# US 5,702,674 A · Framework metal-substituted manganese oxide octahedral molecular sieve and process for its preparation

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- Number: US 5,702,674 A
- Document ID: US5702674A
- Status: Granted
- Kind: A
- Application number: 08/667,487
- Filed: 1996-06-24
- Granted: 1997-12-30
- Earliest claimed: 1994-03-21
- Assignees: Texaco Inc.
- Inventors: Chi Lin O'Young; Yan-Fei Shen; Roberto Nguyen Dequzman; Steven Lawrence Suib
- Web page: https://patentgrep.com/patent/US5702674A

## CPC

- C01G 45/02: Oxides
- 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)
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Manganese oxide octahedral molecular sieves are provided in which a portion of the framework manganese is substituted by at least one other metal, e.g., a transition metal.

## Claims

### Claim 1

A manganese oxide octahedral molecular sieve which possesses a 2.times.2 tunnel structure and in which a portion of the manganese present in the framework structure of the molecular sieve is substituted by another metal.

### Claim 2 (depends on 1)

The molecular sieve of claim 1 possessing at least one counter cation in the tunnel structure thereof.

### Claim 3 (depends on 1)

The molecular sieve of claim 1 wherein the framework-substituting metal is selected from the group consisting of a transition metal and lanthanum.

### Claim 4 (depends on 1)

The molecular sieve of claim 1 wherein the framework substituting metal is selected from the group consisting of Mg, Fe, Co, Ni, Cu, Ti, V, Cd, Mo, W, Cr and Zn.

### Claim 5

A process for preparing a manganese oxide octahedral molecular sieve having a 2.times.2 tunnel structure and in which a portion of the manganese present in the framework structure of the molecular sieve is substituted by another metal, said process comprising heating a reaction mixture containing sufficient concentrations of manganese cation, metal cation other than manganese cation, counter cation and permanganate anion under acidic conditions and at a sufficient pressure and temperature to provide the manganese oxide octahedral molecular sieve.

### Claim 6 (depends on 5)

The process of claim 5 wherein the molar ratio of permanganate anion to manganese cation is from about 0.2 to about 2.0.

### Claim 7 (depends on 5)

The process of claim 5 wherein the molar ratio of permanganate anion to manganese cation is from about 0.2 to about 1.4.

### Claim 8 (depends on 5)

The process of claim 5 wherein the pH of the reaction mixture is less than about 4.5.

### Claim 9 (depends on 5)

The process of claim 5 wherein the pH of the reaction mixture is from about 1 to about 3.

### Claim 10 (depends on 5)

The process of claim 5 wherein heating is carried out at from about 70.degree. C. to about 255.degree. C. under autogenous pressure for from about 0.5 to about 20 hours.

### Claim 11 (depends on 5)

The process of claim 5 wherein heating is carried out at from about 80.degree. C. to about 120.degree. C. under autogenous pressure for from about 1 to about 10 hours.