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, wherein a first peak having intensity of A appears in the 2θ range of 26.3=0.5°, and a second peak having intensity of B appears in the 2θ range of 28.3±0.5° in X ray diffraction analysis by CuKα, and an intensity ratio (A/B) of the first peak to the second peak is 1.5 or more: Mo x Bi a Fe b A c B d C e D f O y Chemical Formula 1 wherein in Chemical Formula 1, A and B are different from each other, and each independently, are one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, C is one or more elements of Li, Na, K, Rb, and Cs, D is one or more elements of Cr, W, B, Al, Ca, and V, a to f, x, and y are respectively mole fractions of each atom or atomic group, a is 0.1 to 7, b is 0.1 to 7, provided that the sum of a and b is 0.1 to 7, c is 0.1 to 10, d is 0.01 to 5, e is 0.1 to 10, f is 0 to 10, x is 11 to 14, y is a value determined by each oxidation number of Mo, Bi, Fe, A, B, C, and D.
1. An ammoxidation catalyst for propylene comprising metal oxide represented by Chemical Formula 1,
wherein a first peak having intensity of A appears in the 2θ range of 26.3±0.5°, and a second peak having intensity of B appears in the 2θ range of 28.3±0.5° in X ray diffraction analysis by CuKα, and
an intensity ratio (A/B) of the first peak to the second peak is 1.5 or more:
Mo x Bi a Fe b A c B d C e D f O y Chemical Formula 1
wherein in Chemical Formula 1,
A and B are different from each other, and each independently, are one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
C is one or more elements of Li, Na, K, Rb, and Cs,
D is one or more elements of Cr, W, B, Al, Ca, and V,
a to f, x, and y are respectively mole fractions of each atom or atomic group,
a is 0.1 to 7, b is 0.1 to 7, provided that the sum of a and b is 0.1 to 7,
c is 0.1 to 10, d is 0.01 to 5, e is 0.1 to 10, f is 0 to 10,
x is 11 to 14, y is a value determined by each oxidation number of Mo, Bi, Fe, A, B, C, and D.
2. The ammoxidation catalyst for propylene according to claim 1 , wherein the intensity ratio (A/B) is 3.0 or more.
3. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst has BET specific surface area of 50 to 300 m 2 /g.
4. The ammoxidation catalyst for propylene according to claim 1 , wherein a pore volume in the catalyst is 0.3 to 1.3 cm 3 /g.
5. The ammoxidation catalyst for propylene according to claim 1 , wherein the metal oxide is represented by Chemical Formula 1-1:
Mo x Bi a Fe b Ni c Co d K e O y Chemical Formula 1-1
wherein in Chemical Formula 1-1,
a is 0.1 to 7, b is 0.1 to 7, provided that the sum of a and b is 0.1 to 7,
c is 0.1 to 10, d is 0.01 to 5, and e is 0.1 to 10,
x is 11 to 14, y is a value determined by each oxidation number of Mo, Bi, Fe, A, B, C, and D.
6. The ammoxidation catalyst for propylene according to claim 1 , wherein the catalyst further comprises a silica carrier supporting the metal oxide.
7. The ammoxidation catalyst for propylene according to claim 6 , wherein a weight ratio of the metal oxide to the silica carrier is 15:85 to 35:65.
8. 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 Fe precursor; and a precursor of one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, or a second precursor solution comprising a Fe precursor; a precursor of one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba; and a precursor of one or more elements of Cr, W, B, Al, Ca, and V,
preparing a third precursor solution comprising a Bi precursor; a precursor of one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba, different from the second precursor solution; and a precursor of one or more elements of Li, Na, K, Rb, and Cs,
mixing the first to third precursor solutions such that a molar ratio of metals satisfies stoichiometric mole ratio Chemical Formula 1,
supporting the mixture of the first to third precursor solutions on a silica carrier,
drying the silica carrier on which the mixture of the first to third precursor solutions is supported, and
calcining the dried material:
Mo x Bi a Fe b A c B d C e D f O y Chemical Formula 1
wherein in Chemical Formula 1,
A and B are different from each other, and each independently, are one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
C is one or more elements of Li, Na, K, Rb, and Cs,
D is one or more elements of Cr, W, B, Al, Ca, and V,
a to f, x, and y are respectively mole fractions of each atom or atomic group,
a is 0.1 to 7, b is 0.1 to 7, provided that the sum of a and b is 0.1 to 7,
c is 0.1 to 10, d is 0.01 to 5, e is 0.1 to 10, f is 0 to 10,
x is 11 to 14, y is a value determined by each oxidation number of Mo, Bi, Fe, A, B, C, and D.
9. The method according to claim 8 , further comprising adding citric acid, oxalic acid or a mixture thereof to the first precursor solution.
10. The method according to claim 8 , wherein preparing the first precursor solution is conducted at 50 to 90° C.
11. The method according to claim 8 , wherein the step of preparing a second precursor solution prepares an aqueous solution comprising water, a Fe precursor, and a Co precursor.
12. The method according to claim 8 , wherein preparing the third precursor solution comprises forming a solution comprising nitric acid, a Bi precursor, a Ni precursor, and a K precursor.
13. The method according to claim 8 , wherein preparing the second precursor solution and the preparing the third precursor solution are respectively conducted at 20 to 50° C.
14. The method according to claim 8 , wherein mixing the first to third precursor solutions comprises:
mixing the second and third precursor solutions, and
adding the mixture of the second and third precursor solutions dropwise to the first precursor solution.
15. The method according to claim 8 , wherein supporting the mixture of the first to third precursor solutions on the silica carrier comprises:
first mixing the silica carrier and the first to third precursor solutions at 20 to 30° C., and
second mixing the first mixture at a temperature range of 70 to 90° C.
16. The method according to claim 15 , wherein the first and second mixing are respectively conducted for 1 to 3 hours.
17. The method according to claim 8 , wherein drying the silica carrier in which the mixture of the first to third precursor solutions is supported is conducted at 100 to 120° C.
18. The method according to claim 8 , wherein drying the silica carrier in which the mixture of the first to third precursor solutions is conducted for 5 to 12 hours.
19. The method according to claim 8 , wherein calcining the dried material is conducted at 500 to 700° C.
20. A method for ammoxidation of propylene comprising the step of reacting propylene and ammonia in the presence of the catalyst of claim 1 , in a reactor.