Catalyst for production of carboxylic acid ester, method for producing catalyst for production of carboxylic acid ester, and method for producing carboxylic acid ester

1 . A catalyst for production of carboxylic acid ester, comprising:

catalyst metal particles; and

a support supporting the catalyst metal particles,

wherein the catalyst has a hollow particle ratio of 40% or less, and

wherein the catalyst metal particles are composite particles comprising:

oxidized nickel and/or cobalt, and

X, wherein X represents at least one element selected from the group consisting of nickel, palladium, platinum, ruthenium, gold, silver, and copper.

2 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the hollow particle ratio is 35% or less.

3 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein a content of the support is from 80.0 to 99.9% by mass with respect to the catalyst for production of carboxylic acid ester.

4 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein a compositional ratio between nickel or cobalt and X in the composite particles, in terms of a Ni/(Ni+X) atomic ratio or a Co/(Co+X) atomic ratio, is from 0.20 to 0.99.

5 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the composite particles comprise oxidized nickel and gold.

6 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the support comprises silica and alumina.

7 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the support further comprises an oxide of at least one basic metal component selected from the group consisting of an alkali metal, an alkaline earth metal, and a rare earth metal.

8 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the support comprises silica, alumina, and magnesia.

9 . A method for producing the catalyst for production of carboxylic acid ester according to claim 1 , the method comprising:

a step (A) of preparing a support precursor slurry comprising raw material for the support at a stirring rotational speed of 120 rpm or more and 600 rpm or less, the slurry being at a temperature of 5° C. or more and 60° C. or less and having a viscosity of 10 cp or more and 550 cp or less,

a step (B) of supplying the support precursor slurry to a spray dryer to spray-dry the support precursor slurry at an inlet temperature of the spray dryer of 150° C. or more and 215° C. or less,

a step (C) of calcining after the step (B) to obtain a support, and

a step (D) of allowing the support to support the catalyst metal particles.

10 . The method for producing a catalyst for production of carboxylic acid ester according to claim 9 , wherein a spray drying apparatus having an inner diameter of 1000 mm or more is employed in the step (B).

11 . A method for producing carboxylic acid ester comprising a step of reacting (a) an aldehyde and an alcohol or (b) one or two or more alcohols in a presence of the catalyst for production of carboxylic acid ester according to claim 1 and oxygen.

12 . The method for producing carboxylic acid ester according to claim 11 , wherein the aldehyde is acrolein and/or methacrolein.

13 . The method for producing carboxylic acid ester according to claim 11 , wherein the aldehyde is acrolein and/or methacrolein, and the alcohol is methanol.

14 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the catalyst comprises a supported layer, the supported layer comprising a region of the support where the composite particles are concentrated, and wherein the supported layer is present in a region extending from a surface of the catalyst to 40% of an equivalent diameter of the catalyst.

15 . The catalyst for production of carboxylic acid ester according to claim 1 , wherein the composite particles comprise cobalt.