Stabilized oxyborates and their use for oxidative conversion of hydrocarbons
An oxygen transfer agent comprising a metal-boron oxide is provided. The average oxidation state of the metal in the metal-boron oxide is about 3+, and has 10% or less of a stoichiometric excess in moles of Mn with respect to the boron. The oxygen transfer agent may further comprise a magnesia-phosphate cement. The oxygen transfer agent is capable of oxidatively dehydrogenating a hydrocarbon feed at reaction conditions to produce a dehydrogenated hydrocarbon product and water. The oxidative dehydrogenation can take place under reaction conditions of less than 1000 ppm weight molecular oxygen, or in the presence of more than 1000 ppm weight of molecular oxygen. Also provided are methods of using the oxygen transfer agents, and an apparatus for effecting the oxidative dehydrogenation of the hydrocarbon feed.
1. A method of oxidatively dehydrogenating a hydrocarbon feed to produce a dehydrogenated hydrocarbon product and water, the method comprising:
a) contacting the hydrocarbon feed with at least one oxygen transfer agent comprising a metal-boron oxide, wherein the average oxidation state of the metal in the metal-boron oxide is from 2.7+ to less than 4.0+, and the at least one oxygen transfer agent comprises 10% or less of a stoichiometric excess in moles of Mn with respect to the boron; and
b) oxidatively dehydrogenating the hydrocarbon feed at reaction conditions to produce the dehydrogenated hydrocarbon product and the water,
wherein the at least one oxygen transfer agent is selected from the group consisting of a compound that satisfies the formula M 3 BO 5 , a compound that satisfies the formula M′ 2 M″BO 5 , and mixtures thereof; and
wherein M is selected from the group consisting of alkaline earth metals, actinide metals, lanthanide metals, trivalent transition metals, and combinations thereof; M′ is selected from the group consisting of alkaline earth metals, actinide metals, lanthanide metals, and combinations thereof; and M″ is selected from group consisting of trivalent transition metals, and combinations thereof.
2. The method according to claim 1 , wherein the reaction conditions comprise less than 1000 ppm weight of molecular oxygen with respect to the total amount of the hydrocarbon feed, the oxygen transfer agent and the molecular oxygen, and wherein at least a portion of the oxygen transfer agent is reduced to produce a reduced oxygen transfer agent.
3. The method according to claim 2 , wherein the step b) oxidatively dehydrogenating the hydrocarbon feed proceeds according to the reaction:
z C n H 2n+2−2β +( z− 1+δ)“O”→C (z×n) H 2(z×n)+2−2β−2δ +( z− 1+δ)H 2 O
wherein: z=the number of reactant molecules; n=the number of atomic units in the reactant molecule; β=the degree of unsaturation in the reactant molecule, where the value is zero for single bonds, and one for double bonds and molecular rings; δ=the change in the degree of unsaturation from the reactant molecule to the product molecule; and “O” is atomic oxygen; and wherein the atomic oxygen is supplied by the at least one oxygen transfer agent.
4. The method according to claim 2 , further comprising:
d) removing a portion of the reduced oxygen transfer agent;
e) contacting the portion of the reduced oxygen transfer agent with a gas comprising molecular oxygen to produce a regenerated oxygen transfer agent; and
f) feeding the regenerated oxygen transfer agent to step a).
5. The method according to claim 1 , wherein the reaction conditions comprise providing a source of molecular oxygen in an amount greater than 1000 ppm weight.
6. The method according to claim 5 , wherein
the at least one oxygen transfer agent has a shape characterized by an aspect ratio of less than 10.
7. The method according to claim 5 , wherein the step b) oxidatively dehydrogenating the hydrocarbon feed proceeds according to the reaction:
z C n H 2n+2−2β +( z− 1+δ)“O”→C (z×n) H 2(z×n)+2−2β−2δ +( z− 1+δ)H 2 O
wherein: z=the number of reactant molecules; n=the number of atomic units in the reactant molecule; β=the degree of unsaturation in the reactant molecule, where the value is zero for single bonds, and one for double bonds and molecular rings; δ=the change in the degree of unsaturation from the reactant molecule to the product molecule; and “O” is atomic oxygen; and wherein the atomic oxygen is supplied by the source of molecular oxygen.
8. The method according to claim 1 , wherein M′ is selected from the group consisting of Mg, Ca, Sr, Ba, and mixtures thereof.
9. The method according to claim 1 , wherein M″ is selected from the group consisting of Mn, Fe, Co, Cu, V, Nb, Ta, Cr, Mo, W, and mixtures thereof.
10. The method according to claim 1 , wherein the compound that satisfies the formula M 3 BO 5 is selected from the ludwigite class minerals, and combinations thereof.
11. The method according to claim 10 , wherein the ludwigite class mineral is selected from the group consisting of pinakiolite, orthopinakiolite, takeuchiite, fredrikssonite, and combinations thereof.
12. The method according to claim 1 , wherein the at least one oxygen transfer agent further comprises a magnesia-phosphate cement that satisfies the formula:
MgM″′PO 4 .m H 2 O;
wherein M″′ is selected from the group consisting of sodium, lithium, potassium, and mixtures thereof; and m is an integer from 0 to 6.
13. The method according to claim 12 , wherein the magnesia-phosphate cement comprises at least one of MgKPO 4 .mH 2 O and MgNaPO 4 .mH 2 O, wherein m is an integer from 0 to 6.
14. The method according to claim 13 , wherein the metal-boron oxide comprises Mg 2 MnO 2 (BO 3 ) and the magnesia-phosphate cement comprises NaMg(PO 4 ).mH 2 O.
15. The method according to claim 1 , wherein the at least one oxygen transfer agent further comprises at least one promotor selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof.
16. The method according to claim 15 , wherein the at least one promoter is selected from the group consisting of Li 2 WO 4 , Na 2 WO 4 , K 2 WO 4 , SrWO 4 , Li 2 MoO 4 , Na 2 MoO 4 , K 2 MoO 4 , CsMoO 4 , Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , CaSO 4 , Na 2 SO 4 , NaHSO 4 , and mixtures thereof.
17. The method according to claim 1 , wherein the step b) oxidatively dehydrogenating the hydrocarbon feed proceeds according to the reaction:
z C n H 2n+2−2β +( z− 1+δ)“O”→C (z×n) H 2(z×n)+2−2β−2δ +( z− 1+δ)H 2 O
wherein: z=the number of reactant molecules; n=the number of atomic units in the reactant molecule; β=the degree of unsaturation in the reactant molecule, where the value is zero for single bonds, and one for double bonds and molecular rings; δ=the change in the degree of unsaturation from the reactant molecule to the product molecule; and “O” is atomic oxygen.
18. The method according to claim 17 , wherein z=2, n=1, β=0, and δ=0.
19. The method according to claim 17 , wherein z=1, n=2, β=0, and δ=1.
20. The method according claim 1 , further comprising a step c) of contacting the at least one oxygen transfer agent with a gas-phase promoter.
21. The method according claim 20 , wherein the gas-phase promoter is selected from the group consisting of gas phase water, steam, CO 2 , halide gases, hydrogen halides, sulfur containing gases, and mixtures thereof.
22. The method according to claim 20 , wherein the step c) is performed at the same time as the step a).
23. A method of oxidatively dehydrogenating a hydrocarbon feed to produce a dehydrogenated hydrocarbon product and water, the method comprising:
a) contacting the hydrocarbon feed with at least one oxygen transfer agent comprising a metal-boron oxide, wherein the average oxidation state of the metal in the metal-boron oxide is from 2.7+ to less than 4.0+, and the at least one oxygen transfer agent comprises 10% or less of a stoichiometric excess in moles of Mn with respect to the boron; and
b) oxidatively dehydrogenating the hydrocarbon feed at reaction conditions to produce the dehydrogenated hydrocarbon product and the water,
wherein the at least one oxygen transfer agent further comprises a magnesia-phosphate cement that satisfies the formula:
MgM″′PO 4 .m H 2 O;
wherein M″′ is selected from the group consisting of sodium, lithium, potassium, and mixtures thereof; and m is an integer from 0 to 6.
24. The method according to claim 23 , wherein the at least one oxygen transfer agent comprises a compound that satisfies the formula M 3 BO 5 ,
wherein M is selected from the group consisting of alkaline earth metals, actinide metals, lanthanide metals, trivalent transition metals, and combinations thereof.
25. The method according to claim 23 , wherein the at least one oxygen transfer agent comprises a compound that satisfies the formula M′ 2 M″BO 5 ,
wherein M′ is selected from the group consisting of alkaline earth metals, actinide metals, lanthanide metals, and combinations thereof; and M″ is selected from group consisting of trivalent transition metals, and combinations thereof.
26. The method according to claim 23 , wherein the magnesia-phosphate cement comprises at least one of MgKPO 4 .mH 2 O and MgNaPO 4 .mH 2 O, wherein m is an integer from 0 to 6.
27. The method according to claim 26 , wherein the metal-boron oxide comprises Mg 2 MnO 2 (BO 3 ) and the magnesia-phosphate cement comprises NaMg(PO 4 ).mH 2 O.