High performance polyoxometal catalyst and method for producing the same

Patent metadata

Field	Value
Publication number	US-2016175818-A1
Application number	US-201514890545-A
Country	US
Kind code	A1
Filing date	Jul 6, 2015
Priority date	Jul 9, 2014
Publication date	Jun 23, 2016
Grant date	—

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.

First claim

What is claimed is:

1 . A polyoxometalate catalyst comprising a metal oxide represented by Formula 1 below:
Mo a A b V c B d C e D f O g   [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 V 4+ relative to a sum of V 4+ and V 5+ is 0.47 to 1.

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

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

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

5 . 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.

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

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]

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

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

10 . 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.

11 . 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.

12 . The method according to claim 7 , wherein a ligand of the metal precursor is one or more selected from —NH 4 , —NH 2 , —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 C 1 to C 20 alkoxide.

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

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

15 . 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.

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

17 . 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.

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

19 . 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.

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

Assignees

• Lg Chemical Ltd

Inventors

• Choi Byung Yul
• Shin Hyun Jong
• Park Ju Yeon
• Choi Young Hyun
• Kim Duk Ki
• Lim Hyun Sub

Classifications

• B01J23/8885 Primary

  containing also molybdenum · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J37/0215

  Coating · CPC title

• C07C51/235

  of —CHO groups or primary alcohol groups · CPC title

• B01J23/8892 Primary

  Manganese · CPC title