WO2006037436A2 - Aluminophosphate molecular sieve, its synthesis and use - Google Patents
Aluminophosphate molecular sieve, its synthesis and use Download PDFInfo
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- WO2006037436A2 WO2006037436A2 PCT/EP2005/009878 EP2005009878W WO2006037436A2 WO 2006037436 A2 WO2006037436 A2 WO 2006037436A2 EP 2005009878 W EP2005009878 W EP 2005009878W WO 2006037436 A2 WO2006037436 A2 WO 2006037436A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
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- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates (APO compounds)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- 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 invention relates to a large pore aluminophosphate molecular sieve, or a substituted derivative thereof, to a method of its synthesis in a low fluoride or fluoride-free medium and to its use in organic conversion reactions.
- Crystalline molecular sieves have a 3 -dimensional, four-connected framework structure of corner-sharing [TO 4 ] tetrahedra, where T is any tetrahedrally coordinated cation.
- aluminosilicates which contain a three-dimensional microporous crystal framework structure of [SiO 4 ] and [AlO 4 ] corner sharing tetrahedral units
- aluminophosphates APOs
- the framework structure is composed of [AlO 4 ] and [PO 4 ] corner sharing tetrahedral units
- SAPOs silicoaluminophosphates
- the framework structure is composed of [SiO 4 ], [AlO 4 ] and [PO 4 ] corner sharing tetrahedral units.
- Molecular sieves are typically described in terms of the size of the ring that defines a pore, where the size is based on the number of T atoms in the ring.
- Other framework-type characteristics include the arrangement of rings that form a cage, and when present, the dimension of channels, and the spaces between the cages. See van Bekkum, et al., Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition, Volume 137, pages 1-67, Elsevier Science, B.V., Amsterdam, Netherlands (2001).
- molecular sieves can be divided into small, medium and large pore materials.
- small pore molecular sieves typically have pores defined by a ring of no more than 8 T atoms and have an average pore size less than about 0.5 nm (5A).
- Medium pore molecular sieves typically have pores defined by a ring of 10 T atoms and have an average pore size about 0.5 to 0.6 nm (5 to 6A), whereas large pore materials have pores defined by rings of 12 or more T atoms and a pore size greater than 0.6 nm (6A).
- Crystalline molecular sieves as exemplified by zeolites and
- 6,680,278 that a crystalline silicoaluminophosphate molecular sieve of the CHA framework type (a small pore material), can be synthesized in the presence of an organic directing agent mixture comprising tetraethylammonium cations and one or more dimethylamino moieties selected from one or more of N,N-dimethylethanolarnine, N 5 N- dimethylpropanolamine, N,N-dimethylbutanolamine, N 5 N- dimethylheptanolamine, N,N-dimethylhexanolamine, N 5 N- dimethylethylenediamine, N,N-dimethylbutylenediamine, N 5 N- dimethylheptylenediamine, N,N-dimethylhexylenediamine l-dimethylamino-2- propanol, N,N-dimethylethylamine, N,N-dimethylpropylamine, N 5 N- dimethylpenty
- organic directing agents that have been used in the synthesis of CHA framework type materials include isopropylamine or di-n-propylamine triethylamine, cyclohexylamine, 1-methylamidazole, morpholine, pyridine, piperidine, di ethyl ethanolamine, and N,N,N',N'-tetraethylethylene diamine.
- fluoride-containing compounds such as hydrogen fluoride
- EP-A-337,479 discloses the use of hydrogen fluoride in water at low pH to mineralize silica in glass for the synthesis of ZSM-5.
- Patent Application Publication No. 2003/0231999 published December 18, 2003 and incorporated herein by reference discloses that aluminophosphate or silicoaluminophosphate molecular sieves having the CHA framework type can be synthesized in the presence of fluoride ions using the dimethylamino compounds disclosed in U.S. Patent No. 6,680,278 as directing agents.
- fluoride- based syntheses pose environmental problems in that they use hydrogen fluoride in the synthesis medium and/or produce hydrogen fluoride on calcination to remove the organic directing agent from the molecular sieve product.
- an entirely rational approach that leads to the synthesis of unique framework materials is not available, due to the fact that all crystalline microporous materials are metastable phases and they are kinetic products. Their discovery is therefore often serendipitous.
- Figure 1 provides a comparison of the X-ray diffraction pattern of NK- 101 with that of EMM-8 and it is apparent from this comparison that the material of the invention is different from NK-101.
- the most prominent diffraction peaks are at 2-theta values of approximately 17° and 19°, whereas these peaks are not present in the X-ray diffraction pattern of EMM-8.
- SSZ-51 a new aluminophosphate zeotype framework structure, SSZ-51 , having the empirical formula AI 4 (PCM) 4 F 1 C 7 N 2 H 1 !'0.5H 2 O.
- the synthesis employs 4- dimethylaminopyridine as a structure directing agent and requires the presence of fluoride ion as a mineralizing agent.
- the structure of SSZ-51 is said to be closely related to that of S APO-40, an AFR framework type material, and to contain intersecting channels defined by 8- and 12-membered ring windows. It appears that SSZ-51 is isostructural with EMM-8.
- EP-A-O 324 082 discloses the synthesis of non-zeolite molecular sieves by contacting alumina or silica-alumina bodies with a liquid reaction mixture containing a reactive source of phosphorus and an organic templating agent.
- the invention resides in a crystalline molecular sieve having a framework comprising tetrahedrally coordinated atoms (T) connected by bridging atoms and having the coordination sequence and vertex symbols listed in Table 3 below.
- the invention resides in a crystalline molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern including the lines listed in Table 4 below.
- the crystalline molecular sieve of the invention has an X-ray diffraction pattern including the lines listed in Table 5 below.
- the phrase "including the lines” as used herein means that peaks are expected to be present at or close to the lines indicated in the Tables, but not necessarily in the relative intensities specified, which can vary depending on a number of factors as discussed later.
- the invention resides in a crystalline material having, in its as-synthesized form, an X-ray diffraction pattern including the lines listed in Table 4 below and represented, in its as-synthesized form and on an anhydrous basis, by the empirical formula: mR:F a :(M x Al y P z )0 2 wherein R represents at least one directing agent, preferably A- dimethylaminopyridine; m is the number of moles of R per mole of (M x Al y P z )O 2 and m has a value from 0 to 1, such as from 0.1 to about 0.5, for example from 0.1 to about 0.3; wherein a is the number of moles of fluoride ion (F) per mole of (M x AIyP 2 )O 2 and a/y is less than 0.25 and preferably is 0; wherein x, y, and z represent the mole fraction of M, Al
- M is silicon.
- x is from 0 to about 0.25, y is from about 0.3 to about 0.7 and z is from about 0.25 to about 0.7.
- x is from 0 to about 0.15, y is from about 0.4 to about 0.6 and z is from about 0.3 to about 0.6.
- x is from about 0 to about 0.12, y is from about 0.45 to about 0.55 and z is from about 0.35 to about 0.55.
- x is zero.
- the invention resides in a method of synthesizing the crystalline material of the invention, the process comprising: (a) forming a reaction mixture comprising water, a source of aluminum, a source of phosphorus, at least one structure directing agent comprising A- dimethylaminopyridine, optionally a source of metal M and optionally a source of fluoride ion, wherein F: Al 2 O 3 molar ratio of said reaction mixture is preferably less than 0.5 and most preferably is 0; (b) inducing crystallization of said crystalline material from the reaction mixture; and (c) recovering said crystalline material from the reaction mixture.
- the invention resides in a method of synthesizing a crystalline material having the CHA framework type, the process comprising: (a) forming a reaction mixture comprising a source of aluminum, a source of phosphorus, optionally a source of metal M, at least one directing agent comprising 4-dimethylaminopyridine and seeds of a CHA framework type material, such as SAPO-34; (b) inducing crystallization of said crystalline material from the reaction mixture; and (c) recovering said crystalline material from the reaction mixture.
- the invention resides in the use of the crystalline material of said one aspect of the invention as a sorbent and as a catalyst in organic conversion reactions.
- Figure 1 is a comparison of the X-ray diffraction pattern of NK-101 with the X-ray diffraction pattern of Sample A in Example 1 after calcination as in
- Example 4 The ordinates for the two patterns are to the same scale and reflect intensity counts.
- Figure 2 gives the X-ray diffraction patterns of the as-synthesized products of Example 1 after crystallization for 2 days and 4 days.
- Figure 3 compares the X-ray diffraction pattern of Sample A of
- Example 1 and Sample B of Example 2.
- Figure 5 is a comparison of the X-ray diffraction patterns of Sample A of Example 1 and Samples C and D of Example 3.
- Figure 6 is a comparison of the X-ray diffraction pattern of Sample
- Figure 7 gives the X-ray diffraction patterns of Sample C as- synthesized and after undergoing a series of calcination, hydration and dehydration treatments as described in Example 5.
- Figure 8 gives the X-ray diffraction patterns of the as-synthesized products of Example 8 after crystallization for 2 days and 4 days.
- Figure 9 is an illustration of the framework structure of EMM-8 showing only the tetrahedral atoms.
- the present invention relates to a porous crystalline material, EMM-8, and its synthesis in a low fluoride or fluoride-free medium with the organic directing agent, 4-dimethylaminopyridine.
- the crystalline structure remains intact after calcination to remove the directing agent and adsorption data indicate that the resultant material has large pores, hi particular, the calcined material adsorbs a significant amount of mesitylene, as well as 2,2-dimethylbutane, n-hexane, and methanol.
- the invention also resides in the use of EMM-8 as a sorbent and as a catalyst in organic conversion reactions and to synthesis of CHA framework materials with the organic directing agent, 4- dimethylaminopyridine.
- the EMM-8 of the invention is a porous crystalline material having a framework of tetrahedral atoms connected by bridging atoms, the tetrahedral atom framework being defined by the interconnections between the tetrahedrally coordinated atoms in its framework.
- EMM-8 can be defined by the interconnections between the tetrahedrally coordinated atoms in its framework, hi particular, EMM-8 has a framework of tetrahedral (T) atoms connected by bridging atoms, wherein the tetrahedral atom framework is defined by connecting the nearest tetrahedral (T) atoms in the manner shown in Table 1 below.
- Table 1 Table 1
- EMM-8 In addition to describing the structure of EMM-8 by the interconnections of the tetrahedral atoms as in Table 1 above, it may be defined by its unit cell, which is the smallest repeating unit containing all the structural elements of the material.
- the pore structure of EMM-8 is illustrated in Figure 9 (which shows only the tetrahedral atoms) down the direction of the 12-member ring channel.
- Table 2 lists the typical positions of each tetrahedral atom in the unit cell in units of Angstroms. Each tetrahedral atom is bonded to bridging atoms, which are also bonded to adjacent tetrahedral atoms.
- Tetrahedral atoms are those capable of having tetrahedral coordination, including one or more of, but not limiting, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, gallium, germanium, arsenic, indium, tin, and antimony.
- Bridging atoms are those capable of connecting two tetrahedral atoms, examples of which include, but are not limited to oxygen, nitrogen, fluorine, sulfur, selenium, and carbon atoms.
- bridging oxygen is also connected to a hydrogen atom to form a hydroxyl group (-OH-).
- carbon it is also possible that the carbon is also connected to two hydrogen atoms to form a methylene group (-CH 2 -).
- bridging methylene groups have been seen in the zirconium diphosphonate, MIL-57. See: C. Serre, G. Ferey, J. Mater. Chem. 12, p. 2367 (2002). Bridging sulfur and selenium atoms have been seen in the UCR-20-23 family of microporous materials. See: N. Zheng, X. Bu, B. Wang, P.
- tetrahedral atoms may move about due to other crystal forces (presence of inorganic or organic species, for example), or by the choice of tetrahedral and bridging atoms, a range of ⁇ 0.1 nm ( ⁇ 1 Angstrom) is implied for the x and y coordinate positions and a range of ⁇ 0.05 nm ( ⁇ 0.5 Angstrom) for the z coordinate positions in Table 2.
- EMM-8 The complete structure of EMM-8 is built by connecting multiple unit cells as defined above in a fully-connected three-dimensional framework.
- the tetrahedral atoms in one unit cell are connected to certain tetrahedral atoms in all of its adjacent unit cells. While Table 1 lists the connections of all the tetrahedral atoms for a given unit cell of EMM-8, the connections may not be to the particular atom in the same unit cell but to an adjacent unit cell. All of the connections listed in Table 1 are such that they are to the closest tetrahedral (T) atoms, regardless of whether they are in the same unit cell or in adjacent unit cells.
- T tetrahedral
- the N 2 atoms in the second shell are connected to N 3 T-atoms in the third shell, and so on.
- Each T-atom is only counted once, such that, for example, if a T-atom is in a 4-membered ring, at the fourth shell the N 0 atom is not counted a second time, and so on.
- a coordination sequence can be determined for each unique T-atom of a 4-connected net of T- atoms. The following line lists the maximum number of T-atoms for each shell.
- N 0 1 N 1 ⁇ 4 N 2 ⁇ 12 N 3 ⁇ 36 N k ⁇ 4-3 k"!
- the Structure Commission of the International Zeolite Association recognize that the combination of coordination sequence and vertex symbol together appear unique for a particular framework topology such that they can be used to unambiguously distinguish microporous frameworks of different types (see “Atlas of Zeolite Framework Types", Ch. Baerlocher, W.M. Meier, D.H. Olson, Elsevier, Amsterdam (2001).
- One way to determine the coordination sequence and vertex symbol for a given structure is from the atomic coordinates of the framework atoms using the computer program zeoTsites (see G. Sastre, J.D. Gale, Microporous and mesoporous Materials 43, p. 27 (2001).
- T-atom connectivity as listed in Table 3 is for T-atoms only. Bridging atoms, such as oxygen usually connect the T-atoms. Although most of the T-atoms are connected to other T-atoms through bridging atoms, it is recognized that in a particular crystal of a material having a framework structure, it is possible that a number of T-atoms may not be connected to one another. Reasons for non-connectivity include, but are not limited by, T-atoms located at the edges of the crystals and by defect sites caused by, for example, vacancies in the crystal.
- the framework listed in Table 3 is not limited in any way by its composition, unit cell dimensions or space group symmetry.
- the idealized structure contains only 4-coordinate T-atoms
- some of the framework atoms may be 5- or 6-coordinate. This may occur, for example, under conditions of hydration when the composition of the material contains mainly phosphorus and aluminum T- atoms.
- T-atoms may be also coordinated to one or two oxygen atoms of water molecules (-OH 2 ), or of hydroxyl groups (-OH).
- the molecular sieve A1PO 4 -34 is known to reversibly change the coordination of some aluminum T-atoms from 4-coordinate to 5- and 6-coordinate upon hydration as described by A. Tuel et al. in J. Phys. Chem.
- T-atoms can be coordinated to fluoride atoms (-F) when materials are prepared in the presence of fluorine to make materials with 5-coordinate T-atoms as described by H. Koller in J. Am. Chem Soc. 121, p. 3368 (1999).
- EMM-8 In its as-synthesized form, EMM-8 typically has an X-ray diffraction pattern including the lines listed in Table 4 below:
- EMM-8 In its as-calcined anhydrous form, EMM-8 is porous and has an X- ray diffraction pattern including the lines listed in Table 5 below: Table 5
- the interplanar spacings, d's, were calculated in nanometres (nm), and the relative intensities of the lines, I/ Io, where Io is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine (or second derivative algorithm).
- the intensities are uncorrected for Lorentz and polarization effects.
- diffraction data listed for this sample as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallite sizes or very high experimental resolution or crystallographic change, may appear as resolved or partially resolved lines.
- crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in topology of the 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, and thermal and/or hydrothermal history, hi practice, therefore, at least some of the lines in the X-ray patterns of the crystalline material of the invention may exhibit significant variations in relative intensity from the values indicated in Tables 4 and 5.
- the XRD patterns of Tables 4 and 5 can be indexed to a monoclinic unit cell, in the space group C2/c (#15), having the following unit cell dimensions in nm:
- EMM-8 comprises at least [AlO 4 ] and
- [PO 4 ] corner sharing tetrahedral units and, in its as-synthesized, anhydrous form, is represented by the empirical formula: mR:F a :(M x Al y P z )O 2
- R represents at least one directing agent, preferably an organic directing agent and most preferably 4-dimethylaminopyridine
- m is the number of moles of R per mole of (M x AIyP 2 )O 2 and m has a value from 0 to 1, such as from 0.1 to about 0.5, preferably from 0.1 to about 0.3
- F represents fluoride ion which may be present in the synthesis mixture
- a is the number of moles of F per mole Of (M x AIyP 2 )O 2 and a/y is less than 0.25 and preferably is 0
- x, y, and z represent the mole fraction of M, Al and P as tetrahedral oxides
- M is a
- M is selected from B, Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Si, Sn, Ti, Zn and Zr. Most preferably, M is silicon.
- x is from 0 to about 0.25
- y is from about 0.3 to about 0.7
- z is from about 0.25 to about 0.7.
- x is from about 0 to about 0.15
- y is from about 0.4 to about 0.6
- z is from about 0.3 to about 0.6.
- x is from about 0 to about 0.12
- y is from about 0.45 to about 0.55 and z is from about 0.35 to about 0.55.
- x is zero.
- the large pore (metallo) aluminophosphate of the present invention typically has an alpha value of at least 0.1, and more preferably at least 0.5, indicating that the material is useful as an acid catalyst in organic, and in particular hydrocarbon, conversion reactions.
- the alpha value test is a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of Catalysis. Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each incorporated herein by reference as to that description.
- the experimental conditions of the test used herein include a constant temperature of 538 0 C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395.
- the crystalline (metallo)aluminophosphate material of the present invention can be produced from a synthesis mixture containing water, a source of phosphorus, a source of aluminum, optionally a source of metal M, such as silicon, optionally a source of fluoride ions and 4-dimethylaminopyridine (R).
- the synthesis mixture typically has a composition, expressed in terms of mole ratios of oxides, as follows:
- a suitable source of phosphorus in the above mixture is phosphoric acid.
- suitable aluminum sources include hydrated aluminum oxides such as boehmite and pseudoboehmite.
- suitable sources of silicon include silicates, e.g., fumed silica, such as Aerosil and Cabosil, tetraalkyl orthosilicates, and aqueous colloidal suspensions of silica, for example that sold by E.I. du Pont de Nemours under the tradename Ludox.
- the source of fluoride ions may be any compound capable of releasing fluoride ions in the synthesis mixture.
- Non-limiting examples of such sources of fluoride ions include salts containing one or several fluoride ions, such as metal fluorides, preferably, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, ammonium fluoride, tetraalkylammonium fluorides, such as tetramethylammonium fluoride, tetraethylammonium fluoride, hydrogen fluoride, and mixtures thereof.
- the preferred source of fluoride is hydrogen fluoride but, more preferably, the synthesis is conducted in the absence of added fluoride, that is with the F: Al 2 O 3 molar ratio being zero.
- Crystallization is carried out under either stirred or static conditions, preferably stirred conditions, at a temperature between about 100 0 C and about 250°C, typically between about 15O 0 C and about 200 0 C, preferably between about 155°C and about 18O 0 C.
- crystallization is conducted for about 2 to about 150 hours, preferably about 20 to about 100 hours, whereafter the resultant crystalline material is separated from the mother liquor and recovered, such as by centrifugation or filtration.
- the separated product can also be washed, recovered by centrifugation or filtration and dried.
- the crystalline product is typically in the form of platelets having a d 5 o (50 % by volume of crystals is smaller than the ds 0 value) particle size less than 1 ⁇ m.
- Synthesis of the large pore (metallo)aluminophosphate material of the invention maybe facilitated by the presence of at least 0.1 ppm, such as at least 10 ppm, for example at least 100 ppm, conveniently at least 500 ppm of seed crystals from a previous synthesis based on total weight of the reaction mixture.
- the resultant product is a CHA framework-type molecular sieve rather than the large pore (metallo)aluminophosphate material of the invention.
- the recovered crystalline product contains within its pores at least a portion of the organic directing agent used in the synthesis.
- activation is performed in such a manner that the organic directing agent is removed from the molecular sieve, leaving active catalytic sites within the microporous channels of the molecular sieve open for contact with a feedstock.
- the activation process is typically accomplished by calcining, or essentially heating the molecular sieve comprising the template at a temperature of from about 200°C to about 800°C, typically in the presence of an oxygen-containing gas. This type of process can be used for partial or complete removal of the organic directing agent from the intracrystalline pore system.
- the crystalline material of the invention Once the crystalline material of the invention has been synthesized, it can be formulated into a catalyst composition by combination with other materials, such as binders and/or matrix materials, that provide additional hardness or catalytic activity to the finished catalyst.
- Materials which can be blended with the crystalline material of the invention can be various inert or catalytically active materials. These materials include compositions such as kaolin and other clays, various forms of rare earth metals, other non-zeolite catalyst components, zeolite catalyst components, alumina or alumina sol, titania, zirconia, quartz, silica or silica sol, and mixtures thereof. These components are also effective in reducing overall catalyst cost, acting as a thermal sink to assist in heat shielding the catalyst during regeneration, densifying the catalyst and increasing catalyst strength. When blended with such components, the amount of crystalline material contained in the final catalyst product ranges from 10 to 90 weight percent of the total catalyst, preferably 20 to 80 weight percent of the total catalyst.
- the large pore crystalline material described herein can be used to dry gases and liquids; for selective molecular separation based on size and polar properties; as an ion-exchanger; as a catalyst in organic conversion reactions, such as cracking, hydrocracking, disproportionation, alkylation, isomerization, oxidation and synthesis of monoalkylamines and dialkylamines; as a chemical carrier; in gas chromatography; and in the petroleum industry to remove normal paraffins from distillates.
- Solid product yield of Sample A was 13.2%, based on the total weight of the starting gel. Elemental analysis gave the following results: Al, 16.0%; P, 17.9%. These results correspond to AIi O P ⁇ 975 in composition and 71.2% for calculated total oxides. The residual weight was separately determined with TGA (Thermal Gravimetric Analysis) to be 72.6%. Sample A gave the scanning electron micrograph shown in Figure 4 and had an XRD pattern with the peaks listed Table 6 below.
- Example 1 The procedure of Example 1 was repeated to produce two additional samples, Samples C and D, except that CabosilTM silica was added to each synthesis mixture after the CatapalTM alumina and before 4- dimethylaminopyridine.
- the ingredient molar ratios were as follows: 2.0DMAPy: 1.0Al 2 O 3 :(0.1 & 0.3)SiO 2 :1.0P 2 O 5 :40H 2 O
- the product yield was 18.9 and 19.6 wt%, for 0.1 SiO 2 and 0.3 SiO 2 , respectively.
- the powder pattern of Sample C was indexed successfully in the same monoclinic unit cell as Sample A, in the Space Group C2/c(#15).
- the unit cell volume is 2.0983 nm 3 .
- Samples C and D having Si/Al ratio of 0.058 and 0.154, respectively, were calcined at 600 0 C for 2 hours before n-hexane cracking test was conducted.
- the standard ⁇ -test conditions (538 0 C) were used.
- the ⁇ -numbers for these two samples were determined to be 9.1 and 23.3, respectively. These values show that the new material has potential for hydrocarbon conversion applications.
- Example 8 [0077] The synthesis procedure was identical to Example 1, except that
Abstract
Description
Claims
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JP2007533898A JP4990145B2 (en) | 2004-10-01 | 2005-09-12 | Aluminophosphate molecular sieve, its synthesis and use |
EP05791629.8A EP1791786B1 (en) | 2004-10-01 | 2005-09-12 | Aluminophosphate molecular sieve, its synthesis and use |
CA2581583A CA2581583C (en) | 2004-10-01 | 2005-09-12 | Aluminophosphate molecular sieve, its synthesis and use |
AU2005291587A AU2005291587B2 (en) | 2004-10-01 | 2005-09-12 | Aluminophosphate molecular sieve, its synthesis and use |
CN200580033411XA CN101031511B (en) | 2004-10-01 | 2005-09-12 | Aluminophosphate molecular sieve, its synthesis and use |
NO20072261A NO20072261L (en) | 2004-10-01 | 2007-05-02 | Aluminum phosphate molecules term, its synthesis and use |
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EP (1) | EP1791786B1 (en) |
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CN (1) | CN101031511B (en) |
AU (1) | AU2005291587B2 (en) |
CA (1) | CA2581583C (en) |
NO (1) | NO20072261L (en) |
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WO2007005250A2 (en) | 2005-06-30 | 2007-01-11 | Uop Llc | Enhancement of molecular sieve performance |
FR2923477A1 (en) * | 2007-11-12 | 2009-05-15 | Inst Francais Du Petrole | IM-18 CRYSTALLIZED SOLID AND PROCESS FOR PREPARING THE SAME |
JP2009544552A (en) * | 2006-07-21 | 2009-12-17 | バーラト ペトローリアム コーポレーション リミテッド | Microporous crystalline silicoalumino / (metallo) aluminophosphate molecular sieve and synthesis method thereof |
US9492818B2 (en) | 2009-06-12 | 2016-11-15 | Albemarle Europe Sprl | SAPO molecular sieve catalysts and their preparation and uses |
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- 2005-09-12 EP EP05791629.8A patent/EP1791786B1/en not_active Not-in-force
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JP2009544552A (en) * | 2006-07-21 | 2009-12-17 | バーラト ペトローリアム コーポレーション リミテッド | Microporous crystalline silicoalumino / (metallo) aluminophosphate molecular sieve and synthesis method thereof |
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US9492818B2 (en) | 2009-06-12 | 2016-11-15 | Albemarle Europe Sprl | SAPO molecular sieve catalysts and their preparation and uses |
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AU2005291587B2 (en) | 2011-03-10 |
EP1791786A2 (en) | 2007-06-06 |
CA2581583C (en) | 2013-03-05 |
CN101031511A (en) | 2007-09-05 |
US20060074267A1 (en) | 2006-04-06 |
NO20072261L (en) | 2007-06-29 |
JP2008514538A (en) | 2008-05-08 |
AU2005291587A1 (en) | 2006-04-13 |
US7498011B2 (en) | 2009-03-03 |
JP4990145B2 (en) | 2012-08-01 |
EP1791786B1 (en) | 2017-10-18 |
CN101031511B (en) | 2010-06-30 |
ZA200702117B (en) | 2008-07-30 |
CA2581583A1 (en) | 2006-04-13 |
WO2006037436A3 (en) | 2006-09-28 |
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