Porous materials

• US 5,304,363 A
• Filed: 07/02/1992
• Issued: 04/19/1994
• Est. Priority Date: 01/25/1990
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Roth, Wieslaw J., Vartuli, James C., Beck, Jeffrey S., Kresge, Charles T., McCullen, Sharon B.
• Primary Examiner(s): MCFARLANE, ANTHONY R
• Application Number:
  US07/907,941
• Time in Patent Office: 656 Days
• Field of Search: 423/718, 502/60, 502/64, 502/77, 502/241, 502/242
• US Class Current: 423/328.1
• CPC Class Codes: B01D 53/8628 Processes characterised by a specific catalyst
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/34 Reaction with organic or organometallic compounds with organo-silicium compounds B01J2229/32
• CPC Class Codes: B01J 2229/36 Steaming
• CPC Class Codes: B01J 2229/40 Special temperature treatment, i.e. other than just for template removal
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/0308 Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
• CPC Class Codes: B01J 29/041 Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: B01J 29/82 Phosphates B01J29/005 takes precedence
• CPC Class Codes: B01J 29/83 Aluminophosphates [APO compounds]
• CPC Class Codes: B01J 29/85 Silicoaluminophosphates [SAPO compounds]
• CPC Class Codes: C01B 37/00 Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C01B 37/02 : Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 37/08 : Silicoaluminophosphates [SAPO compounds] , e.g. CoSAPO
• CPC Class Codes: C01B 39/00 : Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14
• CPC Class Codes: C10G 11/05 : Crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/16 : Crystalline alumino-silicate carriers

Abstract

There is provided a porous material. A process for preparing this material involves adding an amphiphilic compound to the reaction mixture for preparing a crystalline oxide. The amphiphilic compound may be a quaternary ammonium cationic surfactant. These surfactants may be in the form of lamellar liquid crystals, and may function as templates for the formation of the present mesoporous oxide materials.

Claims

1. A composition of matter comprising an inorganic, porous material exhibiting, after calcination, an X-ray diffraction pattern according to Table 1 with no peaks at positions less than about 10 Angstroms d-spacing with relative intensity greater than 20% of the strongest peak.

2. A composition of matter according to claim 1 which is an oxide material.

3. A composition of matter according to claim 1 having a composition expressed as follows:

space="preserve" listing-type="equation">M.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h)

wherein M is one or more ions;

n is the charge of the composition excluding M expressed as oxides;

q is the weighted molar average valence of M;

n/q is the number of moles or mole fraction of M;

W is one or more divalent elements;

X is one or more trivalent elements;

Y is one or more tetravalent elements;

Z is one or more pentavalent elements;

a, b, c, and d are mole fractions of W, X, Y, and Z, respectively;

h is a number of from 1 to 2.5; and

(a+b+c+d)=1.

4. A composition of matter according to claim 3, wherein the sum (a+b+c) is greater than d, and h=2.

5. A composition of matter according to claim 3, wherein W is a divalent first row transition metal or magnesium;

X is an element selected from the group consisting of aluminum, boron, gallium and iron;

Y is an element selected from the group consisting of silicon, titanium and germanium; and

Z is phosphorus.

6. A composition of matter according to claim 1 having a benzene adsorption capacity of greater than 15 grams of benzene per 100 grams of said composition at 6.7 kPa and 25°

C.

7. A composition of matter according to claim 1 which is composed of silica.

8. A composition of matter according to claim 2, having an X-ray diffraction pattern with 3 or more peaks and having the values shown in Table 2.

9. A composition of matter according to claim 2, having an X-ray diffraction pattern with 4 or more peaks and having the values shown in Table 3.

10. A composition of matter according to claim 1, wherein said X-ray diffraction pattern has no peaks at positions less than about 10 Angstroms d-spacing with relative intensity greater than 10% of the strongest peak.

11. A composition of matter according to claim 3, wherein said composition of matter is prepared by a process comprising the steps of:

(a) preparing a reaction mixture having a composition in terms of mole ratios, within the following ranges;

space="preserve" listing-type="tabular">______________________________________ 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 + WO + Z.sub.2 O.sub.5) = 0.1 to 100 R'"'"'.sub.2 O/(X.sub.2 O.sub.3 + YO.sub.2 + WO + Z.sub.2 O.sub.5) = 0.3 to 2.0 Solvent/(X.sub.2 O.sub.3 + YO.sub.2 + WO + Z.sub.2 O.sub.5) = 1 to 1500 ______________________________________

wherein R comprises an organic agent having the formula R₁ R₂ R₃ R₄ Q⁺, wherein Q is nitrogen or phosphorus, and at least one of R₁, R₂, R₃, R₄ is aryl or alkyl group having 6 to 36 carbon atoms and each of the remainder of R₁, R₂, R₃, and R₄ is selected from hydrogen and an alkyl group having 1 to 5 carbon atoms and wherein the solvent is a C₁ to C₆ alcohol or diol, or water;

(b) maintaining said mixture under sufficient conditions of pH, temperature and time for formation of an inorganic oxide containing residual organic compound;

(c) recovering said inorganic oxide containing residual organic compound from step (b);

(d) treating said inorganic oxide of step (c) with a compound of the formula

space="preserve" listing-type="equation">M'"'"'X'"'"'.sub.2 Y'"'"'.sub.m

where M'"'"' is boron, aluminum, silicon or titanium;

X'"'"' represents alkyl halides having from 1-6 carbon atoms and/or alkoxides having 1-6 carbon atoms;

Y'"'"' represents X'"'"' and/or alkyls with 1-12 carbon atoms; and

m=1-2; and

(e) calcining said material from step (d) under conditions sufficient to remove residual organic compounds.

12. A composition of matter according to claim 11, wherein said reaction mixture of step (a) comprises tetraethylammonium ions.

13. A composition of matter according to claim 11, wherein the source of oxide in step (a) is titanium ethoxide.

14. A composition of matter according to claim 1, exhibiting a benzene adsorption capacity of greater than about 15 grams benzene per 100 grams anhydrous crystal at 50 torr and 25°

F.

15. A composition of matter according to claim 11, wherein M'"'"'X'"'"'₂ Y'"'"'_m is tetraethylorthosilicate.

16. A composition of matter according to claim 11, wherein M'"'"'X'"'"'₂ Y'"'"'_m is an aluminum tri-butoxide.