Mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins

• US 7,361,791 B2
• Filed: 05/24/2007
• Issued: 04/22/2008
• Est. Priority Date: 03/31/2003
• Status: Expired due to Fees

• Current Assignee: Saudi Basic Industries Corporation (Government of Saudi Arabia)
• Original Assignee: Saudi Basic Industries Corporation (Government of Saudi Arabia)
• Inventors: Ledford, John S., Stevenson, Scott A., Liang, Wugeng, Kauffman, James W., Linzer, Joseph R.
• Primary Examiner(s): Witherspoon; Sikarl A.
• Application Number:
  US11/805,805
• Publication Number:
  US 20070238904A1
• Time in Patent Office: 334 Days
• Field of Search: None
• US Class Current: 568/476
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/8876 Arsenic, antimony or bismuth
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/15 Caesium
• CPC Class Codes: B01J 2523/22 Magnesium
• CPC Class Codes: B01J 2523/27 Zinc
• CPC Class Codes: B01J 2523/34 Thallium
• CPC Class Codes: B01J 2523/48 Zirconium
• CPC Class Codes: B01J 2523/53 Antimony
• CPC Class Codes: B01J 2523/54 Bismuth
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 2523/842 Iron
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: C07C 45/34 in unsaturated compounds
• CPC Class Codes: C07C 45/35 in propene or isobutene
• CPC Class Codes: C07C 47/22 Acryaldehyde; Methacryaldehyde

Abstract

A catalyst for production of unsaturated aldehydes, such as methacrolein, by gas phase catalytic oxidation of olefins, such as isobutylene, contains oxides of molybdenum, bismuth, iron, cesium and, optionally, other metals. The catalyst has a certain relative amount ratio of cesium to bismuth, a certain relative amount ratio of iron to bismuth and a certain relative amount ratio of bismuth, iron, cesium and certain other metals to molybdenum and, optionally, tungsten. For a catalyst of the formula:
Mo₁₂Bi_aW_bFe_cCo_dNi_eSb_fCs_gMg_hZn_iP_jO_x
wherein a is 0.1 to 1.5, b is 0 to 4, c is 0.2 to 5.0, d is 0 to 9, e is 0 to 9, f is 0 to 2.0, g is from 0.4 to 1.5, h is 0 to 1.5, i is 0 to 2.0, j is 0 to 0.5 and x is determined by the valences of the other components, c:g=3.3-5.0, c:a=2.0-6.0 and (3a+3c+2d+2e+g+2h+2i)/(2×12+2b)=0.95-1.10.

Claims

1. A process of producing an unsaturated aldehyde from an olefin by gas phase catalytic oxidation comprising contacting the olefin and a molecular oxygen-containing gas in the presence of a catalyst having the formula:

Mo₁₂Bi_aW_bFe_cCs_gM_mO_x

wherein a is in the range from 0.1 to 1.5, b is in the range from 0 to 9, c is in the range from 0.2 to 5.0, g is in the range from 0.1 to 1.5, M is one or more selected from calcium, strontium, lithium, sodium, selenium, cobalt, nickel, magnesium, zinc, potassium, rubidium, thallium, manganese, barium, chromium, tin, lead, cadmium and copper, m is in the range from 0 to 9, x is determined by the valences of the other components and

wherein the relative amount ratio of c to g is from 3.3 to 5.0, the relative amount ratio of c to a is from 2.0 to 6.0 and the relative amount ratio of (3a+3c+g+Σ

v_nm_n)/(2×

12+2b) is from 0.95 to 1.10 with v being valence of each M and n being the total number of M.

2. The process of claim 1 wherein the catalyst has the formula:

Mo₁₂Bi_aW_bFe_cCs_gM_mM′

_m′

O_x

wherein M′

is one or more selected from antimony, phosphorus, boron, sulfur, silicon, aluminum, titanium, tellurium, vanadium, zirconium and niobium, m′

is in the range from 0 to 9.

3. The process of claim 2 wherein catalyst has the formula:

Mo₁₂Bi_aW_bFe_cCo_dNi_eSb_fCs_gMg_hZn_iP_jO_x

wherein b is 0 to 4, d is 0 to 9, e is 0 to 9, f is 0 to 2.0, h is 0 to 1.5, i is 0 to 2.0, j is 0 to 0.5 and wherein the relative amount ratio of (3a+3c+2d+2e+g+2h+2i)/(2×

12+2b) is from 0.95 to 1.10.

4. The process of claim 3 wherein the relative amount ratio of c to a is from 2.4 to 4.8, the relative amount ratio of c to g is from 3.3 to 4.8 and the relative amount ratio of (3a+3c+2d+2e+g+2h+2i)/(2×

12+2b) is from 0.95 to 1.09.

5. The process of claim 1 wherein the olefin is propylene and the aldehyde is acrolein.

6. The process of claim 1 wherein the olefin is isobutylene and the aldehyde is methacrolein and g is in the range from 0.4 to 1.5.

7. The process of claim 1 additionally comprising contacting the olefin, the molecular oxygen-containing gas in the presence of the catalyst and an inert gas.

8. The process of claim 7 wherein the inert gas is nitrogen.

9. The process of claim 1 wherein the molecular oxygen-containing gas is oxygen in a diluent gas.

10. The process of claim 9 wherein the diluent gas is nitrogen, a hydrocarbon which is gaseous under the process conditions or carbon dioxide.

11. The process of claim 1 wherein the reaction temperature is from 250 to 450°

C.

12. The process of claim 11 wherein the reaction temperature is from 330°

C. to 410°

C.

13. The process of claim 1 wherein the reaction pressure is from 0 to 100 psig.

14. The process of claim 13 wherein the reaction pressure is from 0 to 55 psig.

15. The process of claim 1 wherein the space velocity is from 1000 to 12,500 hr⁻

1.

16. The process of claim 15 wherein the space velocity if from 5000 to 10,000 hr⁻

1.

17. The process of claim 16 wherein the space velocity is from 7500 to 10,000 hr⁻

1.