# US 9,751,822 B2 · Method for producing unsaturated carboxylic acid and supported catalyst

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- Number: US 9,751,822 B2
- Document ID: US9751822B2
- Status: Granted
- Kind: B2
- Application number: 15/027,351
- Filed: 2014-10-07
- Published: 2016-08-25
- Granted: 2017-09-05
- Earliest claimed: 2013-10-10
- Assignees: Nippon Kayaku Kabushiki Kaisha
- Applicants: Nippon Kayaku Kabushiki Kaisha
- Inventors: Tatsuhiko Kurakami; Hideomi Sakai; Toru Toki
- Web page: https://patentgrep.com/patent/US9751822B2

## CPC

- C07C 51/252: {of propene, butenes, acrolein or methacrolein}
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/8885: {containing also molybdenum}
- B01J 27/199: with chromium, molybdenum, tungsten or polonium
- B01J 27/24: Nitrogen compounds
- B01J 31/36: of vanadium, niobium or tantalum
- B01J 35/612: {less than 10 m2/g}
- B01J 35/613: {10-100 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 37/0036: {Grinding}
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 37/088: {Decomposition of a metal salt}
- C07C 51/215: of saturated hydrocarbyl groups
- C07C 51/235: of —CHO groups or primary alcohol groups
- 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 invention relates to a method for producing an unsaturated carboxylic acid using a catalyst having both a high catalytic performance and a high mechanical strength, and in the method, a supported catalyst obtained by feeding a liquid binder component and a catalytic active component containing molybdenum and vanadium and/or a precursor thereof into a rolling granulator and conducting granulation at a relative centrifugal acceleration of 0.5 G or more and 30 G or less is used.

## Claims

### Claim 1

A method for producing acrylic acid, comprising:
partially oxidizing acrolein in the presence of molecular oxygen and
using a supported catalyst obtained by feeding a liquid binder component and a catalytic active component containing molybdenum and vanadium and/or a precursor thereof into a rolling granulator and conducting granulation at a relative centrifugal acceleration of 0.5 G to 30 G, said obtained catalyst having a formulation of a composite metal oxide represented by the following formula (1):
(Mo)12(V)a(W)b(Cu)c(Sb)d(X)e(Y)f(Z)g(a)h (1)
wherein Mo, V, W, Cu, Sb and O represent molybdenum, vanadium, tungsten, copper, antimony and oxygen, respectively; X represents at least one element selected from the group consisting of an alkali metal and thallium; Y represents at least one element selected from the group consisting of magnesium, calcium, strontium, barium and zinc; Z represents at least one element selected from the group consisting of niobium, cerium, tin, chromium, manganese, iron, cobalt, samarium, germanium, titanium and arsenic; and a, b, c, d, e, f, g, and h represent atomic ratios of the respective elements, in which a is (0<a≦10), b is (0≦b≦10), c is (0<c≦6), d is (0≦d≦10), e is (0≦e≦0.5), f is (0≦f≦1) and g is (0≦g<6) relative to 12 of the molybdenum atom, and h is a number of oxygen atoms necessary for satisfying valences of the above-described respective components.

### Claim 2

A supported catalyst, which is obtained by feeding a liquid binder component and a catalytic active component containing molybdenum and vanadium and/or a precursor thereof into a rolling granulator and conducting granulation at a relative centrifugal acceleration of 0.5 G to 30 G.

### Claim 3 (depends on 2)

The supported catalyst according to claim 2,
wherein the catalytic active component and/or the precursor thereof contains molybdenum, vanadium and copper.

### Claim 4 (depends on 2)

The supported catalyst according to claim 2,
wherein the catalytic active component and/or the precursor thereof contains molybdenum, vanadium and phosphorus.

### Claim 5

A method for producing methacrylic acid comprising:
partially oxidizing methacrolein in the presence of molecular oxygen and
using a supported catalyst obtained by feeding a liquid binder component and a catalytic active component containing molybdenum and vanadium and/or a precursor thereof into a rolling granulator and conducting granulation at a relative centrifugal acceleration of 0.5 G to 30 G, said obtained catalyst having a formulation of a composite metal oxide represented by the following formula (3):
(MO)10VaPb(NH4)c(X)d(Y)e(Z)g(O)f (3)
wherein Mo represents molybdenum; V represents vanadium; P represents phosphorus; (NH4) represents an ammonium group; X represents at least one element selected from the group consisting of K, Rb and Cs; Y represents at least one element selected from the group consisting of Sb, As, Cu, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce and Th; and a to e represent atomic ratios of the respective elements, in which a is (0.1≦a≦6.0), b is (0.5≦b≦6.0), c is (0≦c≦10.0), d is (0≦d≦3.0), e is (0≦e≦3), and f is a numerical value determined by oxidized states of the respective elements other than O and atomic ratios thereof.

### Claim 6 (depends on 5)

The method of claim 5, wherein a is (0.3≦a≦2.0), b is (0.7≦b≦2.0), c is (0≦c≦5), d is (0≦d≦1.5), and e is (0.01≦e≦0.5).