Microporous amorphous mixed metal oxides for form-selective catalysis

• US 6,319,876 B1
• Filed: 08/28/1997
• Issued: 11/20/2001
• Est. Priority Date: 02/28/1995
• Status: Expired due to Fees

• Current Assignee: Studiengesellschaft Kohle MBH
• Original Assignee: Studiengesellschaft Kohle MBH
• Inventors: Maier, Wilhelm F.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Hailey, Patricia L.
• Application Number:
  US08/913,516
• Time in Patent Office: 1,545 Days
• Field of Search: 501/39, 501/12, 502/178, 502/350, 502/351, 502/355, 502/306, 502/307, 502/308, 502/309, 502/312, 502/314, 502/1, 502/316, 502/318, 502/319, 502/321, 502/326, 502/327, 502/330, 502/331, 502/332, 502/302, 502/333-339
• US Class Current: 502/178
• CPC Class Codes: B01J 37/033 Using Hydrolysis
• CPC Class Codes: B01J 37/036 to form a gel or a cogel
• CPC Class Codes: C03C 1/006 to produce glass through wet route
• CPC Class Codes: C03C 11/00 Multi-cellular glass ; Porous or hollow glass or glass particles
• CPC Class Codes: C07C 1/043 characterised by the composition
• CPC Class Codes: C07C 1/0435 containing a metal of group 8 or a compound thereof
• CPC Class Codes: C07C 1/044 containing iron
• CPC Class Codes: C07C 2521/02 Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2521/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2521/10 Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2523/02 of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: C07C 2523/04 Alkali metals
• CPC Class Codes: C07C 2523/06 of zinc, cadmium or mercury
• CPC Class Codes: C07C 2523/08 of gallium, indium or thallium
• CPC Class Codes: C07C 2523/10 of rare earths
• CPC Class Codes: C07C 2523/14 of germanium, tin or lead
• CPC Class Codes: C07C 2523/18 Arsenic, antimony or bismuth
• CPC Class Codes: C07C 2523/20 Vanadium, niobium or tantalum
• CPC Class Codes: C07C 2523/22 Vanadium
• CPC Class Codes: C07C 2523/26 Chromium
• CPC Class Codes: C07C 2523/28 : Molybdenum
• CPC Class Codes: C07C 2523/30 : Tungsten
• CPC Class Codes: C07C 2523/34 : Manganese
• CPC Class Codes: C07C 2523/36 : Rhenium
• CPC Class Codes: C07C 2523/42 : Platinum
• CPC Class Codes: C07C 2523/44 : Palladium
• CPC Class Codes: C07C 2523/46 : Ruthenium, rhodium, osmium or iridium
• CPC Class Codes: C07C 2523/50 : Silver
• CPC Class Codes: C07C 2523/52 : Gold
• CPC Class Codes: C07C 2523/72 : Copper
• CPC Class Codes: C07C 2523/745 : Iron
• CPC Class Codes: C07C 2523/75 : Cobalt
• CPC Class Codes: C07C 2523/755 : Nickel
• CPC Class Codes: C07C 41/06 : by addition of organic compounds only
• CPC Class Codes: C07C 43/046 : Alkyl tert-alkyl ether, e.g. CH3OC(CH3)3
• CPC Class Codes: C07D 301/19 : with organic hydroperoxides
• CPC Class Codes: C07D 303/04 : containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Abstract

The invention relates to the catalytic activity and selectivity of microporous, amorphous glasses of mixed metal oxides and the application thereof in the form of shape selective, heterogeneous catalysts. Microporous, amorphous mixed metal oxides (glasses) can be formed by polycondensation of soluble metal compounds. These new materials show a temperature stability up to 800° C. These amorphous glasses shown in heterocatalytic reactions selective oxidation, hydrogenation, hydrocracking and condensation catalysis.

Claims

1. A microporous, amorphous, non-ceramic glass, which consists of a matrix of mixed metal oxides, wherein the matrix comprises micropores, at least about 90% of said micropores are of substantially equal size, and said size is a diameter between 0.3 and 1.2 nm, and wherein the matrix has a surface area of more than 50 m²/g.

2. The microporous, amorphous, non-ceramic glass according to claim 1 wherein the matrix of mixed metal oxides consists of at least two compounds selected from the group consisting of oxides of titanium, silicon, aluminum, zirconium and cerium.

3. The microporous, amorphous, non-ceramic glass according to claim 1, wherein the matrix of mixed metal oxides consists of at least two compounds selected from the group consisting of SiO₂, TiO₂, zirconium oxide, corium oxide, spinel, mullite, silicon carbide, silicon nitride and titanium nitride.

4. The microporous, amorphous, non-ceramic glass according to claim 1, wherein the matrix of mixed metal oxides consists of at least 50% by weight of a metal oxide selected from the group consisting of oxides of titanium, silicon, aluminum, zirconium and cerium, and up to 50% per weight of one or more metal oxides in an atomic distribution selected from the group of metals consisting of Mo, Sn, Zn, V, Mn, Fr, Co, Ni, As, Pb, Sb, Bi, Ru, Re, Cr, W, Nb, Hf, La, Ce, Gd, Ga, In, Tl, Ag, Cu, Li, K, Na, Be, Mg, Ca, Sr and Ba.

5. The microporous, amorphous, non-ceramic glass according to claim 1, additionally containing up to 5% by weight of at least one of the noble metals Pt, Rh, Ir, Os, Ag, Au, Cu, Ni, Pd, Co in a highly dispersed form in a metallic or oxidized stage.

6. The microporous, amorphous, non-ceramic glass according to any one of claims 1 or 2-5, which is obtained by a process comprising:

a) acid or fluoride catalyzed linear polymerization or polycondensation of at least two hydrolyzable, liquid or dissolved compounds comprising metals selected from the group consisting of titanium, silicon, aluminum, zirconium and cerium at a pH of 0 to 7 in a sol-gel process; and

followed by

b) drying of the product of a) at a temperature of 60 to 70°

C. and calcination of the product of a) at a temperature of 120 to 800°

C.

7. The microporous, amorphous, non-ceramic glass according to claim 6, which is obtained by a process comprising:

a) acid or fluoride catalyzed linear polymerization or polycondensation of at least two hydrolyzable, liquid or dissolved compounds selected from the group consisting of pure alkoxy, mixed alkoxy, alkoxyoxo or acetylacetonate derivatives comprising metals selected from the group consisting of titanium, silicon, aluminum, zirconium and cerium at a pH of 0 to 7 in a sol-gel process;

followed by

b) drying of the product of a) at a temperature of 60 to 70°

C. and calcination of the product of a) at a temperature of 120 to 800°

C.

8. A shape selective catalyst consisting of a microporous, amorphous, non-ceramic glass according to claim 6.

9. A shape selective catalyst consisting of a microporous, amorphous, non-ceramic glass according to any one of the claims 1, 2-5, or 7.