Process for preparing a catalyst for the oxidation and ammoxidation of olefins
View Patent ↗A process for preparing an antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, wherein the catalyst is represented by the empirical formula Me a Sb b X c Q d R e O f , wherein Me, X, Q, R, a, b, c, d, e, and f are as defined herein, comprising (a) contacting an aqueous Sb 2 O 3 slurry with HNO 3 and one or more Me compounds, and, optionally, one or more compounds selected from X, Q, or R compounds to form a first mixture; (b) heating and drying the first mixture to form a solid product; and (c) calcining the solid product to form the catalyst, the catalysts prepared by the process, and the use of the catalysts in ammoxidation and oxidation processes. The catalysts of the invention are particularly useful for the production of acrylonitrile from propylene, ammonia, and an oxygen-containing gas.
1. A process for preparing an antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst represented by the empirical formula:
Me a Sb b X c Q d R e O f
wherein Me is at least one element selected from Fe, Go, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm, or Nd; X is at least one element selected from V, Mo, or W; Q is at least one element selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf Nb, Ta, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element selected from Bi, B, P, or Te; and the subscripts a, b, c, d, e, and f denote atomic ratios and are as follows: a is 0.1 to 15, b is 1 to 100, c is 0 to 20, d is 0 to 20, e is 0 to 10, and f is a number taken to satisfy the valence requirements of the metals present in said catalyst in the oxidation states in which they exist in said catalyst, comprising:
(a) contacting an aqueous Sb 2 O 3 slurry with HNO 3 and one or more Me compounds, and, optionally, one or more compounds selected from X, Q, or R compounds under controlled pH conditions to form a first mixture which is substantially free of silica sol;
(b) heating and drying said first mixture to form a solid product; and
(c) calcining said solid product to form said catalyst.
2. The process of claim 1 further comprising adding a support material selected from silica, zirconia, alumina, or titania to said first mixture after step (a) of contacting an aqueous Sb 2 O 3 slurry with HNO 3 and one or more Me compounds but prior to step (b) of heating and drying said first mixture, wherein said catalyst contains from about 10% to about 90% by weight of said support material based on the total weight of said catalyst.
3. The process of claim 2 wherein said catalyst contains from about 35% to about 65% by weight of said support material based on the total weight of said catalyst.
4. The process of claim 3 wherein said support material is silica sol.
5. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 2 .
6. The process of claim 1 wherein c is 0.01 to 10, and e is 0.01 to 5.
7. The process of claim 6 wherein Me is selected from Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, or Ce; and R is selected from Bi, Te, or P.
8. The process of claim 7 wherein Me a comprises Fe a and U a′ , and a and a′ are independently selected from 0.1 to 10.
9. The process of claim 8 wherein R is Bi, and X is Mo.
10. The process of claim 9 wherein said catalyst is represented by the empirical formula:
U a′ Fe a Sb b MO c Bi e O f
wherein a and a′ are independently selected from 0.1 to 5, b is 1 to 10, c is 0.001 to 0.2, and e is 0.001 to 0.2.
11. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 10 .
12. The process of claim 1 wherein the calcining temperature is from about 500° C. to about 1150° C.
13. The process of claim 12 wherein said calcining temperature is from about 600° C. to about 900° C.
14. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 1 .
15. A process for preparing an antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst represented by the empirical formula:
U a′ Fe a Sb b Mo c Bi e O f
wherein the subscripts a, a′, b, c, e, and f denote atomic rations and are as follows: a is 0.1 to 5, a′ is 0.1 to 5, b is 1 to 10, c is 0.001 to 0.2, e is 0.001 to 0.2, and f is a number taken to satisfy the valence requirements of Sb, U, Fe, Bi, and Mo present in said catalyst in the oxidation states in which they exist in said catalyst, comprising:
(a) contacting an aqueous Sb 2 O 3 slurry with HNO 3 , oxides or nitrates of bismuth, and oxides or nitrates of uranium to form a first mixture;
(b) heating said first mixture at a temperature and for a time sufficient to induce formation of desired crystalline oxides of antimony and form a second mixture;
(c) adding an aqueous solution of a ferric compound to said second mixture to form a third mixture;
(d) adjusting the pH of said third mixture to about 7 to about 8.5, thereby forming a hydrated mixed oxide precipitate in an aqueous phase;
(e) separating the hydrated mixed oxide precipitate from the aqueous phase;
(f) forming an aqueous slurry of the hydrated mixed oxide precipitate component;
(g) adding a molybdate to the hydrated mixed oxide component slurry;
(h) forming the hydrated mixed oxide—molybdate component slurry into dry particles; and
(i) calcining the dry particles to form said catalyst.
16. The process of claim 15 wherein a is 0.1 to 1, a′ is 0.1 to 1, b is 1 to 5, c is 0.01 to 0.1, and e is 0.01 to 0.05.
17. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 16 .
18. The process of claim 15 wherein said first mixture is formed from bismuth trioxide, and triuranium octoxide.
19. The process of claim 18 wherein said third mixture is formed from ferric nitrate.
20. The process of claim 15 wherein said first mixture is heated at a temperature from about 80° C. to about 110° C. for a period from about 1 hour to about 6 hours.
21. The process of claim 15 wherein the molybdate is ammonium molybdate.
22. The process of claim 15 further comprising adding a support material selected from silica, zirconia, alumina, or titania to said hydrated mixed oxide component slurry prior to drying said hydrated mixed oxide—molybdate component slurry, wherein said catalyst contains from about 10% to about 90% by weight of said support material based on the total weight of said catalyst.
23. The process of claim 22 wherein said catalyst contains from about 35% to about 65% by weight of said support material based on the total weight of said catalyst.
24. The process of claim 22 wherein said support material is silica sol.
25. The process of claim 22 wherein said support material is added to said hydrated mixed oxide component slurry prior to adding said molybdate.
26. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 22 .
27. The process of claim 15 wherein said dry particles are formed by spray-drying an aqueous slurry.
28. The process of claim 15 wherein the calcining temperature is from about 500° C. to about 1150° C.
29. The process of claim 28 wherein said calcining temperature is from about 600° C. to about 900° C.
30. An antimonate-based mixed metal oxide catalyst in a catalytically active oxidized state, said catalyst prepared by the process of claim 15 .