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US5156828A Expired / Lapsed US ⏱️ 0.0 years remaining

Method for manufacturing synthetic mesoporous crystalline material

Assignee: Mobil Oil AS
•
Filing: 1991-07-18
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Granted: 1992-10-20
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Expires: 2011-07-18
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Abstract

Abstract This invention relates to a method for synthesizing an ultra-large pore crystalline material and the use of such crystalline material as a sorbent and in catalytic conversion of organic and inorganic compounds. The synthesis method includes hydrothermally treating the as-synthesized crystalline material in the presence or absence of a binder. In a preferred embodiment, the crystalline material contains organic directing agent and is composited in an alumina binder. The crystalline material exhibits unusually large sorption capacity demonstrated by its benzene adsorption capacity of greater than about 15 grams benzene/100 grams at 50 torr and 25 DEG C., a hexagonal electron diffraction pattern that can be indexed with a d100 value greater than about 18 Angstrom Units and a hexagonal arrangement of uniformly sized pores with a maximum perpendicular cross section of at least about 13 Angstrom units.

Inventors

  • 👤 Thomas F. Degnan
  • 👤 Ivy D. Johnson
  • 👤 Kathleen M. Keville

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-28 08:26
CPC Classifications
C; C01; C01B; C01B37/00; C01B37/02; B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/70; C01B39/00; B01J2229/00; B01J2229/10; B01J2229/26; B01J2229/30; B01J2229/36; B01J2229/42

Claims Analysis

Total Claims: 46
Claim 1
Independent Claim 255 words
A method for synthesizing a composition of matter comprising an inorganic, non-layered, porous crystalline phase material having, after calcination, an arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units, exhibiting an X-ray diffraction pattern with at least one peak at a position greater than about 18 Angstrom Units d-spacing and exhibiting a benzene adsorption capacity of greater than about 15 grams benzene per 100 grams at 50 torr and 25° C., which comprises (i) preparing a reaction mixture capable of forming said composition, said mixture comprising one or a combination of oxides selected from the group consisting of divalent element, trivalent element, tetravalent element and pentavalent element, organic directing agent and solvent or solvent mixture, said organic directing agent comprising an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, (ii) maintaining said mixture under sufficient conditions of pH, temperature and time for formation of said composition of matter, (iii) recovering said composition of matter containing said organic directing agent, and (iv) contacting said recovered composition of matter of step (iii) with steam at elevated temperature.
Claim 2
Independent Claim 255 words
A method for synthesizing a composition of matter comprising an inorganic, non-layered, porous crystalline phase material having, after calcination, an arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units, exhibiting an X-ray diffraction pattern with at least one peak at a position greater than about 18 Angstrom Units d-spacing and exhibiting a benzene adsorption capacity of greater than about 15 grams benzene per 100 grams at 50 torr and 25° C., which comprises (i) preparing a reaction mixture capable of forming said composition, said mixture comprising one or a combination of oxides selected from the group consisting of divalent element, trivalent element, tetravalent element and pentavalent element, organic directing agent and solvent or solvent mixture, said organic directing agent comprising an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, (ii) maintaining said mixture under sufficient conditions of pH, temperature and time for formation of said composition of matter, (iii) recovering said composition of matter containing said organic directing agent, and (iv) contacting said recovered composition of matter of step (iii) with steam at elevated temperature.
Claim 3
Dependent Claim 17 words
The method of claim 1 wherein R comprises cetyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium or dimethyldidodecylammonium.
Claim 4
Dependent Claim 13 words
The method of claim 1 wherein said organic directing agent comprises cetyltrimethylammonium hydroxide.
Claim 5
Dependent Claim 29 words
The method of claim 1 further comprising compositing said recovered composition of matter with a binder prior to contacting said recovered composition of matter with steam at elevated temperature.
Claim 6
Dependent Claim 10 words
The method of claim 4 wherein said binder is inert.
Claim 7
Dependent Claim 10 words
The method of claim 4 wherein said binder comprises alumina.
Claim 8
Dependent Claim 27 words
The method of claim 1 further comprising contacting said recovered composition of matter with an ammonium-containing compound prior to contacting said recovered composition of matter with steam.
Claim 9
Dependent Claim 15 words
The method of claim 7 wherein said ammonium-containing compound is NH 4 NO 3 .
Claim 10
Dependent Claim 18 words
The method of claim 1 wherein said steam contacting step (iv) is conducted at temperature above 220° F.
Claim 11
Dependent Claim 18 words
The method of claim 9 wherein said steam contacting step (iv) is conducted at temperature above 300° F.
Claim 12
Dependent Claim 24 words
The method of claim 10 wherein said steam contacting step (iv) is conducted at temperatures of from about 300° F. to about 900° F.
Claim 13
Dependent Claim 22 words
The method of claim 1 wherein said steam contacting step (iv) is conducted at pressures from about 0.1 to about 10 Bar.
Claim 14
Dependent Claim 27 words
The method of claim 1 further comprising contacting said recovered composition of matter with steam at elevated temperature for from about 5 minutes to about 24 hours.
Claim 15
Dependent Claim 168 words
The method of claim 1 wherein said reaction mixture has a composition, in terms of mole ratios, within the following ranges: ______________________________________ X.sub.2 O.sub.3 /YO.sub.2 0 to 0.5 Al.sub.2 O.sub.3 /SiO.sub.2 0 to 0.01 X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5) 0.1 to 100 X.sub.2 O.sub.3 /(YO.sub.2 + W'O + Z.sub.2 O.sub.5) 0.1 to 100 Solvent/ 1 to 1500 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) OH.sup.- /YO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O)/ 0.01 to 20 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) M.sub.2/e O/ 0 to 10 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2.0 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, W' is said divalent element, X is said trivalent element, Y is said tetravalent element, Z is said pentavalent element, R is said organic directing agent, and e and f are the weighted average valences of M and R, respectively.
Claim 16
Dependent Claim 17 words
The method of claim 14 wherein R comprises cetyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium or dimethyldidodecylammonium.
Claim 17
Dependent Claim 13 words
The method of claim 14 wherein said organic directing agent comprises cetyltrimethylammonium hydroxide.
Claim 18
Dependent Claim 29 words
The method of claim 14 further comprising compositing said recovered composition of matter with a binder prior to contacting said recovered composition of matter with steam at elevated temperature.
Claim 19
Dependent Claim 297 words
The method of claim 1 wherein said reaction mixture has a composition, in terms of mole ratios, within the following ranges: ______________________________________ X.sub.2 O.sub.3 /YO.sub.2 0 to 0.5 X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5) 01 to 100 X.sub.2 O.sub.3 /(YO.sub.2 + W'O + Z.sub.2 O.sub.5) 0.1 to 100 Solvent/ 1 to 1500 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) OH.sup.- /YO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O)/ 0.01 to 20 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) M.sub.2/e O/ 0 to 10 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2.0 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, W' is said divalent element, X is said trivalent element, Y is said tetravalent element, Z is said pentavalent element, R comprises a mixture of component (a) an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, and component (b) an additional ion of the formula R 1 R 2 R 3 R 4 Q+ wherein R 1 , R 2 , R 3 and R 4 are selected from the group consisting of hydrogen, alkyl of 1 to 5 carbon atoms and combinations thereof, and wherein e and f are the weighted average valences of M and R, respectively.
Claim 20
Dependent Claim 17 words
The method of claim 18 wherein R comprises cetyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium or dimethyldidodecylammonium,
Claim 21
Dependent Claim 13 words
The method of claim 18 wherein said organic directing agent comprises cetyltrimethylammonium hydroxide.
Claim 22
Dependent Claim 29 words
The method of claim 18 further comprising compositing said recovered composition of matter with a binder prior to contacting said recovered composition of matter with steam at elevated temperature.
Claim 23
Dependent Claim 10 words
The method of claim 21 wherein said binder is inert.
Claim 24
Dependent Claim 10 words
The method of claim 21 wherein said binder comprises alumina.
Claim 25
Dependent Claim 97 words
The method of claim 1 wherein said reaction mixture has a composition, in terms of mole ratios, within the following ranges: ______________________________________ Al.sub.2 O.sub.3 /SiO.sub.2 0 to 0.1 Solvent/SiO.sub.2 1 to 1500 OH.sup.- /SiO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O)/ 0.01 to 20 (SiO.sub.2 + Al.sub.2 O.sub.3) M.sub.2/e O/ 0 to 5 (SiO.sub.2 + Al.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2 (SiO.sub.2 + Al.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, R is said organic directing agent, e and f are the weighted average valences of M and R, respectively.
Claim 26
Dependent Claim 17 words
The method of claim 24 wherein R comprises cetyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium or dimethyldidodecylammonium.
Claim 27
Dependent Claim 13 words
The method of claim 24 wherein said organic directing agent comprises cetyltrimethylammonium hydroxide.
Claim 28
Dependent Claim 17 words
The method of claim 25 wherein said source of an oxide of silicon comprises an organic silicate.
Claim 29
Dependent Claim 14 words
The method of claim 27 wherein said organic silicate comprises a quaternary ammonium silicate.
Claim 30
Dependent Claim 11 words
The method of claim 27 wherein said organic silicate comprises tetraethylorthosilicate.
Claim 31
Dependent Claim 29 words
The method of claim 24 further comprising compositing said recovered composition of matter with a binder prior to contacting said recovered composition of matter with steam at elevated temperature.
Claim 32
Dependent Claim 10 words
The method of claim 30 wherein said binder is inert.
Claim 33
Dependent Claim 10 words
The method of claim 30 wherein said binder comprises alumina.
Claim 34
Dependent Claim 49 words
The method of claim 1 wherein said crystalline phase has, after calcination, a hexagonal arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units and exhibits a hexagonal electron diffraction pattern than can be indexed with a d 100 value greater than about 18 Angstrom Units.
Claim 35
Dependent Claim 17 words
The method of claim 33 wherein R comprises cetyltrimethylammonium, octadecyltrimethylammonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium or dimethyldidodecylammonium,
Claim 36
Dependent Claim 13 words
The method of claim 34 wherein said organic directing agent comprises cetyltrimethylammonium hydroxide.
Claim 37
Dependent Claim 29 words
The method of claim 33 further comprising compositing said recovered composition of matter with a binder prior to contacting said recovered composition of matter with team at elevated temperature.
Claim 38
Dependent Claim 10 words
The method of claim 36 wherein said binder is inert.
Claim 39
Dependent Claim 10 words
The method of claim 36 wherein said binder comprises alumina.
Claim 40
Dependent Claim 168 words
The method of claim 33 wherein said reaction mixture has a composition, in terms of mole ratios, within the following ranges: ______________________________________ X.sub.2 O.sub.3 /YO.sub.2 0 to 0.5 Al.sub.2 O.sub.3 /SiO.sub.2 0 to 0.01 X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5) 0.1 to 100 X.sub.2 O.sub.3 /(YO.sub.2 + W'O + Z.sub.2 O.sub.5) 0.1 to 100 Solvent/ (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 1 to 1500 OH.sup.- /YO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O)/ 0.01 to 20 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) M.sub.2/e O/ 0 to 10 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2.0 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, W' is said divalent element, X is said trivalent element, Y is said tetravalent element, Z is said pentavalent element, R is said organic directing agent, and e and f are the weighted average valences of M and R, respectively.
Claim 41
Dependent Claim 297 words
The method of claim 33 wherein said reaction mixture has a composition, in terms of mole ratios, within the following ranges: ______________________________________ X.sub.2 O.sub.3 /YO.sub.2 0 to 0.5 X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5 0.1 to 100 X.sub.2 O.sub.3 /(YO.sub.2 + W'O + Z.sub.2 O.sub.5) 0.1 to 100 Solvent/ 1 to 1500 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) OH.sup.- /YO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O)/ 0.01 to 20 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) M.sub.2/e O/ 0 to 10 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2.0 (YO.sub.2 + W'O + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, W' is said divalent element, X is said trivalent element, Y is said tetravalent element, Z is said pentavalent element, R comprises a mixture of component (a) an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, and component (b) an additional ion of the formula R 1 R 2 R 3 R 4 Q+ wherein R 1 , R 2 , R 3 and R 4 are selected from the group consisting of hydrogen, alkyl of 1 to 5 carbon atoms and combinations thereof, and wherein e and f are the weighted average valences of M and R, respectively.
Claim 42
Dependent Claim 97 words
The method of claim 33 wherein said reaction mixture has a composition, in terms of mole ratios within the following ranges: ______________________________________ Al.sub.2 O.sub.3 /SiO.sub.2 0 to 0.1 Solvent/SiO.sub.2 1 to 1500 OH.sup.- /SiO.sub.2 0 to 10 (M.sub.2/e O + R.sub.2/f O) 0.01 to 20 (SiO.sub.2 + Al.sub.2 O.sub.3) M.sub.2/e O/ 0 to 5 (SiO.sub.2 + Al.sub.2 O.sub.3) R.sub.2/f O/ 0.01 to 2 (SiO.sub.2 + Al.sub.2 O.sub.3) ______________________________________ wherein M is said alkali or alkaline earth metal cation, R is said organic directing agent, e and f are the weighted average valences of M and R, respectively.
Claim 43
Dependent Claim 269 words
In a method for synthesizing a composition of matter comprising an inorganic, non-layered, porous crystalline phase material having, after calcination, an arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units, exhibiting an X-ray diffraction pattern with at least two peaks at positions greater than about 10 Angstrom Units d-spacing, at least one of which is at a position greater than about 18 Angstrom Units d-spacing, and no peaks at positions less than about 10 Angstrom Units d-spacing with relative intensity greater than about 20% of the strongest peak, which comprises (i) preparing a reaction mixture capable of forming said composition, said mixture comprising one or a combination of oxides selected from the group consisting of divalent element, trivalent element, tetravalent element and pentavalent element, organic directing agent and solvent or solvent mixture, said organic directing agent comprising an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, (ii) maintaining said mixture under sufficient conditions of pH, temperature and time for formation of said composition of matter and (iii) recovering said composition of matter, the improvement comprising contacting said recovered composition of matter of step (iii) with steam at elevated temperature.
Claim 44
Dependent Claim 269 words
In a method for synthesizing a composition of matter comprising an inorganic, non-layered, porous crystalline phase material having, after calcination, an arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units, exhibiting an X-ray diffraction pattern with at least two peaks at positions greater than about 10 Angstrom Units d-spacing, at least one of which is at a position greater than about 18 Angstrom Units d-spacing, and no peaks at positions less than about 10 Angstrom Units d-spacing with relative intensity greater than about 20% of the strongest peak, which comprises (i) preparing a reaction mixture capable of forming said composition, said mixture comprising one or a combination of oxides selected from the group consisting of divalent element, trivalent element, tetravalent element and pentavalent element, organic directing agent and solvent or solvent mixture, said organic directing agent comprising an ion of the formula R 1 R 2 R 3 R 4 Q+, wherein Q is nitrogen or phosphorus and wherein at least one of R 1 , R 2 , R 3 and R 4 is aryl or alkyl of from 6 to about 36 carbon atoms or combinations thereof, the remainder of R 1 , R 2 , R 3 and R 4 being selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and combinations thereof, (ii) maintaining said mixture under sufficient conditions of pH, temperature and time for formation of said composition of matter and (iii) recovering said composition of matter, the improvement comprising contacting said recovered composition of matter of step (iii) with steam at elevated temperature.
Claim 45
Dependent Claim 49 words
The method of claim 42 wherein said crystalline phase has, after calcination, a hexagonal arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units and exhibits a hexagonal electron diffraction pattern than can be indexed with a d 100 value greater than about 18 Angstrom Units.
Claim 46
Dependent Claim 64 words
The method of claim 42 wherein said crystalline phase has an X-ray diffraction pattern with at least one peak at a position greater than about 18 Angstrom Units d-spacing (4.909 degrees two-theta for Cu K-alpha radiation) with a relative intensity of 100 and exhibits an equilibrium benzene adsorption capacity of greater than about 15 grams benzene/100 grams crystal at 50 torr and 25° C.

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