0 of hydration and having a particle size of about 0.02 micron
  • the Y0 2 e.g., silica
  • the Y0 2 contains at least about 30 wt.% solid Y0 2 , e.g., silica, and more preferably at least about 40 wt.% solid Y0 2 , e.g., silica.
  • Crystallization of the crystalline material having the X-ray diffraction pattern of Table 1 can be carried out at either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or teflon lined or stainless steel autoclaves. Crystallization is generally conducted at a temperature of 80 to 225 ⁇ C for a time of 24 hours to
  • the organic directing agent for use in synthesizing the present crystalline material from the above reaction mixture is preferably hexamethyleneimine, but other which may be used include 1,4-diazacycloheptane, azacyclooctane, aminocyclohexane, aminocycloheptane, aminocyclopentane, N,N,N-trimethyl-l-adamantanammmonium ions, and N,N,N-trimethyl-2-adamantanammmonium ions.
  • the organic directing agent may be selected from the group consisting of heterocyclic imines, cycloalkyl amines and adamantane quaternary ammonium ions.
  • Synthesis of crystals may be facilitated by the presence of at least 0.01 percent, e.g., 0.10 percent or 1 percent, seed crystals (based on total weight) of crystalline product.
  • the crystalline material having the X-ray diffraction pattern of Table 1 passes through an intermediate stage, in which the material has a different X-ray diffraction pattern than that set forth in Table 1. It has been discovered that this intermediate material is swellable with the use of suitable swelling agents such as cetyltrimethylammonium compounds, e.g., cetyltrimethylammonium hydroxide.
  • the swollen intermediate material may have relatively high interplanar distance (d-spacing) , e.g., greater than 6 Angstrom, e.g., greater than 10 Angstrom
  • the swollen material may be converted into a pillared product.
  • the resultant pillared product particularly where the pillars contain silica, may be capable of being exposed to calcination conditions, e.g., at temperatures of about 450"C for about two or more hours, e.g., four hours, in nitrogen or air, without significant decrease, e.g., less than about 10%, in interlayer distance.
  • the material having the X-ray diffraction pattern of Table 1, when intercepted in a swellable, intermediate state and prior to final calcination, may have the X-ray diffraction pattern shown in Table 2.
  • FIG. 1 An X-ray diffraction pattern trace for an example of such an as-synthesized, swellable material is shown in Figure 1.
  • a particular example of such an as-synthesized, swellable material is the material of Example 1 of the aforementioned U.S. Patent No.
  • this swellable material may be swollen and pillared by methods generally discussed in the aforementioned U.S. Patent No. 4,859,648. These modifications are discussed hereinafter and include the selection of proper swelling pH and swelling agent.
  • the swollen material may have the X-ray diffraction pattern shown in Table 4.
  • the X-ray diffraction pattern of this swollen material may have additional lines with a d(A) spacing less than the line at 12.41 + 0.25, but none of said additional lines have an intensity greater than that of the line at the d(A) spacing of 12.41 + 0.25 or at 3.44 + 0.07, whichever is more intense. More particularly, the X-ray diffraction pattern of this swollen material may have the lines shown in the following Table 5.
  • the X-ray diffraction pattern may have additional lines at the following d(A) spacings (intensities given in parentheses): 16.7 + 4.0 (w-m); 6.11 + 0.24 (w) ; 4.05 + 0.08 (w) ; and 3.80 + 0.08 (w) .
  • the pattern for the swollen material is essentially like the one given in Table 2 for the unswollen material, but with the possibility of broadening of peaks.
  • SUBSTITUTESHEET upper profile is a 10-fold magnification of the lower profile in Figure 2.
  • the swollen material having the X-ray diffraction pattern shown in Table 4 may be converted into a material having the X-ray diffraction pattern shown in Table 6.
  • the X-ray diffraction pattern of this pillared material may have additional lines with a d(A) spacing less than the line at 12.38 + 0.25, but none of said additional lines have an intensity greater than that of the line at the d(A) spacing of 12.38 + 0.25 or 3.42 + 0.07, whichever is more intense. More particularly, the X-ray diffraction pattern of this pillared material may have the lines shown in the following Table 7.
  • the X-ray diffraction pattern may have additional lines at the following d(A) spacings
  • An example of a swollen, non-pillared material, which has been calcined, has the pattern as shown in
  • the X-ray powder pattern shown in Table 8 is similar to that shown in Table 1 except that most of the peaks in Table 8 are much broader than those in Table 1.
  • the calcined material corresponding to the X-ray diffraction pattern of Table 1 is designated MCM-22.
  • the pillared material corresponding to the X-ray diffraction pattern of Table 6 is designated herein as MCM-36.
  • the swollen material corresponding to the X-ray diffraction pattern of Table 4 is designated herein as the swollen MCM-22 precursor.
  • the as-synthesized material corresponding to the X-ray diffraction pattern of Table 2 is referred to herein, simply, as the MCM-22 precursor.
  • the layers of the swollen MCM-22 precursor may have a composition involving the molar relationship:
  • MCM-22 precursor is one example of a layered crystalline oxide which can be intercepted prior to calcination and swollen and pillared (MCM-36) to prevent the transformation of the layered oxide into a zeolite (MCM-22) .
  • MCM-39 Another example of such a layered crystalline oxide is MCM-39.
  • MCM-39 may be prepared from a material known as Nu-6(1). Details of the synthesis, composition and X-ray diffraction pattern of Nu-6(1) are set forth in U.S. Patent No. 4,397,825. Nu-6(1) may be converted to MCM-39 by an acid treatment. MCM-39 has the X-ray diffraction pattern shown in Table 9.
  • this swellable material may be swollen and pillared by methods generally discussed in the aforementioned U.S, Patent No. 4,859,648.
  • the present modifications are discussed hereinafter and include the selection of proper swelling pH and swelling agent.
  • the swollen MCM-39 may have the X-ray diffraction pattern shown in Table 10.
  • the swollen MCM-39 material having the X-ray diffraction pattern shown in Table 10 may be converted into a material having the X-ray diffraction pattern shown in Table 11.
  • the present swollen products may have relatively high interplanar distances (d-spacing) , e.g., greater than about 6 Angstroms, e.g., greater than about 10 Angstroms and even exceeding 30 Angstroms.
  • These swollen materials may be converted into pillared materials.
  • These pillared materials, especially silica pillared materials may be capable of being exposed to severe conditions such as those encountered in calcining, e.g., at temperatures of about 450"C for about two or more hours, e.g., four hours, in nitrogen or air, without significant decrease, e.g., less than about 10%, in interlayer distance.
  • Nu-6(1) may be made from an aqueous reaction mixture containing at least one source of an oxide Y0 2 , e.g. silica; at least one source of an oxide X 2 ° 3 ' e *9* alumina; and a 4,4'- bipyridyl compound.
  • This reaction mixture may have the following molar composition:
  • Y0 2 /X 2 0_ 10 to 5000 preferably 20 to 3000 M0H/Y0 2 0 to 0.1, preferably 0.01 to 0.3 Z-/X 0 10 to 5000, preferably 10 to 100 Q/X 2 0 3 0.1 to 5000, preferably 1 to 500 H 2 0/Y0 2 10 to 500, preferably 15 to 300 BOH/X 2 0_ 0 to 500,000, preferably 0 to 1000
  • Y is silicon and/or germanium
  • X is one or more of aluminum, gallium, iron, chromium, vanadium, molybdenum, antimony, arsenic, manganese, or boron
  • M is an alkali metal or ammonium
  • Q is the aforesaid 4,4 '-bipyridyl compound
  • Z- is a strong acid radical present as a salt of M and may be added as a free acid to reduce the free 0H " ⁇ level to a desired value.
  • M and/or Q can be present as hydroxides or salts or inorganic or organic acids provided the M0H/Y0 2 requirement is fulfilled.
  • BOH is an aliphatic or aromatic alcohol, preferably an alkanol. While not essential, an alcohol improves crystallization in viscous reaction mixtures.
  • the bipyridyl may be partially or fully alkylated, e.g. methylated.
  • the preferred bipyridyl compound is 4,4'-bipyridyl itself.
  • the preferred alcohol (BOH) is methanol.
  • the preferred alkali metals (M) are sodium and potassium.
  • the preferred oxide Y0 2 is silica (Si0 2 ) and the preferred oxide X 0_ is alumina (Al 2 0 3 ) .
  • the silica source can be any of those commonly considered for use in synthesizing zeolites, for example powdered solid silica, silicic acid, colloidal silica, or dissolved silica.
  • powdered silicas usable are precipitated silicas, especially those made by precipitation from an alkali metal silicate solution, such as the type known as "KS 300" made by AKZO, and similar products, aerosol silicas, fume silicas, and silica gels suitably in grades for use in reinforcing pigments for rubber or silicone rubber.
  • Colloidal silicas of various particle sizes may be used, for example 10-15 or 40-50 microns, as sold under the registered trademarks "LUDOX,” “NALCOAG,” and “SYTON.”
  • the usable dissolved silicas include commercially available water glass silicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of Si0 2 per mole of alkali metal oxide, "active" alkali metal silicates as defined in U.K. Pat. No 1,193,254, and silicates made by dissolving silica in an alkali metal hydroxide or quaternary ammonium hydroxide or a mixture thereof.
  • the alumina source is most conveniently sodium aluminate, but can be or can include aluminum, an aluminum salt of, for example, the chloride, nitrate or sulphate, an aluminum alkoxide or alumina itself, which should preferably be in a hydrated or hydratable form such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina or the alpha or beta trihydrate.
  • the reaction mixture is reacted usually under autogeneous pressure, optionally with added gas, e.g. nitrogen, at a temperature between 85° and 250"C until crystals of Nu-6(1) form, which can be from 1 hour to many months depending on the reactant composition and the operating temperature. Agitation is optional, but is preferable since it reduces the reaction time.
  • gas e.g. nitrogen
  • the solid phase may be collected on a filter and washed and is then ready for further steps.
  • Nu-6(1) may have a molar composition with ratio of X 2 0 3 :YO_ of at least 10. To the extent that this portion of Nu-6(1) results in negative charges, Nu-6(1) also has cations to balance the negative charges. More particularly, Nu-6(1) may have a mole ratio of 0.5 to 1.5 R 2 0:X 2 0 3 , where R is a monovalent cation or 1/m of a cation of valency m. Nu-6(1) may also have water of hydration additional to water when R is H. As indicated in the aforementioned U.S. Patent No. 4,397,825, this additional water (H 2 0) may be quantified in terms of the molar ratio, X 2 0 3 :o to 2000 H 2 0.
  • the freshly prepared Nu-6(1) may also contain nitrogen-containing compounds well in excess of the 1.5 moles set out in the above-mentioned ratio of 0.5 to 1.5 R 2 0:X 2 0 3 .
  • These nitrogen-containing compounds (Q) can be removed by thermal or oxidative degradation or by displacement by suitably small molecules. Physically trapped nitrogen-containing compounds do not constitute part of the R cations as discussed hereinabove.
  • Nu-6(1) as made may have the following molar composition:
  • M2_O 0.1 to 400
  • M is an alkali metal and/or ammonium and can include hydrogen
  • M 2 0 + Q is equal to or greater than 1.0.
  • the Nu-6(1) structure may retain from 0.1 to 0.15 moles of Q per mole of Y0 2 , Q in this case being a 4,4-bipyridyl compound.
  • the H-0 content of freshly prepared zeolite Nu-6(1) depends on the conditions in which it has been dried after synthesis. Indeed, if dried at
  • Nu-6(1) is recognizable by its X-ray diffraction pattern. According to the aforementioned U.S. Patent No. 4,397,825, Nu-6(1) as prepared has the X-ray diffraction pattern listed in the following Table:
  • NU-6(1) may be converted to MCM-39 by an acid treatment.
  • the acid used to treat Nu-6(1) may be a mineral or other strong acid such as hydrochloric acid, sulfuric acid, nitric acid, or trifluoroacetic acid.
  • the acid may be used in solution, especially in aqueous solution, having a molar concentration of 0.1 M to 10 M, e.g., 0.5 M to 2.0 M.
  • the duration of contact with acid may be from 1 to 48 hours and the temperature of the acid treatment may be from ambient to 100 ⁇ C, for example, 90"C.
  • the acid treatment is repeated one or more times under the same or different conditions in order to more fully convert Nu-6(1) to MCM-39.
  • the layers of MCM-39 may have the same molar X,0.:Y0 2 ratio as the Nu-6(1) from which it is prepared. More particularly, for example, the layers
  • SUBSTITUTESHEET of MCM-39 may have a composition involving the molar relationship:
  • X 2 0 3 :(n)Y0 2 wherein 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, and n is at least about 10, usually from about 20 to about 1000, and more usually from about 20 to about 70. To the extent that the layers of MCM-36 and MCM-39 have negative charges, these negative charges are balanced with cations.
  • the layers of MCM-36 and MCM-39 may have a ratio of 0.5 to 1.5 R 2 0:X 2 0 3 , where R is a monovalent cation or 1/m of a cation of valency m.
  • the swellable material, used to form the swollen material of the present disclosure may be initially treated with a swelling agent.
  • Such swelling agents are materials which cause the swellable layers to separate by becoming incorporated into the interspathic region of these layers.
  • the swelling agents are removable by calcination, preferably in an oxidizing atmosphere, whereby the swelling agent becomes decomposed and/or oxidized.
  • Suitable swelling agents may comprise a source of organic cation, such as quaternary organoammonium or organophosphonium cations, in order to effect an exchange of interspathic cations.
  • Organoammonium cations, such as n-octylammonium showed smaller swelling efficiency than, for example, cetyltrimethylammonium.
  • a pH range of 11 to 14 for MCM-22 precursor, 10 to 14 for MCM-39, preferably 12.5 to 13.5 for both MCM-22 precursor and MCM-39, is generally employed during treatment with the swelling agent.
  • the swellable material is preferably not dried prior to being swollen.
  • This swellable material may be SUBSTITUTESHEET in the form of a wet cake having a solids content of less than 30 % by weight, e.g., 25 wt % or less.
  • the foregoing swelling treatment results in the formation of a layered oxide of enhanced interlayer separation depending upon the size of the organic cation introduced.
  • a series of organic cation exchanges can be carried out.
  • an organic cation may be exchanged with an organic cation of greater size, thus increasing the interlayer separation in a step-wise fashion.
  • the organic-swollen species may be treated with a compound capable of conversion, e.g., by hydrolysis and/or calcination, to pillars of an oxide, preferably to a polymeric oxide.
  • a compound capable of conversion e.g., by hydrolysis and/or calcination
  • this treatment may be carried out using the water already present in organic-swollen material.
  • the extent of hydrolysis may be modified by varying the extent to which the organic-swollen species is dried prior to addition of the polymeric oxide precursor.
  • the organic cation deposited between the layers be capable of being removed from the pillared material without substantial disturbance or removal of the interspathic polymeric oxide.
  • organic cations such as cetyltrimethylammonium may be removed by exposure to elevated temperatures, e-q., calcination, in nitrogen or air, or by chemical oxidation preferably after the interspathic polymeric oxide precursor has been converted to the polymeric oxide pillars in order to form the pillared layered product.
  • These pillared layered products especially when calcined, exhibit high surface area, e.g., greater than
  • SUBSTITUTESHEET they highly useful as catalysts or catalytic supports, for hydrocarbon conversion processes, for example, alkylation.
  • Insertion of the organic cation between the adjoining layers serves to physically separate the layers in such a way as to make the layered material receptive to the interlayer addition of a polymeric oxide precursor.
  • cetyltrimethylammonium cations have been found useful. These cations are readily incorporated within the interlayer spaces of the layered oxide serving to prop open the layers in such a way as to allow incorporation of the polymeric oxide precursor.
  • the extent of the interlayer spacing can be controlled by the size of the organoammonium ion employed.
  • Interspathic oxide pillars which may be formed between the layers of the propped or swollen oxide material, may include an oxide, preferably a polymeric oxide, of zirconium or titanium or more preferably of an element selected from Group IVB of the Periodic
  • the pillars include polymeric silica.
  • the oxide pillars may include an element which provides catalytically active acid sites in the pillars, preferably aluminum.
  • the oxide pillars are formed from a precursor material which may be introduced between the layers of the organic "propped" species as an ionic or electrically neutral compound of the desired elements, e.g., those of Group IVB.
  • the precursor material may be an organometallic compound which is a liquid under ambient conditions.
  • Suitable polymeric silica precursor materials include tetraalkylsilicates, e.g., tetrapropyl- orthosilicate, tetramethylorthosilicate and, most preferably, tetraethylorthosilicate.
  • Suitable polymeric silica precursor materials also include quaternary ammonium silicates, e.g., tetramethylammonium silicate (i.e. TMA silicate) .
  • TMA silicate tetramethylammonium silicate
  • a hydrolyzable aluminum compound can be contacted with the organic "propped" species before, after or simultaneously with the contacting of the propped layered oxide with the silicon compound.
  • the hydrolyzable aluminum compound employed is an aluminum alkoxide, e.g., aluminum isopropoxide.
  • the pillars are to include titania, a hydrolyzable titanium compound such as titanium alkoxide, e.g., titanium isopropoxide, may be used.
  • the final pillared product may contain residual exchangeable cations.
  • Such residual cations in the layered material can be ion exchanged by known methods with other cationic species to provide or alter the catalytic activity of the pillared product.
  • Suitable replacement cations include cesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum, lanthanum, aluminum, ammonium, hydronium and mixtures thereof.
  • the resulting pillared products may exhibit thermal stability at temperatures of 450"C or even higher as well as substantial sorption capacities.
  • the pillared products may possess a basal spacing of at least about 20A, e.g., at least about 32.2A and surface
  • Adsorption capacities for MCM-36, especially the silica pillared material, of the present invention may range at room temperature as follows:
  • Adsorbate Capacity Wt. Percent n-hexane 17-40 cyclohexane 17-40 water 10-40 wherein cyclohexane and n-hexane sorption are measured at 20 Torr and water sorption is measured at 12 Torr.
  • Adsorption capacities for the pillared MCM-39, especially silica pillared MCM-39 may range at room temperature as follows:
  • Adsorbate Capacity Wt. Percent n-hexane 10-40 cyclohexane 10-40 water 10-40 wherein cyclohexane and n-hexane sorption are measured at 20 Torr and water sorption is measured at 12 Torr.
  • the pillared, layered materials described herein can optionally be used 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 where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum,
  • SUBSTITUTESHEET platinum treating the layered material with a solution containing a platinum metal-containing ion.
  • suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
  • the pillared, layered material may be subjected to thermal treatment, e.g., to decompose organoammonium ions.
  • This thermal treatment is generally performed by heating one of these forms at a temperature of at least about 370"C for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is preferred simply for reasons of convenience.
  • the pillared, layered material of the present invention, particularly MCM-36, especially silica pillared MCM-36 is useful as a catalyst component for a variety of organic, e.g., hydrocarbon, compound conversion processes.
  • Such conversion processes include cracking hydrocarbons with reaction conditions including a temperature of 300 to 700 ⁇ C, a pressure of 10 to 3000 kPa (0.1 to 30 atmospheres) and a weight hourly space velocity of 0.1 to 20; dehydrogenating hydrocarbon compounds with reaction conditions including a temperature of 300 to 700 ⁇ C, a pressure of 10 to 1000 kPa (0.1 to 10 atmospheres) and a weight hourly space velocity of 0.1 to 20; converting paraffins to aromatics with reaction conditions including a temperature of 100 ⁇ C to 700"C, a pressure of 10 to 6000 kPa (0.1 to 60 atmospheres), a weight hourly space velocity of 0.5 to 400 and a hydrogen/hydrocarbon mole ratio of 0 to 20; converting olefins to aromatics, e.g. benzene, toluene and xylenes, with reaction conditions including a temperature of 100°C to 700"C, a pressure of 10 to
  • SUBSTITUTESHEET ratio of 0 to 20; converting alcohols, e.g. methanol, or ethers, e.g. ,dimethylether, or mixtures thereof to hydrocarbons including aromatics with reaction conditions including a temperature of 300°C to 550°C, more preferably 370°C to 500 ⁇ C, a pressure of from 70
  • Pa to 14000 kPa (0.01 psi to 2000 psi), more preferably 700 Pa to 3500 kPa (0.1 psi to 500 psi), and a liquid hourly space velocity of 0.5 to 100; isomerizing xylene feedstock components with reaction conditions including a temperature of 230"C to 510°C, a pressure of 300 to 3500 kPa (3 atmospheres to 35 atmospheres) , a weight hourly space velocity of 0.1 to 200 and a hydrogen/hydrocarbon mole ratio of 0 to 100; disproportionating toluene with reaction conditions including a temperature of 200*C to 760 ⁇ C, a pressure of 100 to 6000 kPa (1 to 60 atmospheres) and a weight hourly space velocity of 0.08 to 20; alkylating isoalkanes, e.g.
  • isobutane with olefins, e.g. 2-butene, with reaction conditions including a temperature of -25 ⁇ C to 400*C, e.g. 75 ⁇ C to 200 ⁇ C, a pressure of from below atmospheric to 35000 kPa (5000 psig) , e.g. 100 to 7000 kPa (1 to 1000 psig) , a weight hourly space velocity based on olefin of 0.01 to 100, e.g. 0.1 to 20, and a mole ratio of total isoalkane to total olefin of 1:2 to 100:1, e.g. 3:1 to 30:1; alkylating aromatic hydrocarbons, e.g.
  • alkylating agent e.g., olefins, formaldehyde, alkyl halides and alcohols
  • reaction conditions including a temperature of 340°C to 500"C, a pressure of 100 to
  • pillared, layered material may be desirable to incorporate with another material which is resistant to the temperatures and other conditions employed in the catalytic processes described herein.
  • 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. 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 pillared, layered material, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst.
  • Inactive materials suitably serve as diluents to control the amount of conversion so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into 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 pillared, layered materials include the montmorillonite and kaolin family, which families include the subbent ⁇ nites, and the kaolins commonly
  • SUBSTITUTESHEET 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.
  • Binders useful for compositing with layered materials also include inorganic oxides, notably alumina.
  • the pillared, layered materials 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 sili ⁇ a-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica- ⁇ tagnesia-zirconia.
  • 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 sili ⁇ a-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica- ⁇ tagnesia-zirconia.
  • the relative proportions of finely divided pillared, layered materials and inorganic oxide matrix vary widely, with the pillared, layered material content ranging from 1 to 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range 2 to 80% weight of the composite.
  • the Alpha Test is described in U.S. Patent 3,354,078, in the Journal of Catalysis. Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980).
  • the experimental conditions of the test preferably include a constant temperature of 538 ⁇ C and a variable flow
  • MCM-36 especially when the layers thereof are composed of an aluminosilicate, may be a very catalytically active material.
  • other layered materials such as clays, magadiite, kenyaite, and titanates, in pillared form are much less catalytically active than the very catalytically active forms of the pillared layered oxide, MCM-36.
  • One measure of the catalytic activity of MCM-36 is the
  • MCM-36 Alpha Value for MCM-36.
  • Various catalytically active forms of MCM-36 may have Alpha Values in excess of 10, e.g., 50 or greater.
  • Particularly catalyticaly active forms of MCM-36 comprise those with aluminosilicate layers, these layers having a silica to alumina molar ratio of 300 or less.
  • MCM-36 Another distinguishing feature of MCM-36, relative to other pillared layered oxides, is the porosity of the layers of MCM-36.
  • pillared oxide materials such as pillared clays and the pillared materials, e.g., pillared silicates and titanates, discussed in the aforementioned U.S. Patent No. 4,859,648, have considerable porosity as a result of open interspathic regions, the individual layers of these materials are relatively dense, lacking pore windows formed by 8 or more oxygen atoms.
  • the layers of MCM-36 would appear to have continuous channels having pore windows formed by rings of at least 8 oxygen atoms.
  • these pore windows in the layers of MCM-36 would appear to be formed by rings of 10 oxygen atoms. As indicated by argon physisorption measurements, the channels in the layers of MCM-36 have an effective pore diameter of greater than about 5 Angstroms.
  • EXAMPLE 1 This Example describes the synthesis of a material which may be swollen and pillared. Water, sodium hydroxide, sodium aluminate, silica (Ultrasil) , and hexamethyleneimine (HMI) were combined in the following ratios: 2.5 Na 2 0: A1 2 0 3 : 30 Si0 2 :10 HMI: 580 H 2 0.
  • HMI hexamethyleneimine
  • EXAMPLE 2 A mixture of a 29 % solution of cetyltrimethyl ⁇ ammonium (N, ,N-trimethyl-1-hexadecanaminium) hydroxide, 40 % tetrapropylammonium hydroxide and wet cake of Example 1 (20 % solids) in the relative weight ratio 105:33:27, respectively, was heated in an autoclave at 105 "C with stirring for 42 hours. The solid product was isolated by decantation and filtration, and the wet cake was washed twice by mixing with water and filtration. The swollen material had the X-ray diffraction pattern given in the following Table 12.
  • the swelling reagent was prepared by contacting a 29 % solution of cetyltrimethylammonium (N,N,N-trimethyl-l-hexadecanaminium) chloride with a hydroxide-for-halide exchange resin (one liter of wet resin with 1.4 milliequivalent/ml exchange capacity per 3 1 of the solution) . It will be referred to as 29 % CTMA-OH.
  • Example 1 wet cake (30 % solids) and 150 g of the 29 % CTMA-OH solution was reacted in the steambox for 65 hours.
  • the product was isolated by filtration, washed twice with 50 ml of water and air dried overnight yielding 10.6 g of the swollen product.
  • the X-ray diffraction pattern for this swollen material is shown pictorially in Figure 2.
  • the X-ray diffraction pattern for this swollen material is also given in the following Table 14.
  • This Example describes the pillaring of the swollen material of Example 4.
  • the swollen material (8.6 g) was slurried with 50 g of tetraethylortho ⁇ silicate (TEOS) and heated at 80°C for 24 hours under the stream of nitrogen. After filtration and overnight drying the product (7.15 g) was hydrolyzed in water for 5 hr giving the pillared material (6.6 g) containing 68% solids based upon calcination at 450*C.
  • the X-ray diffraction pattern for this pillared material is shown pictorially in Figure 3. TEM analysis of crystallites confirmed that the layers remained separated after this pillaring procedure.
  • the X-ray diffraction pattern for this pillared, calcined material is also given in the following Table 15. 2 Theta
  • This Example describes another embodiment of swelling the material of Example 1 using a different swelling medium.
  • the swelling reagent was prepared by contacting a solution of cetyltrimethylammonium (N,N,N-trimethyl-l-hexadecanaminium) chloride composed of 50 % of the latter, 35 % 2-propanol and 15 % water, with a hydroxide-for-halide exchange resin (two exchanges using 1/2 liter of wet resin with 1.4 milliequivalent/ml exchange capacity per 1 1 of the solution; 200 ml of ethanol was also added) . It will be referred to as 50 % CTMA-OH.
  • This Example describes swelling of the material prepared from the synthesis mixture of Example 1 that has been crystallized for 48 hours (see below) rather than 96 hours.
  • Example 7 describes pillaring of the swollen material of Example 7. 235 g of the product was ground and combined with 1.4 liter of TEOS and treated by a procedure similar to Example 5. The product contained 65 % solids based on calcination at 540 °C. A sample of the calcined product was examined by argon physisorption which revealed a dual pore system with diameters of 6.3 Angstroms and about 28 Angstroms.
  • a 0.2 gram sample of the product of Example 8 was placed in a glass sample tube and attached to a physisorption apparatus as described in U.S. Patent No. 4,762,010.
  • the sample was heated to 300 ⁇ C for 3 hours in vacuo to remove adsorbed water. Thereafter, the sample was cooled to 87°K by immersion of the sample tube in liquid argon. Metered amounts of gaseous argon were then admitted to the sample in stepwise manner as described in U.S. Patent No. 4,762,010, column 20. From the amount of argon admitted to the sample and the amount of argon left in the gas space above the sample, the amount of argon adsorbed can be calculated. For this calculation, the ideal gas law and the calibrated
  • 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 0 »
  • the adsorption peak (stated in terms of log (P/P ) ) may be related to the physical pore diameter (A) by the following formula:
  • K .10 .10 log(P/P o ) d-0.38 3(L-D/2) 3 9(L-D/2) 9 3(D/2) 3 9(D/2) 9
  • This formula is derived from the method of Horvath and Kawazoe (G. Horvath et al., J. Chem. En ⁇ . Japan f 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 about 60 Angstroms in diameter.
  • This Example describes a preparation involving pillaring with an aqueous solution of tetramethylammomium silicate, TMA-Si, previously defined in Example 3 and formulation of the alumina bound catalyst.
  • the swollen product was obtained by reacting 330 g of the Example 1 wet cake (42 % solids) and 2700 ml of 29 % CTMA-OH for 48 hours in the steambox. The solid was isolated by filtration, washed by contacting with 0.5 1 of water and air dried. The X-ray diffraction pattern of this swollen material is given in the following Table 19.
  • the remainder of the product was mixed with alumina alpha-monohydrate (Kaiser alumina) (solid ratio 65:35) and ion exchanged by contacting three times with 1 M ammonium nitrate. After drying, the solid was pelletized and was calcined by a hybrid method: 3 hr in nitrogen at 450 °C followed by slow bleeding of air and full air calcination at 540 ⁇ C for 6 hours.
  • alumina alpha-monohydrate Karl alumina
  • This Example describes the preparation, swelling and pillaring of the material related to that of Example 1 but with a higher content of alumina (Si/Al 2 ratio around 18) .
  • This Example describes swelling of the material of Example 1 with dodecyltrimethylammonium chloride/hydroxide.
  • the swelling reagent was prepared by contacting a
  • Example 1 The wet cake of Example 1 (50 g, about 20 % solids) was mixed with 500 ml g of DOTMA-OH and heated in the steambox for 48 hours. The solid was isolated by filtration and washed with water. The air dried product showed X-ray diffraction pattern similar to that of Figure 2 with a very intense low angle line. The X-ray diffraction pattern for this swollen material is given in the following Table 21.
  • the Alpha values for the products from Examples 3 and 9 were measured to be 75 and 116, respectively.
  • Table 23 provides common peaks observed in the X-ray diffraction (XRD) patterns for the swollen materials of the foregoing Examples 2, 4, 6, 7, 9, and 11.
  • EXAMPLE 13 120 g of the wet Nu-6(1) material (about 24 g solids), described in U.S. Patent No. 4,397,825, was contacted three times with 1.25 1 of 2 M HCl for 2.5 hr at 90 "C. The solid was washed with water until Cl ⁇ " free and air dried for overnight yielding 25 g of the solid (MCM-39) with an X-ray powder diffraction pattern shown in Table 25.
  • a 9 g sample of the solid was calcined at 450 ⁇ C for 20 hours. It was determined to have a BET surface area of 49 m 2/g and adsorption capacity of 2.9, 2.6 and
  • EXAMPLE 14 This Example describes the preparation of swollen/pillared MCM-39.
  • 24 g of the solid from Example 13 was mixed with 150 ml of the 29 % CTMA-OH. The slurry was gently stirred for overnight at room temperature, filtered, washed with water and air dried for 6 hours.
  • the swollen solid was contacted with 216 g of tetraethylorthosilicate for 24 hr at 80-115 ⁇ C. Following filtration it was hydrolyzed with water (75 g of solid, 100 ml of water) for 4 hours and filtered again. This afforded 65 g of the pillared product, which was found to have, after calcination at 450 "C
  • the pillared product had the X-ray diffraction pattern shown in Table 26.

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WO1991012204A1 (en) * 1990-02-06 1991-08-22 Mobil Oil Corporation Synthesis of kenyaite-type layered silicate material and pillaring of said material

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US4176090A (en) * 1975-11-18 1979-11-27 W. R. Grace & Co. Pillared interlayered clay materials useful as catalysts and sorbents
US4248739A (en) * 1979-09-04 1981-02-03 W. R. Grace & Co. Stabilized pillared interlayered clays
US4859648A (en) * 1984-12-28 1989-08-22 Mobil Oil Corporation Layered metal chalcogenides containing interspathic polymeric chalcogenides
US4954325A (en) * 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use

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EP0163560A2 (fr) * 1984-04-25 1985-12-04 Compagnie De Raffinage Et De Distribution Total France Nouvelle zéolite à structure bidimensionnelle et application de ladite zéolite
WO1991012204A1 (en) * 1990-02-06 1991-08-22 Mobil Oil Corporation Synthesis of kenyaite-type layered silicate material and pillaring of said material

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