WO2008097481A1

WO2008097481A1 - Method of manufacturing m41s family molecular sieve

Info

Publication number: WO2008097481A1
Application number: PCT/US2008/001388
Authority: WO
Inventors: Wenyih Frank Lai; Stephen J. Mccarthy; Robert E. Ellis
Original assignee: Exxonmobil Research And Engineering Company
Priority date: 2007-02-06
Filing date: 2008-02-01
Publication date: 2008-08-14

Abstract

This disclosure relates to method for synthesizing a composition of matter comprising an inorganic, porous crystalline phase material having, after calcination, a substantially hexagonal arrangement of substantially uniformly- sized pores having mean diameters of at least about 13 Angstrom Units and exhibiting a substantially hexagonal electron diffraction pattern that can be indexed with a d1Oo value greater than about 18 Angstrom Units, the method comprising: preparing a mixture capable of forming the composition of matter, the mixture comprising sources of one or a combination of oxides of elements selected from the group consisting of divalent element W, trivalent element X, tetravalent element Y and pentavalent element Z, an organic directing agent (R) and a solvent, wherein at least a portion of the solvent comprises at least one recycle liquid produced during at least one previous process for the manufacture of the composition of matter; (a) maintaining the mixture under sufficient conditions of pH, temperature and time for formation of the composition of matter; (b) separating the composition of matter.

Description

METHOD OF MANUFACTURING M41S FAMILY MOLECULAR SIEVES

FIELD

[0001] This disclosure relates to a method for synthesizing a mesoporous molecular sieve composition, in which at least a portion of the solvent in the reaction mixture comprises recycle liquid from processing of the mesoporous molecular sieve made in at least one previous synthesis batch, e.g., the mother liquor(s), the washing liquid(s), the cleaning liquid(s), and any combination thereof.

BACKGROUND OF THIS DISCLOSURE

[0002] Porous inorganic solids have found great utility as catalysts and separations media for industrial application. The openness of their microstructure allows molecules to access the relatively large surface areas of these materials that enhance their catalytic and sorptive activity. The porous materials in use today can be sorted into three broad categories using the details of their microstructure as a basis for classification. These categories are the amorphous and paracrystalline supports, the crystalline molecular sieves and modified layered materials. The detailed differences in the microstructures of these materials manifest themselves as important differences in the catalytic and sorptive behavior of the materials, as well as in differences in various observable properties used to characterize them, such as their surface area, the sizes of pores and the variability in those sizes, the presence or absence of X-ray diffraction patterns and the details in such patterns, and the appearance of the materials when their microstructure is studied by transmission electron microscopy and electron diffraction methods. [0003] The M41S family of mesoporous molecular sieves is described in J. Amer. Chem. Soc, 1992, 114, 10834. Members of the M41S family of mesoporous molecular sieves include MCM-41, MCM-48 and MCM-50. A preferred member of this class is MCM-41 whose preparation is described in U.S. Pat. No. 5,098,684. MCM-41 is characterized by having a substantially hexagonal crystal structure with an unidimensional arrangement of pores having a cell diameter greater than about 13 Angstroms. The physical structure of MCM-41 is like a bundle of straws wherein the opening of the straws (the cell mean diameters of the pores) ranges from about 13 to 200 Angstroms. MCM-48 has a cubic symmetry and is described for example in U.S. Pat. No. 5,198,203. MCM-50 has a layered or lamellar structure and is described in U. S. Pat. No. 5,246,689.

[0004] M41S family mesoporous molecular sieves may be characterized by their structure, including extremely large pore windows, and high sorption capacity. The term "mesoporous" is used here to indicate crystals having substantially uniform pores within the range of from about 13 Angstroms to about 200 Angstroms in diameter. The materials hereby prepared will have substantially uniform pores within the range of from about 13 Angstroms to about 200 Angstroms, more usually from about 15 Angstroms to about 100 Angstroms in diameter. For the purposes of this application, a working definition of "porous" is a material that adsorbs at least 1 gram of a small molecule, such as Ar, N₂, n-hexane, benzene or cyclohexane, per 100 grams of the solid. The term "substantially uniform" as used herein, means regular arrangement and uniformity of size (pore size distribution within a single phase of, for example, ±25%, usually ±15% or less of the average pore size of that phase).

[0005] M41S family mesoporous molecular sieves have found many applications, such as catalytic cracking, adsorption, separation, oxidation, polymerization, and pharmaceutics. However, the process of manufacturing the M41S family mesoporous molecular sieves requires expensive surfactant. In particular, disposal of surfactant-containing liquid generated in the crystallization, filtration, and washing is difficult, as it causes environmental concerns, and expensive. There is therefore a need to improve the method of manufacturing M41S family mesoporous molecular sieves by finding methods to reduce the need for disposal of surfactant-containing liquid. This disclosure meets this and other needs.

SUMMARY OF THIS DISCLOSURE

[0006] In some embodiments, this disclosure relates to a method for synthesizing a composition of matter comprising an inorganic, porous crystalline phase material having, after calcination, a substantially hexagonal arrangement of substantially uniformly-sized pores having mean diameters of at least about 13 Angstrom Units and exhibiting a substantially hexagonal electron diffraction pattern that can be indexed with a d_1Oo value greater than about 18 Angstrom Units, the method comprising:

(a) preparing a mixture capable of forming the composition, the mixture comprising sources of one or a combination of oxides of elements selected from the group consisting of divalent element W, trivalent element X, tetravalent element Y and pentavalent element Z, an organic directing agent (R) and a solvent, and having a composition, in terms of mole ratios, within the following ranges:

wherein e and f are the weighted average valences of M and R, respectively, M is an alkali or alkaline earth metal ion and R comprises an ion of the formula R₁R₂R₃R₄Q⁺, wherein Q is nitrogen or phosphorus and wherein at least one of R₁, R₂, R₃ and R₄ is selected from the group consisting of aryl groups having from 6 to about 36 carbon atoms, alkyl groups having from 6 to about 36 carbon atoms and combinations thereof, the remainder of R₁, R₂, R₃ and R₄ being selected from the group consisting of hydrogen, alkyl groups having from 1 to 5 carbon atoms and combinations thereof, wherein at least a portion of the solvent comprises at least one recycle liquid from processing of the mesoporous molecular sieve produced in at least one previous synthesis batch;

(b) maintaining the mixture under sufficient conditions of pH, temperature and time for formation of the composition of matter;

(c) separating the composition of matter.

[0007] The method may also include recovering the mother liquor from step (c). If necessary. The method may also include one or several steps of washing the composition of matter, and recovering the washing liquid(s) and/or one or several cleaning step with recovery of the cleaning liquid(s).

[0008] In other embodiments, this disclosure relates to a method for synthesizing a composition of matter comprising an inorganic, porous crystalline phase material having, after calcination, a substantially hexagonal arrangement of substantially uniformly-sized pores having mean diameters of at least about 13 Angstrom Units and exhibiting a substantially hexagonal electron diffraction pattern that can be indexed with a di_Oo value greater than about 18 Angstrom Units, the method comprising:

(a) preparing a reaction mixture capable of forming the composition, the reaction mixture comprising sources of an oxide of silicon or a combination of oxides selected from the group consisting of oxides of silicon and oxides of aluminum, an organic directing agent (R) and a solvent, and having a composition, in terms of mole ratios, within the following ranges:

wherein e and f are the weighted average valences of M and R, respectively, M is an alkali or alkaline earth metal ion and R comprises an ion of the formula RiR₂R₃R₄Q⁺, wherein Q is nitrogen or phosphorus and wherein at least one of Rj, R₂, R₃ and R₄ is selected from the group consisting of aryl groups having from 6 to about 36 carbon atoms, alkyl groups having from 6 to about 36 carbon atoms and combinations thereof, the remainder of R₁, R₂, R₃ and R₄ being selected from the group consisting of hydrogen, alkyl groups having from 1 to 5 carbon atoms and combinations thereof, the step (a) comprising (1) mixing the organic directing agent (R) with the solvent such that the mole ratio of solvent/ R_2/fO is within the range of from about 50 to about 800, (2) adding to the mixture of step (a) (1) the sources of oxides, such that the ratio of R_2/fO/(SiO₂ +Al₂O₃) is within the range of from about 0.01 to about 2.0, (3) agitating the mixture resulting from step (a) (2) at a temperature of from about 20⁰C to about 40⁰C and optionally (4) aging the mixture resulting from step (a) (3) at a temperature of from about 2O⁰C to about 100⁰C for from about 10 minutes to about 24 hours, wherein at least a portion of the solvent comprises at least one recycle liquid produced from processing of the mesoporous molecular sieve made in at least one previous synthesis batch;

(b) maintaining the mixture under sufficient conditions of pH, temperature and time for formation of the composition of matter; and

(c) recovering the composition of matter.

[0009] In one aspect of this disclosure, the mixture comprises an additional organic directing agent ion (R') of the formula R'₁R'₂R'₃R'₄Q⁺, wherein R'_1} R'₂, R'₃ and R'₄ are selected from the group consisting of hydrogen, alkyl groups having 1 to 5 carbon atoms and combinations thereof.

[0010] In a preferred embodiment, R comprises an organic agent selected from the group consisting of cetyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldidodecylammonium.

[0011] In another aspect of this disclosure, at least one of R₁, R₂, R₃ and R₄ is selected from the group consisting of -C₆H₁₃, -C₁₀H₂₁, -C₁₂H₂₅, -C₁₄H₂₉, ~ C₁₆H₃₃, --C₁₈H₃₇ and combinations thereof.

[0012] This disclosure relates to a novel method of making a non-layered inorganic porous crystalline phase composition of matter, wherein the composition of matter comprises a substantially hexagonal arrangement of substantially uniformly-sized pores having an average pore diameter greater than or equal to about 13 A, an X-ray diffraction pattern having a calculated d_1Oo value of greater than or equal to about 18A, an adsorption capacity of greater than or equal to about 15 grams benzene per 100 grams the composition of matter at 6.666118 kPa-a and at 25⁰C, and a pore wall thickness of less then or equal to about 25A.

DETAILED DESCRIPTION OF THIS DISCLOSURE

Introduction

[0013] All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with the present invention and for all jurisdictions in which such incorporation is permitted.

[0014] For the purposes of this disclosure and the claims thereto, a catalytically active material may be interchangeably referred to as a catalytic material, or a catalyst. The term "catalyst" is art-recognized and refers to any substance that notably affects the rate of a chemical reaction without itself being consumed or significantly altered. A catalyst system comprises a catalyst and a support. A reactor is any container(s) in which a chemical reaction occurs. As used in this specification, the term "framework type" is used in the sense described in the "Atlas of Zeolite Framework Types," 2001. As used herein, the numbering scheme for the Periodic Table Groups is used as in Chemical and Engineering News, 63(5), 27 (1985).

[0015] When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. The articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element. The terms "comprise" and "comprising" are used in the inclusive, open sense, meaning that additional elements may be included. The term "including" is used to mean "including but not limited to". "Including" and "including but not limited to" are used interchangeably.

[0016] A porous material is a material that adsorbs at least about 1 gram of nitrogen, n-hexane, cyclohexane, or benzene per 100 grams of the material. A porous material or particle having pores in the mesoporous range comprises pores with a diameter at the surface of the particle of greater than or equal to about 20 angstroms (A) and less than or equal to about 500A. Pore size is the maximum perpendicular cross-sectional pore dimension of the material. Pore wall thickness it the average thickness between pores as measured perpendicular to the pore wall surface. For purposes of this disclosure, pore wall thickness is determined by multiplying the dioo peak value in angstroms by 1.155 and then subtracting the average pore diameter in angstroms (as determined by the BJH adsorption plot of nitrogen adsorption). In the event that the dioo is obscured or otherwise unavailable, then the pore wall thickness is determined by multiplying the d₂oo peak value in angstroms by 2.31 and then subtracting the average pore diameter in angstroms (as determined by the BJH adsorption plot of nitrogen adsorption). In the event that the d_1Oo and d₂oo peaks are obscured or otherwise unavailable, then the pore wall thickness is determined by multiplying the d₃oo peak value in angstroms by 3.465 and then subtracting the average pore diameter in angstroms (as determined by the BJH adsorption plot of nitrogen adsorption).

M41S family mesoporous molecular sieves

[0017] The composition of matter made by the process of this disclosure is a M41S family mesoporous molecular sieve.

[0018] In one embodiment, the M41S family mesoporous molecular sieve made by the process of this disclosure comprises a crystalline phase material. The crystalline phase material has a composition expressed as follows:

M_n/q(W_aX_bY_cZ_dO_h) where M is one or more ions, such as ammonium, Group 1, 2 and 17 ions, preferably 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; W is one or more divalent elements, such as a divalent first row transition metal, e.g. manganese, cobalt, iron, and/or magnesium (for purposes of this disclosure the symbol W is not meant to indicate the element tungsten); X is one or more trivalent elements, such as aluminum, boron, iron and/or gallium, with aluminum being preferred; Y is one or more tetravalent elements such as silicon and/or germanium, with silicon being preferred; Z is one or more pentavalent elements, such as phosphorus; O is oxygen; 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)=l. [0019] A preferred embodiment of the above M41S family mesoporous molecular sieve is when (a+b+c) is greater than d, and h=2.

[0020] Another preferred embodiment is when a=0, d=0, and h=2. More preferably, X is aluminum and Y is silicon. Most preferably the molecular sieve is an aluminosilicate. Preferred aluminosilicates have a silica-to-alumina molar ratio of about 5: 1 to about 1000:1. Suitably, the composition of matter of this disclosure is an aluminosilicate characterized as having an alumina weight percent (Al₂O₃ wt%) of about 0.1 to about 20 Al₂O₃ wt%, based on the total weight of the composition of matter. Within this range, an alumina weight percent of less than or equal to about 15 can be employed, less than or equal to about 10 Al₂O₃ wt% being more preferred. Conveniently, the alumina weight percent is greater than or equal to about 1, preferably greater than or equal to about 4 Al₂O₃ wt%.

[0021] Prior to calcination, (i.e. in the as-synthesized form), the M41S family mesoporous molecular sieve of this disclosure preferably has a composition, on an anhydrous basis, expressed empirically as follows:

TR⁵⁵M_nZq(W₃X_bY₀Z_dO_h); wherein R' ' is the combined amount of R and R' not included in M as an ion, r is the coefficient for R, i.e. the number of moles or mole fraction of R", where W, X, Y, Z, O, n, q, a, b, c, d, and h are as defined above. 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 cations, e.g. sodium or chloride ions, of the as- synthesized material can be replaced at least in part, by ion exchange with other ions. Preferred replacing ions include metal ions, hydrogen ions, hydrogen precursors including ammonium ions, and mixtures of ions.

[0022] Preferably, the M41S family mesoporous molecular sieve of this disclosure is crystalline in that it provides a diffraction pattern with at least one peak by X-ray, electron or neutron diffraction, following calcination. The composition of matter of this disclosure preferably yields an X-ray diffraction pattern with a few distinct maxima in the extreme low angle region. The positions of these peaks preferably approximately fit the positions of the hkO reflections from a hexagonal lattice. The X-ray diffraction pattern, however, may not always be a sufficient indicator of the presence of these materials, as the degree of regularity in the microstructure 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 comprise the present composition of matter.

[0023] In its calcined form, the M41S family mesoporous molecular sieve is a non-layered inorganic porous crystalline phase material which may be characterized by an X-ray diffraction pattern with at least one peak at a position greater than about 18 Angstrom Units (A) d-spacing (4.909 degrees two-theta for Cu Ka radiation). More particularly, the calcined crystalline material of the disclosure may be characterized by an X-ray diffraction pattern with at least two peaks at positions greater than about IOA d -spacing (8.842 degrees two-theta for Cu Ka radiation), at least one of which is at a position greater than about 18A d-spacing, and no peaks at positions less than about IOA d-spacing with relative intensity greater than about 20% of the strongest peak. Still more particularly, the X-ray diffraction pattern of the calcined composition of matter of this disclosure will have no peaks at positions less than about IOA d-spacing with relative intensity greater than about 10% of the strongest peak.

[0024] The calcined non-layered inorganic porous crystalline phase material may be characterized as having a pore size greater than or equal to about 13A as measured by physio-sorption measurements more particularly set forth herein.

[0025] The M41 S family mesoporous molecular sieve of this disclosure may also be characterized based on sorption characteristics. Preferably, the M41S family mesoporous molecular sieve has an equilibrium benzene adsorption capacity of greater than about 15 grams benzene/ 100 grams M41S molecular sieve at 6.666118 kPa-a (50 torr) and 25°C, based on anhydrous crystal material having been treated to insure no pore blockage by incidental contaminants is present. Accordingly, the sorption tests are conducted on the M41S family mesoporous molecular sieve having any pore blockage contaminants and water removed. 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 non-layered inorganic porous crystalline phase material.

[0026] Preferably, the equilibrium benzene adsorption capacity is determined by contacting the anhydrous material of the disclosure, after oxidative calcination at 450°C-700°C for at least one hour, and other treatment, if necessary, to remove any pore blocking contaminants, at 25°C and 6.666118 kPa-a (50 torr) benzene until equilibrium is reached. The weight of benzene sorbed (i.e., adsorbed) is then determined. [0027] The equilibrium benzene adsorption capacity at 6.666118 kPa-a (50 torr) and 25°C, based on anhydrous crystal material having been treated to insure no pore blockage by incidental contaminants is present, is preferably greater than or equal to about 20 grams benzene/ 100 grams M41S molecular sieve, more preferably greater than or equal to about 25 grams benzene/ 100 grams M41S molecular sieve.

[0028] The equilibrium cyclohexane adsorption capacity at 6.666118 kPa-a (50 torr) and 25°C, based on anhydrous crystal material having been treated to insure no pore blockage by incidental contaminants is present is preferably greater than or equal to about 15 grams cyclohexane/ 100 grams M41S molecular sieve, more preferably greater than or equal to about 20 grams cyclohexane/ 100 grams M41S molecular sieve, still more preferably greater than or equal to about 25 grams cyclohexane/ 100 grams M41S molecular sieve.

[0029] The non-layered inorganic porous crystalline phase material may be synthesized with Bronsted acid active sites by incorporating a tetrahedrally coordinated trivalent element, such as Al, Ga, B, or Fe, within the silicate framework. Aluminosilicate materials of this type may be thermally and chemically stable, which are properties favored for acid catalysis. In addition, the mesoporous structures of the composition of matter may be utilized by employing highly siliceous materials or crystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity. In addition to aluminosilicates, gallosilicate, ferrosilicate and borosilicate materials may also be employed.

[0030] The M41S family mesoporous molecular sieve may also be characterized using techniques that illustrate the microstructure of this material, including transmission electron microscopy and electron diffraction. In determining X-ray diffraction patterns, the X-ray diffraction data is preferably collected using an X-ray diffraction system employing theta-theta geometry, Cu Ka radiation, and an energy dispersive X-ray detector such that use of an energy dispersive X-ray detector eliminates the need for incident or diffracted beam monochromators. Both the incident and diffracted X-ray beams are also preferably collimated by double slit incident and diffracted collimation systems. Preferred slit sizes used, starting from the X-ray tube source, include 0.5, 1.0, 0.3 and 0.2 mm, respectively. However, different slit systems may produce differing intensities for the peaks in the X-ray diffraction patterns.

[0031] Diffraction data may be recorded using 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 is used. The interplanar spacings, d's, may be calculated in Angstrom units (A), and the relative intensities of the lines, 1/I₀, where I₀ is one- hundredth of the intensity of the strongest line, above background, are preferably derived with the use of a profile fitting routine. Furthermore, the intensities are preferably uncorrected for Lorentz and polarization effects. It should be understood that diffraction data which appears as a single line 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. Accordingly, 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, peak width/shape variations due to particle size/shape effects, structural disorder, and/or other factors known to those skilled in the art of X-ray diffraction. [0032] Properly oriented specimens of the material preferably show a substantially hexagonal arrangement of large channels and the corresponding electron diffraction pattern gives an approximately hexagonal arrangement of diffraction maxima. As used herein, the d_1Oo 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 ao between channels observed in the electron micrographs through the formula dioo =ao(3/2)^1/2. Accordingly, this dioo 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. A preparation of the material may include greater than or equal to 20 to about 40 distinct spots observable in an electron diffraction pattern. These patterns can be indexed with the hexagonal hkO subset of unique reflections of 100, 110, 200, 210, and the like, and their symmetry-related reflections.

[0033] The dioo may be directly calculated (i.e., determined) from the measured XRD spectrum, and/or may also be calculated based on one or more peaks in the XRD spectrum. For example, the value of the d^o line may be calculated from the d₂oo line based on the formula: d,_Oo- 2(d_2OO) = 2(a_o (3/2)^1/2).

[0034] Accordingly, a calculated dioo value may be used in the event that the dioo value is not directly discernable from the XRD spectrum. As such, the preferred composition of matter has a base configuration consistent in many respects with the compound referred to as MCM-41, a detailed description of which can be found in U.S. Pat. No. 5,098,684.

[0035] The M41S family mesoporous molecular sieve may also comprise structural features and attributes of a group of mesoporous crystalline materials as described in U.S. Pat. Nos. 5,198,203 and 5,211,934, to which reference is made for a detailed description of these materials, their preparation and properties. These materials may be distinguished by the characteristic X-ray diffraction pattern of the calcined material. Using di to indicate the d-spacings of the strongest peak in the X-ray diffraction pattern (relative intensity=100), the X- ray diffraction pattern of the calcined material exhibits di at a position greater than about 18 A d-spacing and at least one additional weaker peak with d- spacing d₂ such that the ratios of these d-spacings relative to di (i.e. d_n/di) correspond to the following ranges:

[0036] More preferably, the X-ray diffraction pattern of the calcined material includes at least two additional weaker peaks at d-spacings d₂ and d₃ such that the ratios of these d-spacings relative to the strongest peak di at a position greater than about 18 A d-spacing) correspond to the following ranges:

[0037] Still more preferably, the X-ray diffraction pattern of the calcined materials includes at least four additional weaker peaks at d-spacings d₂, d₃, 6₄ and d₅ such that the ratios of these d-spacings relative to the strongest peak di (at a position greater than about 18A d-spacing) correspond to the following ranges:

[0038] Calcined materials of this group preferably exhibit an X-ray diffraction pattern including at least two peaks at positions corresponding to the following ranges:

[0039] More preferably, the X-ray diffraction patterns of the calcined examples presented herein can be characterized as including at least three peaks at positions corresponding to the following ranges:

[0040] Still more preferably, the X-ray diffraction patterns can be characterized as including at least five peaks at positions corresponding to the following ranges

[0041] The honeycomb microstructure of the non-layered inorganic porous crystalline phase material may also include several moieties interconnected in a three dimensional matrix or lattice having large hexagonal channels forming the ultra large pores of the catalyst. The repeating units forming the large ring structure of the lattice vary with pore size. In addition, a composition of matter may comprise 5 to 95 wt. % silica, clay and/or an alumina binder.

[0042] The term "substantially hexagonal" is intended 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 present disclosure would be that six nearest neighbor channels at roughly the same distance would surround most channels in the material. However, 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 present ultra-large pore materials. Comparable variations are also observed in the di_Oo values from the electron diffraction patterns. [0043] Furthermore, the M41 S family mesoporous molecular sieve, preferably calcined, of the present disclosure preferably has a pore wall thickness of less than or equal to about 25A. Within this range, a pore wall thickness of less than or equal to about 2θA can be employed, with less than or equal to about 15A more preferred. Also preferred within this range is a pore wall thickness of greater than or equal to about lA, with greater than or equal to about 4A more preferred and greater than or equal to about 6A especially preferred. In a preferred embodiment the pore wall thickness is from about 1 to 25A, preferably, 2 to 25A, more preferably 3 to 25A, more preferably 4 to 23A, more preferably 5 to 2θA, more preferably 5 to 18 A, more preferably 6 to 15 A.

[0044] The calcined M41 S family mesoporous molecular sieve preferably has a uniformity of pore size, wherein greater than or equal to about 80% of the pores have a pore diameter plus or minus about 20% the average pore diameter of the composition of matter; more preferably, greater than or equal to about 90% of the pores present have a pore diameter plus or minus about 5% the average pore diameter of the composition of matter.

The Process of Making the M41S Family Mesoporous Molecular Sieve

[0045] The term "recycle liquids" as used herein means at least one of the mother liquors, the washing liquids, the cleaning liquids, and any combination thereof produced from at least one previous M41S family mesoporous molecular sieve synthesis process.

[0046] The M41S family mesoporous molecular sieve of this disclosure 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 of elements comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; at least one organic directing agent (R), optionally in combination with one or more organic directing agents (R'); and a solvent, preferably water. The reaction mixture is maintained under suitable crystallization conditions to form the M41S family mesoporous molecular sieve. After crystallization, the M41S family mesoporous molecular sieve may be recovered by decantation or filtration as a filtration cake, optionally washed with liquid media.

[0047] After crystallization of the molecular sieve, the residual reaction mixture not incorporated into the M41 S family mesoporous molecular sieve may be collected by decantation or filtration as mother liquor. The term "mother liquor" as used herein, means the liquid media, typically aqueous, separated from the filtration cake by a filtration process, or the liquid media, typically aqueous, separated from the molecular sieve crystals by decantation. The mother liquor collected may contain residual sources of, for example, alkali or alkaline earth metal (M), e.g. sodium or potassium cation, one or a combination of oxides comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R) as well as an organic directing agent (R'); and a solvent, preferably water. The mother liquor may contain small crystals of the M41S family mesoporous molecular sieve which were not retained as a part of the molecular sieve crystals during the filtration or decantation process.

[0048] The filtrated and/or decanted solid M41S family mesoporous molecular sieve may further be subjected to one or several washing steps to remove residual mother liquor or any other impurities from the molecular sieve crystals, preferably with a liquid medium comprising at least one of water, CpC_ό alcohol, Ci-C₆ diol, or any mixture thereof. The liquid media may further comprise a source of, for example, ammonia, ammonium salts, e.g., ammonium nitrate. The term "washing liquid(s)" as used herein means, liquid(s) collected during the washing step(s). The washing liquid(s) collected may contain residual sources of, for example, alkali or alkaline earth metal (M), e.g. sodium or potassium cation, one or a combination of oxides comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R) as well as an organic directing agent (R'); and a solvent, preferably water. The washing liquid(s) may contain small crystals of the M41S family mesoporous molecular sieve which were not retained as a part of the cake during the washing process.

[0049] The process equipments, such as autoclave, pipe(s)/transfer line(s), container(s)/tank(s), or filtration equipment(s), may be subjected to one or several cleaning steps to wash out any residual materials left over from the previous synthetic batch(es), preferably with a liquid media comprising at least one of water, CpC₆ alcohol, Ci-C₆ diol, any mixture thereof. The liquid media may further comprise a source of, for example, ammonia, ammonium salts, e.g., ammonium nitrate. The term "cleaning liquid(s)" as used herein means, liquid collected during the cleaning step(s). The cleaning liquid(s) collected may contain residual sources of, for example, alkali or alkaline earth metal (M), e.g. sodium or potassium cation, one or a combination of oxides comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R) as well as an organic directing agent (R'); and a solvent, preferably water. The cleaning liquid(s) may contain small crystals of the M41 S family mesoporous molecular sieve which were not retained as a part of the cake during the washing process. [0050] The mother liquor(s), the washing liquid(s), and/or the cleaning liquid(s) may be obtained from from one or several of any previous synthesis batch. Mother liquors, washing liquids and/or cleaning liquids may be combined in any way for this purpose. The expression "the mother liquor(s), the washing liquid(s), and/or the cleaning liquid(s) generated from previous synthesis batch(es)" and any variation therefrom is intended to include the mother liquor, the washing liquid(s), and the cleaning liquid(s) collected from any previous synthesis or previous synthesis batches, combined in any way.

[0051] The recycle liquid, such as, the mother liquor(s), the washing liquid(s), and/or the cleaning liquid(s), collected in the manufacturing process normally contains organic template (R), optionally in combination with (R' ), expressed in terms of carbon content and/or nitrogen content), optionally any combination of alkali or alkaline earth metal (M), a divalent element (W), a trivalent element (X), a tetravalent element (Y), a pentavalent element (Z), and a solvent, optionally in combination with an auxiliary organic solvent. The following table (Table I) shows the typical and the preferred ranges of individual components.

Table I: Useful and preferred composition ranges for mother liquor(s) and washing liquid(s)/cleaning liquid(s)^*

^*A11 ranges in the Table I list numbers in the format of greater than about to about .

[0052] In some embodiments, the recycle liquid is used in the synthesis mixture with no intermediate treatment(s), such as, precipitation of silicate, silica-alumina hydrogel formation, or separation and recovering organic template/surfactant, after being collected from at least one previous molecular sieve synthesis process.

[0053] The M41S family mesoporous molecular sieve of this disclosure 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 of elements comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R), optionally in combination with (R' ); and a solvent, wherein at least a portion of said solvent comprises at least a portion of the recycle liquid produced from at least one previous synthesis process, and optionally, at least one of Ci-C₆ alcohol, CpC₆ diol, and water. The reaction mixture preferably has 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.

[0054] In a preferred embodiment X is aluminum and Y is silicon in the above table.

[0055] When no Z and/or W oxides are added to the reaction mixture, the pH is preferably maintained at from about 10 to about 14. When Z and/or W oxides are present in the reaction mixture, the pH may vary between about 1 and 14 for crystallization of the M41S family mesoporous molecular sieve. The pH may conveniently be adjusted by a source of alkali or base. In one embodiment, the pH is adjusted by a source of alkali. In another embodiment, the source of alkali is also the source of R'.

[0056] The M41 S family mesoporous molecular sieve of this disclosure can be prepared by one of several methods. One preferred method may include a reaction mixture having an X₂O₃/YO₂ mole ratio of from 0 to about 0.5, a crystallization temperature of from about 25°C to about 250⁰C, preferably from about 50⁰C to about 175°C, and an organic directing agent (R), or preferably a combination of an organic directing agent (R) with an additional organic directing agent (R'). This preferred method comprises preparing 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 of elements comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R) or combination or organic directing agents (R) and (R'); and a solvent, wherein at least a portion of said solvent comprises at least a portion of the recycle liquid generated from at least one previous synthesis batch, and optionally, at least one of CpC₆ alcohol, CpC₆ diol, and water. The reaction mixture preferably has a composition, in terms of mole ratios of oxides, within the following ranges:

where e and f are the weighted average valences of M and R, respectively. [0057] In this method, when no Z and/or W oxides are added to the reaction mixture, the pH is preferably maintained at from about 9 to about 14. In a preferred embodiment X is aluminum and Y is silicon in the above table.

[0058] A second method for synthesis of the M41S family mesoporous molecular sieve of this disclosure involves a reaction mixture having an X₂O₃AfO₂ mole ratio of from about 0 to about 0.5, a crystallization temperature of from about 25°C to about 250⁰C, preferably from about 50⁰C to about 175°C, and preferably two separate organic directing agents (R) and (R'), i.e. the organic and additional organic directing agents. This preferred method comprises preparing 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 of elements comprising: a divalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y, e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic directing agent (R) and an additional directing agent (R'); and a solvent, wherein at least a portion of said solvent comprises at least a portion of the recycle liquid produced from previous synthesis batch(es), and optionally, at least one of Ci -C₆ alcohol, Cj-C₆ diol, and water. The reaction mixture preferably has a composition, in terms of mole ratios of oxides, within the following ranges:

where e and f are the weighted average valences of M and R, respectively. In a preferred embodiment X is aluminum and Y is silicon in the above table.

[0059] In this second method, when no Z and/or W oxides are added to the reaction mixture, the pH is preferably maintained at from about 9 to about 14.

[0060] A third method for synthesis of the M41S family mesoporous molecular sieve of this disclosure is where X comprises aluminum and Y comprises silicon, the crystallization temperature is preferably from about 25°C to about 175°C, preferably from about 50⁰C to about 150⁰C, and an organic directing agent (R), preferably a combination of organic directing agents (R) and (R') is used. This 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, and a solvent, wherein at least a portion of said solvent comprises at least a portion of the recycle liquid collected from at least one previous synthesis batch, and optionally, at least one of Ci-Ce alcohol, CpCβ diol, and water. The reaction mixture has a composition, in terms of mole ratios of oxides, within the following ranges:

where e and f are the weighted average valences of M and R, respectively. The pH is preferably maintained at from about 9 to about 14.

[0061] Preferred conditions typically involve the following steps:

(1) Mix the organic directing agent (R) or combination of organic directing agents (R) and (R') with the solvent such that the mole ratio of solvent/R_2/fO is within the range of from about 50 to about 800, preferably from about 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/fO/(SiO₂ +Al₂O₃) is within the range of from about 0.01 to about 2.0.

(3) Agitate the mixture resulting from step (2) at a temperature of from about 20⁰C to about 40⁰C, preferably for about 5 minutes to about 3 hours. (4) Allow the mixture to stand with or without agitation, preferably at a temperature of from about 20⁰C to about 100⁰C, and preferably for about 10 minutes to about 24 hours.

(5) Crystallize the product from step (4) at a temperature of about 50⁰C to about 175°C, preferably for about 1 hour to about 72 hours. Crystallization temperatures higher in the given ranges are more preferred.

[0062] Another method for the synthesis of the M41S family mesoporous molecular sieve involves the reaction mixture used for method three, and also includes the following specific procedure using tetraethylorthosilicate as the source of silicon oxide:

(1) Mix the organic directing agent (R) or combination or organic directing agents (R) and (R') with the solvent such that the mole ratio of solvent/R_2/fO is within the range of from about 50 to about 800, preferably from about 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/fO/SiO₂ mole ratio is in the range of from about 0.5 to about 2.0.

(3) Agitate the mixture resulting from step (2) for about 10 minutes to about 6 hours, preferably about 30 minutes to about 2 hours, at a temperature of about 0⁰C to about 25°C, and a pH of less than 12. This step permits hydrolysis/polymerization to take place and the resultant mixture may appear cloudy.

(4) Crystallize the product from step (3) at a temperature of about 25°C to about 250⁰C, preferably about 80⁰C to about 150⁰C, for about 4 to about 72 hours, preferably about 16 to about 48 hours. Crystallization of the composition of matter 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. The range of temperatures for crystallization is preferably about 5O⁰C to about 250⁰C for a time sufficient for crystallization to occur at the temperature used. Preferred crystallization time's range from about 5 minutes to about 14 days. Thereafter, the crystals are separated from the liquid and recovered.

[0063] Non-limiting examples of various combinations of W, X, Y, and Z contemplated for the non-layered inorganic porous crystalline phase material are disclosed in Table II.

Table II - Non-Layered Inorganic Porous Crystalline Phase Material

Components

[0064] The compositions may also include the combinations of W comprising Mg or an element selected from the divalent first row transition metals including Mn, Co and Fe; X comprising B, Ga or Fe; and Y comprising Ge.

[0065] The preferred organic directing agent (R) for use in synthesizing the M41S family mesoporous molecular sieve from the reaction mixture is a quaternary ammonium or phosphonium ion of the formula RiR₂RaRiQ⁺, wherein Q is nitrogen or phosphorus and wherein at least one of Ri, R₂, R₃, and/or R₄ is an aryl group or alkyl group having from 6 to about 36 carbon atoms, preferably wherein at least one of Ri, R₂, R₃, and/or R₄ comprises --C₆ Hj₃, --Ci₀H_2I, -Cj₆ H₃₃₅-Ci₈ H₃₇, or combinations comprising at least one of the foregoing. The remainder of Rj, R₂, R₃, and/or R₄ preferably comprises hydrogen, an alkyl group having from 1 to 5 carbon atoms, and combinations comprising at least one of the foregoing. Preferably, the quaternary ammonium or phosphonium ion is derived from the corresponding hydroxide, halide, or silicate.

[0066] An additional organic directing agent (R') may also be present in the reaction mixture along with the above organic directing agent (R). In one embodiment, an additional organic directing agent (R') may be a quaternary ammonium or phosphonium ion of the formula R'iR'₂R'₃R'₄Q⁺, wherein Q is nitrogen or phosphorus and wherein R'i, R'₂, R' ₃, and R'₄ are each independently selected from hydrogen and alkyl groups having 1 to 5 carbon atoms.

[0067] Preferred organic directing agent (R) include cetyltrimethylammonium, hexadecyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylammonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, decyltrimethylammonium, dimethyldidodecylammonium, and combinations comprising at least one of the foregoing.

[0068] When an additional organic directing agent (R') is used, useful relative amounts of (R') and (R) are typically such that the R'_2/fO/R^_fO molar ratio ranges from 0.05 to 5, preferably from 0.2 to 2, more preferably from 0.5 to 1.5. Conveniently, the R'_2/fO/R_2/fO molar ratio is of about 1.

[0069] The M41S family mesoporous molecular sieve of this disclosure may also be produced using a swelling agent, which may include being pillared to provide materials having a large degree of porosity. Examples of swelling agents include clays that may be swollen with water, whereby the layers of the clay are spaced apart by water molecules. Other materials include those which may be swollen with organic swelling agents as described in U.S. Pat. No. 5,057,296, and the like. Organic swelling agents may include amines, quaternary ammonium compounds, alkyl and aromatic swelling agents. Preferred swelling agents include alkyl-substituted aromatics such as 1,3,5- trimethylbenzene, and the like. Examples of non-water swellable layered materials are described in U.S. Pat. No. 4,859,648 and include silicates, magadiite, kenyaite, trititanates and perovskites. Other examples of a non-water swellable layered materials which can be swollen with organic swelling agents include vacancy-containing titanometallate material, as described in U.S. Pat. No. 4,831,006.

[0070] Once a material is swollen, the material may be pillared by interposing a thermally stable substance, such as silica, between the spaced apart layers. The aforementioned U.S. Pat. Nos. 4,831,006 and 4,859,648 describe methods for pillaring non-water swellable layered materials described therein, and are incorporated herein by reference for definition of pillaring and pillared materials.

[0071] Other patents teaching pillaring of materials and the pillared products include U.S. Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and 4,367,163; and European Patent Application 205,711.

[0072] The X-ray diffraction patterns of pillared materials can vary considerably, depending on the degree that swelling and pillaring disrupt the otherwise usually well-ordered microstructure. The regularity of the microstructure in some pillared materials is so badly disrupted that only one peak in the low angle region on the X-ray diffraction pattern is observed, as a d- spacing corresponding to the repeat distance in the pillared material. Less disrupted materials may show several peaks in this region that are generally orders of this fundamental repeat. X-ray reflections from the crystalline structure of the layers are also sometimes observed. The pore size distribution in pillared materials may be narrower than those in amorphous and paracrystalline materials, but may be broader than that in crystalline framework materials.

[0073] The M41S family mesoporous molecular sieve of this disclosure may also be produced with an auxiliary organic selected from the group consisting of (1) aromatic hydrocarbons and aromatic amines having from 5 to 20 carbons and halogen- and Ci -Ci₄ alkyl-substituted derivatives thereof, (2) cyclic aliphatic hydrocarbons and cyclic aliphatic amines amines having from 5 to 20 carbons and halogen- and Ci -Ci₄ alkyl-substituted derivatives thereof, (3) polycyclic aliphatic hydrocarbons and polycyclic aliphatic amines having from 6 to 20 carbons and halogen- and Ci -C_H alkyl-substituted derivatives thereof, (4) straight and branched aliphatic hydrocarbons and straight and branched aliphatic amines of from 3 to 16 carbons and halogen-substituted derivatives thereof, and (5) combinations thereof, the reaction mixture typically having a composition, in terms of mole ratios, within the following ranges:

Auxiliary Organic/YO₂ 0.05 to 20

Auxiliary Organic/R_2/fO 0.02 to 100

[0074] Of the above group of organic compounds, the aromatic hydrocarbons (e.g. C₆-C_2O), cyclic aliphatic hydrocarbons and polycyclic aliphatic hydrocarbons, and combinations thereof, are preferred. In one aspect of this disclosure, the auxiliary organic is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, dodecane, dihalooctane, p- xylene, trimethylbenzene, triethylbenzene, dimethyladamantane, benzene, alkyl- substituted benzene, alkyl-substituted adamantane and combinations thereof, alkyl being of from 1 to about 14 carbon atoms. The use of an auxiliary organic, in combination with the organic directing agent (R) has proved useful to make ultra large pore M41S mesoporous molecular sieves (see for example US Patent No. 5,057,296).

[0075] In producing the M41S family mesoporous molecular sieve of this disclosure, the reaction mixture components may be supplied by more than one source and the reaction mixture may be prepared either batchwise or continuously. As used herein the expression "previous synthesis batch" intends to refer to molecular sieve prepared by any type previous synthesis process, regardless of whether the reaction mixture was prepared batchwise or continuously. The expression "previous synthesis batch" should thus not be interpreted as limiting the invention to the use of recycle liquid obtained by a synthesis process in which the reaction mixture is prepared batchwise. Furthermore, the non-layered inorganic porous crystalline phase composition of matter can be shaped into a wide variety of particle sizes and include a powder, a granule, or a molded product, such as an extrudate. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.

[0076] By using the mother liquor and/or the washing liquid(s) from one or any previous synthesis process, this disclosure offers an advantageous synthesis method. At least a portion of the organic template is obtained from the recycle liquid. Optionally, at least a portion of the divalent element, trivalent element, tetravalent element, or pentavalent element is obtained from the recycle liquid. The method disclosed in this disclosure is simpler and more economical due to eliminating or at least reducing the amount of the liquid for disposal before discharge. Furthermore, the methods disclosed in this disclosure reuse at least a portion of the costly organic template recovered from previous synthesis processes.

[0077] In the above improved procedure, batch molecular sieve crystallization 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. Useful crystallization temperatures are typically of at least 25°C, preferably of at least 50⁰C, and conveniently of at least 80⁰C. Also, useful crystallization temperatures are no higher than 250⁰C, preferably less than 200⁰C, and conveniently of less than 175°C. Such temperature is applied for a time sufficient for crystallization to occur at the temperature used, e.g. from about 5 minutes to about 14 days. Thereafter, the crystals are separated from the liquid and recovered.

Industrial Applications

[0078] This present disclosure is useful for the synthesis of the M41S family mesoporous molecular sieve, in particular the MCM-41 material. The method of this disclosure uses the recycled recycle liquid (the mother liquor and/or the washing liquid(s)/cleaning liquid(s)) produced/collected/generated from previous processes of MCM-41 crystallization. The M41S family mesoporous molecular sieves made by the method of this disclosure show good quality and high surface area and are suitable for catalytic and/or sorption processes. Reusing the recycle liquid produced from previous processes reduces the amount of recycle liquid for disposal and lowers the production costs.

EXAMPLES [0079] Three types of recycle liquid collected from the previous synthesis batches were provided for testing. Compositions of these recycle liquids were shown in the Table III. Table IV lists the components used in the following examples and their sources.

Table III

Type 1 and type 2 were washing liquid(s)/cleaning liquid(s). Type 3 was mother liquor.

Table IV

Example 1 Comparative example

[0080] A mixture was prepared from fresh DI water, Tetramethylammonium Hydroxide (TMAOH) 25 wt.% solution, ARQUAD^® 16-29 solution, Sodium aluminate 45 wt.% solution, and Ultrasil PM Modified silica. The mixture had the following molar composition:

SiO₂/Al₂O₃ 50/1 H₂O/ SiO₂ 18/1 (TMA)₂O / (HDTMA)₂O ~ 1 SiO₂/ HDTMACl ~ 7

[0081] The mixture was reacted at 250⁰F (121°C) in an autoclave at 150 rotation per minute (RPM) for 27 and 48 hours. The product was discharged and dried at 250⁰F (120⁰C) before use. The XRD pattern of the as-synthesized material showed the typical pure phase of MCM-41 topology. The SEM of the as-synthesized material shows that the material was composed of agglomerates of small crystals. The resulting calcined MCM-41 crystals had a surface area of 850 and 864 m²/g for the 27 and 48 hrs samples respectively.

EXAMPLE 2

[0082] A mixture was prepared from Type 1 recycle liquid, Tetramethylammonium Hydroxide (TMAOH) 25 wt.% solution, ARQUAD^® 16- 29 solution, Sodium aluminate 45 wt.% solution, and Ultrasil PM Modified silica. The mixture had the following molar composition (recycle liquid was calculated as water without counting Si, Al, hydroxide, and surfactant):

SiO₂/Al₂O₃ ~ 50/1

H₂O/ SiO₂ - 18/1

(TMA)₂O / (HDTMA)₂O ~ 1

SiO₂/ HDTMACl ~ 7

[0083] The mixture was reacted at 250⁰F (121⁰C) in an autoclave at 150 RPM for 24 hours. The product was discharged and dried at 250⁰F (120⁰C) before use. The XRD pattern of the as-synthesized material showed the typical pure phase of MCM-41 topology. The SEM of the as-synthesized material showed that the material was composed of agglomerates of small crystals. The resulting calcined MCM-41 crystals had a SiO₂/Al₂O₃ molar ratio of 46.3 and surface area of 864 m²/g. EXAMPLE 3

[0084] A mixture was prepared from Type 2 recycle liquid, Tetramthylammonium Hydroxide (TMAOH) 25 wt.% solution, ARQUAD^® 16- 29 solution, Sodium aluminate 45 wt.% solution, and Ultrasil PM Modified silica. The mixture had the following molar composition (recycle liquid was calculated as water without counting Si, Al, hydroxide, and surfactant):

SiO₂ZAl₂O₃ ~ 50/1

H₂O/ SiO₂ - 18/1

(TMA)₂O / (HDTMA)₂O ~ 1

SiO₂/ HDTMACl ~ 7

[0085] The mixture was reacted at 250⁰F (121°C) in an autoclave at 150 RPM for 24 hours. The product was discharged and dried at 250⁰F (12O⁰C) before use. The XRD pattern of the as-synthesized material showed the typical pure phase of MCM-41 topology. The SEM of the as-synthesized material showed that the material was composed of agglomerates of small crystals. The resulting calcined MCM-41 crystals had a SiO₂/Al₂O₃ molar ratio of 45.2 and surface area of 849 m²/g.

EXAMPLE 4

[0086] A mixture was prepared from Type 3 recycle liquid, Tetramthylammonium Hydroxide (TMAOH) 25 wt.% solution, ARQUAD^® 16- 29 solution, Sodium aluminate 45 wt.% solution, and Ultrasil PM Modified silica. The mixture had the following molar composition (recycle liquid was calculated as water without counting Si, Al, hydroxide, and surfactant):

SiO₂/Al₂O₃ ~ 50/1

H₂O/ SiO₂ - 18/1

(TMA)₂O / (HDTMA)₂O ~ 1

SiO₂/ HDTMACl ~ 7 [0087] The mixture was reacted at 250⁰F (121⁰C) in a 2-liter autoclave at 150 RPM for 24 hours. The product was discharged and dried at 250⁰F (120⁰C) before use. The XRD pattern of the as-synthesized material showed the typical pure phase of MCM-41 topology. The SEM of the as-synthesized material showed that the material was composed of agglomerates of small crystals. The resulting calcined Al-MCM-41 crystals had a SiO₂/Al₂O₃ molar ratio of 43.2 and surface area of 773 m²/g.

RESULTS AND CONCLUSIONS

[0088] High quality MCM-41 products with high surface area can be prepared from a reaction mixture containing recycled recycle liquid generated from previous production batches. The results demonstrated that all 3 types of recycle liquid are useful for the MCM-41 crystallization. These include the mother liquor separated from the final reaction slurry and two types of recycle liquid generated during the washing step of filtration. Recycling and reusing recycle liquid significantly reduces the amount of the eco-toxic surfactant containing recycle liquid generated in the MCM-41 production and, therefore reduce disposal and/or production costs for making the M41 S family molecular sieves.

Claims

CLAIMS:

1. A method for synthesizing a composition of matter comprising an inorganic, porous crystalline phase material having, after calcination, a substantially hexagonal arrangement of substantially uniformly-sized pores having mean diameters of at least about 13 Angstrom Units and exhibiting a substantially hexagonal electron diffraction pattern that can be indexed with a dioo value greater than about 18 Angstrom Units, the method comprising:

(a) preparing a mixture capable of forming the composition of matter, the mixture comprising sources of one or a combination of oxides of elements selected from the group consisting of divalent element W, trivalent element X, tetravalent element Y and pentavalent element Z, an organic directing agent (R) and a solvent, and having a composition, in terms of mole ratios, within the following ranges:

wherein e and f are the weighted average valences of M and R, respectively, M is an alkali or alkaline earth metal ion and R comprises an ion of the formula R₁R₂R₃R₄Q⁺, wherein Q is nitrogen or phosphorus and wherein at least one of Ri, R₂, R₃ and R₄ is selected from the group consisting of aryl groups having from 6 to about 36 carbon atoms, alkyl groups having from 6 to about 36 carbon atoms and combinations thereof, the remainder of Ri, R₂, R₃ and R₄ being selected from the group consisting of hydrogen, alkyl groups having from 1 to 5 carbon atoms and combinations thereof, wherein at least a portion of the solvent comprises at least one recycle liquid produced during at least one previous process for the manufacture of the composition of matter;

(c) separating the composition of matter .

2. The method of claim 1, wherein said recycle liquid comprises at least one of the mother liquors produced from at least one previous synthesis batch, at least one washing liquid produced from at least one previous synthesis batch, at least one cleaning liquid produced from at least one previous synthesis batch, or any combination thereof.

3. The method of any of the preceding claims, wherein said recycle liquid comprises water, and optionally, at least one Cpcβ alcohol and/or at least one CpC₆ diol.

4. The method of any of the preceding claims, wherein said recycle liquid comprises at least 0.01 wt% of carbon element and 0.001 wt% of nitrogen element.

5. The method of any of the preceding claims, wherein said mixture comprises an additional organic directing agent ion (R') of the formula R'₁R'₂R'₃R'₄Q⁺, wherein R'i, R'₂, R'₃ and R'₄ is independently selected from the group consisting of hydrogen, alkyl groups having 1 to 5 carbon atoms and combinations thereof.

6. The method of claim 5, wherein R and R' are present in the mixture in amounts such that the R'_2/fO/R_2/fO molar ratio ranges from 0.05 to 5.

7. The method of any of the preceding claims, wherein R comprises an organic agent selected from the group consisting of cetyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldidodecylammonium.

8. The method of any one of claims 1 to 6, wherein said Ri, R₂, R₃ and R₄ are selected from the group consisting of -C₆Hn, --C₁₀H₂₁, -Ci₂H_2S, ~ C_HH₂₉, -C₁₆H₃₃, -C_I8H₃₇ and combinations thereof.

9. The method of any of the preceding claims, wherein X is aluminum and Y is silicon.

10. The method of any of the preceding claims, wherein no divalent element W is used.

11. The method of any of the preceding claims, wherein no pentavalent element Z is used.