# US 9,433,931 B2 · High performance polyoxometal catalyst and method for producing the same

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- Number: US 9,433,931 B2
- Document ID: US9433931B2
- Status: Granted
- Kind: B2
- Application number: 14/890,545
- Filed: 2015-07-06
- Published: 2016-06-23
- Granted: 2016-09-06
- Earliest claimed: 2014-07-09
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Byung Yul Choi; Hyun Jong Shin; Ju Yeon Park; Young Hyun Choi; Duk Ki Kim; Hyun Sub Lim
- Web page: https://patentgrep.com/patent/US9433931B2

## CPC

- B01J 23/8892: {Manganese}
- B01J 23/8885: {containing also molybdenum}
- B01J 23/8898: {containing also molybdenum}
- B01J 35/51: Spheres
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 37/0215: {Coating}
- B01J 37/0228: {in several steps}
- 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 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C07C 51/235: of —CHO groups or primary alcohol groups
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Disclosed are a high-performance polyoxometalate catalyst and a method of preparing the same. More particularly, disclosed are a high-performance polyoxometalate catalyst which may enhance activity and selectivity by controlling the content of vanadium, etc. exhibits superior reproducibility, and may produce unsaturated carboxylic acid with high yield and long lifespan from unsaturated aldehyde, and a method of preparing the same.

## Claims

### Claim 1

A polyoxometalate catalyst comprising a metal oxide represented by Formula 1 below:
MoaAbVcBdCeDfOg [Formula 1]
wherein A is at least one element selected from W and Cr, B is at least one element selected from the group consisting of P, As, B, Sb, Ce, Pb, Mn, Nb and Te, C is at least one element selected from the group consisting of Si, Al, Zr, Rh, Cu, Ni, Ti, Ag, Fe, Co and Sn, D is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr and Ba, and a, b, c, d, e, f and g denote an atomic ratio of each element, but, when a=12, b is 0.01 to 15, c is 0.01 to 15, d is 0 to 20, e is 0 to 20, f is 0 to 20, and g is determined according to an oxidation state of each of the ingredients,
wherein, in the vanadium (V), a mole ratio of V4+ relative to a sum of V4+ and V5+ is 0.47 to 1.

### Claim 2 (depends on 1)

The polyoxometalate catalyst according to claim 1, wherein each of d, e and f is 0.01 to 20.

### Claim 3 (depends on 1)

The polyoxometalate catalyst according to claim 1, wherein a mole ratio of V to A (V/A) is 0.01 to 10.

### Claim 4 (depends on 1)

The polyoxometalate catalyst according to claim 1, wherein the polyoxometalate catalyst comprises an inactive carrier as a support of the metal oxide.

### Claim 5 (depends on 4)

The polyoxometalate catalyst according to claim 4, wherein a coating amount of the metal oxide coated on the inactive carrier is 30 to 80% by weight.

### Claim 6 (depends on 1)

The polyoxometalate catalyst according to claim 1, wherein the polyoxometalate catalyst is a partial vapor-phase oxidation catalyst generating carboxylic acid from unsaturated aldehyde.

### Claim 7

A method of preparing a polyoxometalate catalyst, the method comprising: A) preparing a suspension including metal precursors in order to produce a metal oxide represented by Formula 1 and, as needed, adjusting pH to 0 to 7.5 through addition of acid, and then forming polyoxometalate by increasing viscosity using a homogenizer; B) preparing a support material by coating an inactive carrier with 20 to 50% by weight of the polyoxometalate; C) obtaining a support material having a ligand sublimation rate of 0% or more as calculated according to Equation 1 below by drying the support material; and D) obtaining a polyoxometalate catalyst by firing the dried support material:
Ligand sublimation rate (%)=(Mass of sublimated ligand/mass of ligand before sublimation)×100. [Equation 1]

### Claim 8 (depends on 7)

The method according to claim 7, wherein a viscosity of the polyoxometalate of step (A) is 5,000 to 20,000 cP.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the polyoxometalate of step (A) is ground after drying, or filtrating and drying.

### Claim 10 (depends on 7)

The method according to claim 7, wherein the coating of step (B) is performed by spraying the polyoxometalate, or the polyoxometalate with water to the inactive carrier.

### Claim 11 (depends on 7)

The method according to claim 7, wherein the suspension of step (A) is prepared by inputting an aqueous vanadium solution treated with acid and metal to a suspension comprising all or a portion of metal precursors except for a vanadium precursor.

### Claim 12 (depends on 7)

The method according to claim 7, wherein a ligand of the metal precursor is one or more selected from —NH4, —NH2, —NOx (x being an integer of 1 to 3), —Cl, —F, —N, —OH, —SOx (x is an integer of 3 to 4), —CO, —COO, —SCN, —CN, —NCS, —ONO, —NC, —CnHmOx (n being an integer of 1 to 20, m being an integer of 1 to 40, and x being an integer of 1 to 10) and C1 to C20 alkoxide.

### Claim 13 (depends on 7)

The method according to claim 7, wherein, in step (A), a concentration of the suspension is 25 to 45% by weight.

### Claim 14 (depends on 7)

The method according to claim 7, wherein, in step (C), the drying is hot air drying.

### Claim 15 (depends on 7)

The method according to claim 7, wherein the coating of step (B) is performed by repeatedly coating and drying the polyoxometalate on the inactive carrier once or more.

### Claim 16 (depends on 7)

The method according to claim 7, wherein the drying of step (C) is performed at 100 to 230° C.

### Claim 17 (depends on 7)

The method according to claim 7, wherein, in step (A), the polyoxometalate is formed by increasing a viscosity of the suspension by means of a homogenizer at 25 to 50° C.

### Claim 18 (depends on 7)

The method according to claim 7, wherein the firing of step (D) is performed at 350 to 550° C. for 1 to 10 hr.

### Claim 19 (depends on 1)

A method of preparing unsaturated carboxylic acid wherein partial vapor-phase oxidation to produce unsaturated carboxylic acid from unsaturated aldehyde gas is preformed in a fixed-bed catalyst reactor filled with the polyoxometalate catalyst according to claims 1 at 240 to 450° C. under 0.1 to 10 atm.

### Claim 20 (depends on 19)

The method according to claim 19, wherein the fixed-bed catalyst reactor is a shell-and-tube heat exchanger.