# US 10,479,760 B2 · Synthetic methods for the preparation of propylene ammoxidation catalysts

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- Number: US 10,479,760 B2
- Document ID: US10479760B2
- Status: Granted
- Kind: B2
- Application number: 15/427,351
- Filed: 2017-02-08
- Published: 2018-08-09
- Granted: 2019-11-19
- Earliest claimed: 2017-02-08
- Assignees: Clariant GmbH
- Applicants: Clariant Corporation
- Inventors: Claus G. Lugmair; Hailian Li
- Web page: https://patentgrep.com/patent/US10479760B2

## CPC

- C07C 253/26: containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/8876: {Arsenic, antimony or bismuth}
- B01J 23/8898: {containing also molybdenum}
- B01J 35/38: Abrasion or attrition resistance
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- C07C 45/35: in propene or isobutene
- B01J 35/613: {10-100 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/80: characterised by their amorphous structures
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 37/088: {Decomposition of a metal salt}
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The present disclosure relates generally to catalyst materials and processes for making and using them. More particularly, the present disclosure relates to molybdenum, bismuth and iron-containing metal oxide catalyst materials useful, for example, in the partial oxidation or ammoxidation of propylene or isobutylene, processes for making them, and processes for making acrolein, methacrolein, acrylonitrile, and methacrylonitrile using such catalysts.

## Claims

### Claim 1

A process for producing a catalyst material, the catalyst material comprising
an inert carrier having a specific surface of 1 to 500 m2/g in an amount in the range of about 25 wt % to about 75 wt %, and
a metal oxide catalyst in an amount in the range of about 25 wt % to about 75 wt %, the metal oxide catalyst having the formula MoxBiyFezNiaCeb1Mab2Mnb3Kd1Csd2Ov, wherein
x is in the range of 12 to 14;
y is in the range of 0.05 to 0.4;
z is in the range of 1 to 2.5;
a is in the range of 5 to 7;
b1 is in the range of 0.2 to 0.6;
b2 is in the range of 1 to 3;
b3 is in the range of 0.1 to 1.0;
d1 is in the range of 0.01 to 0.15;
d2 is in the range of 0.01 to 0.8; and
v is the number of oxygen atoms required to satisfy the valence requirements of the other component elements Mo, Bi, Fe, Ni, Ce, Mg, Mn, K, and Cs,
the process comprising:
providing a metal oxide precursor fluid comprising a solvent in admixture with a plurality of metal oxide precursors, the plurality of metal oxide precursors comprising at least
a molybdenum oxide precursor,
a bismuth oxide precursor, and
an iron oxide precursor,
wherein less than about 20 wt % of each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent;
impregnating the inert carrier with the metal oxide precursor fluid to provide impregnated carrier;
drying the impregnated carrier to provide a dried, impregnated carrier; and
heating the dried, impregnated carrier to provide the catalyst material.

### Claim 2 (depends on 1)

The process of claim 1, wherein between about 0.01 wt % and about 20 wt % of each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent.

### Claim 3 (depends on 2)

The process of claim 2, wherein between about 0.1 wt % and about 5 wt % of one or more of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent.

### Claim 4 (depends on 1)

The process of claim 1, wherein molybdenum oxide precursor is provided as a heptamolybdate.

### Claim 5 (depends on 1)

The process of claim 1, wherein the solvent is an aqueous organic acid selected from glycolic acid, acetic acid, lactic acid and mixtures thereof, at a concentration in the range of 45-90 wt %.

### Claim 6 (depends on 1)

The process of claim 1, wherein providing a metal oxide precursor fluid comprises:
dissolving a molybdenum oxide precursor and a bismuth oxide precursor in the solvent to obtain a clear solution; and
adding the iron oxide precursor and optionally one or more metal oxide precursors to the clear solution.

### Claim 7 (depends on 1)

The process of claim 1, wherein heating includes calcination in the presence of air at a temperature of about 200° C. to about 700° C.

### Claim 8 (depends on 1)

The process of claim 1, wherein the inert carrier and the metal oxide catalyst are together present in the catalyst material in an amount of at least about 90 wt %.

### Claim 9 (depends on 1)

The process of claim 1, wherein the inert carrier is selected from SiO2, Al2O3, ZrO2, Nb2O5, TiO2, HfO2, Ta2O5, Sb2O5, and their mixed oxides.

### Claim 10 (depends on 1)

The process of claim 1, wherein x is 12.

### Claim 11 (depends on 1)

The process of claim 1, wherein the catalyst material has an attrition resistance of less than 0.1.

### Claim 12 (depends on 1)

The process of claim 1, wherein, of the crystalline content of the catalyst material, no more than 10% is Fe2(MoO4)3.

### Claim 13 (depends on 1)

A catalyst material prepared by the process according to claim 1.

### Claim 14 (depends on 13)

A process for the conversion of propylene, isobutylene, or a mixture thereof to acrylonitrile, methacrylonitrile, or a mixture thereof, the process comprising reacting the propylene, isobutylene, or the mixture thereof with ammonia and oxygen in the vapor phase in contact with a catalyst material according to claim 13.

### Claim 15 (depends on 13)

A process for the conversion of propylene, isobutylene, or a mixture thereof to acrolein, methacrolein, or a mixture thereof, the process comprising reacting the propylene, isobutylene, or the mixture thereof with oxygen in the vapor phase in contact with a catalyst material according to claim 13.

### Claim 16 (depends on 1)

The process of claim 1, wherein less than about 5 wt % of each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent.

### Claim 17 (depends on 16)

The process of claim 16, wherein the solvent is an aqueous organic acid selected from glycolic acid, acetic acid, lactic acid and mixtures thereof, at a concentration in the range of 45-90 wt %.

### Claim 18 (depends on 1)

The process of claim 1, wherein the inert carrier is silica.

### Claim 19 (depends on 1)

The process of claim 1, wherein divalent and trivalent metal oxide precursors are provided as acetate salts.