Ammoximation process
A redox ammoximation process in which a ketone or aldehyde is reacted with ammonia and oxygen in the presence of a catalyst, wherein: the catalyst is an aluminophosphate based redox catalyst having the qualitative general formula (I) M 1 M 2 AlPO-5 (I) in which M 1 is at least one transition metal atom having redox catalytic capability; M 2 is at least one metal atom in the (IV) oxidation state; M 1 and M 2 are different from each other; and a proportion of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms.
1. A redox ammoximation process comprising reacting a C 6 -C 12 cyclic ketone with ammonia and oxygen in the presence of a catalyst to form an oxime, wherein:
the catalyst is an aluminophosphate based redox catalyst having the formula (I)
M 1 M 2 AlPO-5 (I)
wherein M 1 is at least one selected from Co(III), Mn(III), Fe(III), Cu(III), V(V), and Ru(III) having redox catalytic capability;
M 2 is at least one selected from Ge(IV), Sn(IV), Ti(IV), and Re(IV); and
a proportion of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms.
2. A process according to claim 1 when M 2 is Ti (IV).
3. A process according to claim 2 wherein the catalyst is selected from Co III Ti IV AlPO-5, Mn III Ti IV Alpo-5, Fe III Ti IV AlPO-5, Cu III Ti IV AlPO-5, V v Ti IV AlPO-5, and Ru III Ti IV AlPO-5.
4. A process according to claim 3 wherein the catalyst is selected from Co III Ti IV AlPO-5, Mn III Ti IV AlPO-5 and Fe III Ti IV AlPO-5.
5. A process according to claim 1 wherein the M 1 is selected from Co(III), Mn(III) and Fe (III).
6. A process according to claim 1 wherein the ammonia is in the form of aqueous ammonium hydroxide.
7. A process according to claim 1 which is carried out at a temperature of from 40 to 200° C.
8. A process according to claim 7 which is carried out at a temperature of from 50 to 90° C.
9. A process according to claim 1 which is carried out at a pressure of from 0.5 MPa [5 bar] to 10 MPa [100 bar].
10. A process according to claim 1 wherein the C 6 -C 12 ketone is cyclohexanone and the oxime is cyclohexanone-oxime.
11. A process of forming an ε-caprolactam comprising reacting cyclohexanone with ammonia and oxygen in the presence of a catalyst to form an cyclohexanone oxime, wherein:
the catalyst is an aluminophosphate based redox catalyst having the formula (I)
M 1 M 2 AlPO-5 (I)
wherein M 1 is at least one selected from Co(III), Mn(III), Fe(III), Cu(III), V(V), and Ru(III) having redox catalytic capability;
M 2 is at least one selected from Ge(IV), Sn(IV), Ti(IV), and Re(IV); and
a proportion of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms; and
converting the oxime to an ε-caprolactam.
12. An aluminophosphate based redox catalyst having the formula (I)
M 1 M 2 AlPO-5 (I)
in which M 1 is at least one selected from Co(III), Mn(III), Fe(III), Cu(III), V(V), and Ru(III) having redox catalytic capability;
M 2 is at least one selected from Ge(IV), Sn(IV), Ti(IV), and Re(IV); and
a proportion of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms.
13. A process according to claim 1 wherein 2 to 18 wt % by weight of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms.
14. A catalyst according to claim 12 wherein 2 to 18 wt % by weight of the phosphorous atoms in the M 1 M 2 AlPO-5 type structure are replaced by M 2 atoms.