# US 10,479,759 B2 · Synthetic methods for the preparation of propylene ammoxidation catalysts

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- Number: US 10,479,759 B2
- Document ID: US10479759B2
- Status: Granted
- Kind: B2
- Application number: 15/427,331
- Filed: 2017-02-08
- Published: 2018-08-09
- Granted: 2019-11-19
- Earliest claimed: 2017-02-08
- Assignees: Clariant GmbH
- Applicants: Clariant Corporation
- Inventors: Hailian Li; Claus G. Lugmair
- Web page: https://patentgrep.com/patent/US10479759B2

## 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 23/8898: {containing also molybdenum}
- B01J 35/38: Abrasion or attrition resistance
- B01J 35/397: {Egg shell like}
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/651: {50-500 nm}
- B01J 35/653: {500-1000 nm}
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/086: {Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid}
- B01J 37/088: {Decomposition of a metal salt}
- C07C 45/35: in propene or isobutene
- C07C 253/18: by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
- B01J 35/23: in a colloidal state
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## 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
a metal oxide catalyst in an amount in the range of at least about 25 wt %, the metal oxide catalyst having the formula MoxBiyFezAaBbCcDdOv, wherein
x is in the range of 10 to 14;
y is in the range of 0.05 to 5;
z is in the range of 0.2 to 5;
A is at least one element selected from Ni and Co;
a is in the range of 1 to 10;
B is at least one element selected from the lanthanides, Mg, Cr, Mn, Zn and Ca;
b is in the range of 0.01 to 6;
C is at least one element selected from W, Sn, V, Ti, Zr, Ga, Hf, Nb, Ta, In and Al;
c is in the range of 0 to 8;
D is at least one element selected from Li, Na, K, Rb and Cs;
d is in the range of 0.02 to 2; and
v is the number of oxygen atoms required to satisfy the valence requirements of the other component elements Mo, Bi, Fe, A, B, C, and D,
the process comprising:
providing a suspension or slurry of an inert carrier in a metal oxide precursor fluid, the inert carrier having an average particle size less than about 10 microns, the 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 5 wt % of each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent;
spray drying the suspension or slurry of the inert carrier in the metal oxide precursor fluid to obtain a spray-dried precursor material; and
heating the spray-dried precursor material to obtain the catalyst material.

### Claim 2 (depends on 1)

The process of claim 1, wherein each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor are essentially completely dissolved in the solvent.

### Claim 3 (depends on 1)

The process of claim 1, wherein the catalyst material further comprises an inert carrier, and wherein the inert carrier is combined with the metal oxide precursor fluid to provide a suspension or slurry of the inert carrier in the metal oxide precursor fluid.

### Claim 4 (depends on 1)

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

### Claim 5 (depends on 1)

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

### Claim 6 (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 7 (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 8 (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 9 (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 10 (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 11 (depends on 1)

The process of claim 1, wherein x is 12.

### Claim 12 (depends on 1)

The process of claim 1, wherein
A is Ni, or A is Co, or A is a combination of Ni and Co;
B is at least one element selected from Ce, Mg, Cr, Mn, Zn and Ca;
C is at least one element selected from Sn, V, Ti, Zr, Ga, Hf, Nb, Ta, In and Al; and
D is at least one element selected from Li, K and Cs, and
wherein the material does not include W.

### Claim 13 (depends on 1)

The process of claim 1, wherein c is substantially zero.

### Claim 14 (depends on 1)

The process of claim 1, wherein the metal oxide catalyst has the formula MoxBiyFezNiaCeb1Mgb2Mnb3Kd1Csd2Oy, in which 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, and d2 is in the range of 0.01 to 0.8.

### Claim 15 (depends on 1)

The process of claim 1, wherein the catalyst material has an attrition resistance of less than 0.6.

### Claim 16 (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 17 (depends on 1)

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

### Claim 18 (depends on 17)

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 17.

### Claim 19 (depends on 17)

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 17.

### Claim 20 (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 %; and
less than about 1 wt % of each of the molybdenum oxide precursor, the bismuth oxide precursor, and the iron oxide precursor is not dissolved in the solvent.

### Claim 21 (depends on 20)

The process of claim 20, wherein the inert carrier has an average particle size less than about 1 microns.