Inorganic oxides with mesoporosity or combined meso-and microporosity and process for the preparation thereof

• US 6,814,950 B1
• Filed: 07/17/2002
• Issued: 11/09/2004
• Est. Priority Date: 09/07/1999
• Status: Expired due to Fees

• Current Assignee: ABB Lummus Global Inc., Technische Universiteit Delft
• Original Assignee: ABB Lummus Global Inc., Technische Universiteit Delft
• Inventors: Shan, Zhiping, Maschmeyer, Thomas, Jansen, Jacobus Cornelis
• Primary Examiner(s): Silverman, Stanley S.
• Assistant Examiner(s): MEDINA SANABRIA, MARIBEL
• Application Number:
  US10/070,711
• Time in Patent Office: 846 Days
• Field of Search: 423/326, 423/327.1, 423/327.2, 423/328.1, 423/328.2, 423/328.3, 423/329.1, 423/332, 423/625, 423/628, 423/701-707, 423/718, 423/334-339, 502/60, 502/62, 502/63, 502/64
• US Class Current: 423/326
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 2229/62 in or on other molecular sieves
• CPC Class Codes: B01J 29/005 Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
• 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 29/084 Y-type faujasite
• 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 29/7007 Zeolite Beta
• CPC Class Codes: B01J 29/80 Mixtures of different zeolites
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 37/10 in the presence of water, e.g. steam
• CPC Class Codes: C01B 13/366 by hydrothermal processing
• CPC Class Codes: C01B 33/126 Preparation of silica of undetermined type
• CPC Class Codes: C01B 37/00 Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C01B 37/005 Silicates, i.e. so-called metallosilicalites or metallozeosilites
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/02 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
• CPC Class Codes: C01B 39/085 Group IVB- metallosilicates
• CPC Class Codes: C01P 2006/12 : Surface area
• CPC Class Codes: C01P 2006/14 : Pore volume
• CPC Class Codes: C01P 2006/16 : Pore diameter
• CPC Class Codes: C07C 15/073 : Ethylbenzene
• CPC Class Codes: C07C 2/66 : Catalytic processes

Abstract

Bimodal inorganic material that in a pore size distribution plot has distinct mesopore and micropore peaks. A process for producing a bimodal material or a material that contains essentially only mesopores involves heating an inorganic oxide in the presence of material that bonds to the inorganic oxide by hydrogen bonding. The micropores may or may not include a crystalline structure.

Claims

1. A process for producing an inorganic oxide that contains micro- and mesopores, comprising:

heating a mixture comprising water, an inorganic oxide, a crystalline zeolite in finely divided form, and at least one compound that binds to the inorganic oxide by hydrogen bonding, said compound being selected from the group consisting of triethanolamine, sulfolane, tetraethylpentamine, diethylgycoldibenzoate, and a glycol, said heating being to a temperature and for a time to produce an inorganic oxide that contains both micropores and mesopores.

2. The process of claim 1 wherein said compound is triethanolamine.

3. The process of claim 1 wherein the mixture further includes a micropore forming agent.

4. The process of claim 3 wherein said micropore forming agent is a quaternary ammonium cation.

5. The process of claim 3 wherein the inorganic oxide is an amorphous silicate.

6. The process of claim 5 wherein the heating includes maintaining the mixture about the boiling point of water to evaporate water and volatile organics from the inorganic oxide, followed by calcining at a temperature of above 300°

C.

7. The process of claim 1 wherein the inorganic oxide is a silicate material selected from the group consisting of tetraethyl orthosilicate, fumed silica, sodium silicate and silica sol.

8. The process of claim 1 wherein the glycol has a boiling point of at least 150°

C.

9. The process of claim 8 wherein the glycol is selected from the group consisting of glycerol, diethylene glycol, triethylene glycol and tetraethylene glycol.

10. The process of claim 9 wherein the mixture additionally contains a source of ions selected from the group consisting of IVA, VB, VIB, VIIB, VIII, IB, IIB and IIIA elements.

11. The process of claim 9 wherein the mixture additionally contains a source of aluminium ions.

12. The process of claim 1 wherein the inorganic oxide comprises alumina.

13. The process of claim 1 wherein the average particle size of the zeolite is from 5 to 1500 nanometers.

14. A product comprising:

an inorganic oxide and zeolite beta, said product including mesopores and micropores, said micropores being present in an amount of from 3% to 60%, by pore volume, based on micropores and mesopores, said mesopores having been generated by an organic pore-forming agent selected from the group consisting of triethanolamine, sulfolane, tetraethylpentamine, diethylglycoldibenzoate, and a glycol.

15. The product of claim 14 wherein the BET surface area is from 50 to 1250 m²/g.

16. The product of claim 14 wherein the combined micro- and mesopore volume is from 0.3 to 2.2 ml/g.

17. The product of claim 14 wherein the pore size distribution of the mesopores produces a pore size distribution plot in which the ratio of the width of the plot at half the height of the plot to the pore size at the maximum height of the plot is no greater than 0.75.

18. The product of claim 14 wherein a pore size distribution plot of mesopores and micropores includes distinct mesopore and micropore peaks.

19. The product of claim 14 wherein the inorganic oxide comprises alumina.

20. The product of claim 14 wherein the average particle size of the zeolite beta is from 5 to 1500 nanometers.

21. A process for producing an inorganic oxide that contains mesopores and a substantial amount of micropores, comprising:

heating a mixture comprising water, an inorganic oxide, a crystalline zeolite, and at least one compound that binds to the inorganic oxide by hydrogen bonding, said compound being selected from the group consisting of triethanolamine, sulfolane, tetraethylpentamine, diethylglycoldibenzoate and a glycol, said heating being to a temperature below the temperature at which there is substantial formation of mesopores, and removing said at least one compound at a temperature below the temperature at which there is substantial formation of mesopores to produce an inorganic oxide that contains mesopores and a substantial amount of micropores.

22. The process of claim 21 wherein said zeolite is zeolite beta.

23. The process of claim 21 wherein the mixture additionally contains a source of ions selected from the group consisting of IVA, VB, VIB, VIIB, VIII, IB, IIB, and IIIA elements.

24. The process of claim 21 wherein the mixture additionally contains a source of aluminum ions.

25. The process of claim 21 wherein the inorganic oxide comprises alumina.

26. The process of claim 21 wherein the average particle size of the zeolite is from 5 to 1500 nanometers.