Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation method using the same catalyst
An ammoxidation catalyst includes a metal oxide represented by Chemical Formula 1 supported on a silica carrier, wherein the catalyst has pores having a diameter of 5 to 200 nm, a pore volume of 0.1 to 3.0 cm 3 /g, and a BET surface area of 50 m2/g to 1,000 m2/g: Mo 12 Bi a Fe b A c B d C e O x Chemical Formula 1 wherein in Chemical Formula 1, A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, B is one or more elements of Li, Na, K, Rb, and Cs, C is one or more elements of Cr, W, B, Al, Ca, and V, and a to e, and x are respectively fractions of each atom or atomic group, wherein a is 0.1 to 5, b is 0.1 to 5, c is 0.1 to 10, d is 0.1 to 2, e is 0 to 10, and x is 24 to 48.
1. An ammoxidation catalyst for propylene in which metal oxide represented by Chemical Formula 1 is supported on a silica carrier,
wherein the catalyst comprises pores having a diameter of 5 to 200 nm, a pore volume of 0.1 to 3.0 cm 3 /g, and
wherein the catalyst has BET specific surface area of 50 m 2 /g to 1000 m 2 /g:
Mo 12 Bi a Fe b A c B d C e O x Chemical Formula 1
wherein in Chemical Formula 1,
A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
B is one or more elements of Li, Na, K, Rb, and Cs,
C is one or more elements of Cr, W, B, Al, Ca, and V, and
a to e, and x are respectively fractions of each atom or atomic group, wherein a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, e is 0 to 10, and x is 24 to 48.
2. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst comprises
a silica carrier comprising second pores;
an internal coating layer that coats wall surfaces of the second pores, and comprises the metal oxide represented by the Chemical Formula 1; and
first pores positioned inside of the second pores, and occupying empty spaces except the internal coating layer.
3. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst has BET specific surface area of 60 to 500 m 2 /g.
4. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst comprises pores having a diameter of 10 to 100 nm.
5. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst comprises pores having a volume of 0.6 to 2.0 cm 3 /g.
6. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst has a D50 particle diameter of 50 to 200 μm.
7. The ammoxidation catalyst for propylene according to claim 1 , wherein the metal oxide is represented by Chemical Formula 1-1:
Mo 12 Bi a Fe b Co c K d O x Chemical Formula 1-1
wherein in Chemical Formula 1-1, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, and x is 24 to 48.
8. The ammoxidation catalyst for propylene according to claim 1 , wherein a weight ratio of the metal oxide and the silica carrier is 15:85 to 35:65.
9. A method for preparing the ammoxidation catalyst for propylene according to claim 1 , comprising:
preparing a first precursor solution comprising a Mo precursor,
preparing a second precursor solution comprising a Bi precursor, a Fe precursor, an A precursor, wherein A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, and a B precursor, wherein B is one or more elements of Li, Na, K, Rb, and Cs, or a second precursor solution comprising a Bi precursor, a Fe precursor, an A precursor, wherein A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, a B precursor, wherein B is one or more elements of Li, Na, K, Rb, and Cs, and a C precursor, wherein C is one or more elements of Cr, W, B, Al, Ca, and V,
mixing the first and second precursor solutions such that a molar ratio of metals satisfies stoichiometric molar ratio of Chemical Formula 1,
supporting the mixture of the first and second precursor solutions on a silica carrier,
drying the silica carrier in which the mixture of the first and second precursor solutions is supported, and
calcining the dried material:
Mo 12 Bi a Fe b A c B d C e O x Chemical Formula 1
wherein in Chemical Formula 1,
A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
B is one or more elements of Li, Na, K, Rb, and Cs,
C is one or more elements of Cr, W, B, Al, Ca, and V, and
a to e, and x are respectively fractions of each atom or atomic group, wherein a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, e is 0 to 10, and x is 24 to 48.
10. The method according to claim 9 , wherein the second precursor solution further comprising a C precursor, wherein C is one or more elements of Cr, W, B, Al, Ca, and V.
11. The method according to claim 9 , wherein the second precursor solution comprises a Bi precursor, a Fe precursor, a Co precursor, and a K precursor.
12. The method according to claim 9 , wherein the silica carrier comprises pores having a diameter of 10 to 200 nm and a volume of 0.1 to 3 cm 3 /g.
13. The method according to claim 9 , wherein the silica carrier has BET specific surface area of 50 m 2 /g to 1000 m 2 /g.
14. The method according to claim 9 , wherein drying the silica carrier in which a mixture of the first and second precursor solutions is supported comprises:
a first vacuum drying of the silica carrier in which a mixture of the first and second precursor solutions is supported at 120 to 160 mbar, and
a second vacuum drying of the first vacuum dried material at 30 to 50 mbar, to obtain a silica carrier in which a mixture of the first and second precursor solutions is supported.
15. The method according to claim 14 , wherein the first vacuum drying is conducted at 60 to 80° C.
16. The method according to claim 14 , wherein the second vacuum drying is conducted at 80 to 100° C.
17. The method according to claim 14 , further comprising a third drying the second vacuum dried material at atmospheric pressure.
18. The method according to claim 17 , wherein the third drying is conducted at 100 to 150° C.
19. The method according to claim 9 , wherein the calcining of the dried material is conducted at 500 to 700° C.
20. A method for ammoxidation of propylene, comprising reacting propylene and ammonia in the presence of the catalyst of claim 1 , in a reactor.