Integrated interstitial metal hydride catalyst support systems and associated processes
View Patent ↗Exemplary embodiments of the present invention relate to the processing of hydrocarbon-containing feedstreams in the presence of an interstitial metal hydride comprising a surface, with a metal oxide integrally synthesized and providing a coating on the surface of the interstitial metal hydride. The catalysts and processes of the present invention can improve overall hydrogenation, product conversion, as well as sulfur and nitrogen reduction in hydrocarbon feedstreams.
1. A catalyst comprising:
a metal oxide layer, the metal oxide being doped with a mixed valence metal selected from vanadium, cerium, tin, antimony, and combinations thereof; and
an interstitial metal hydride;
wherein an interfacial compound containing at least one element from each the metal oxide layer and the iMeH is formed between the metal oxide layer and the iMeH.
2. The catalyst of claim 1 , wherein the metal oxide layer forms a coating around the interstitial metal hydride.
3. The catalyst of claim 1 , wherein the interstitial metal hydride has a compositional formula of A 1−x M x T 5−y−z B y C z , wherein:
A=Mm (mischmetal); T=Ni; M=La, Pr, Nd or Ce; B=Co; C=Mn, Al or Cr; and
x=0.0 to 1.0; y=0.0 to 2.5; and z=0.0 to 0.5.
4. The catalyst of claim 1 , wherein the interstitial metal hydride has a compositional formula of A 2−x M x T 14−y C y D z B, wherein:
A=Nd or Pr; T=Fe; M=La, Pr, Nd or Ce; B=Boron; C=Co; D=Cr, Ni or Mn; and
x=0.0 to 2.0; y=0.0 to 14; and z=0.0 to 3.0.
5. The catalyst of claim 1 , wherein the interstitial metal hydride has a compositional formula of A 2−x M x T 1−y B y , wherein:
A=Mg; T=Ni or Cu; M=La; B=Fe or Co; and
x=0.0 to 0.5; and y=0.0 to 0.5.
6. The catalyst of claim 1 , wherein the interstitial metal hydride has a compositional formula of A 1−x B x T (2−y)+d1 C y+d2 , wherein:
A=Nd or Zr; B=at least one of La, Ce, Pr, Gd, Tb, Dy, Er, Ho, Ti and Hf; T=at least one of Fe and V; C=at least one of Cr, Mn, Fe, Co, Ni and Cu;
x=0.0 to 1.0; and y=0.0 to 2.0; and
d 1 =0.00 to 0.2; and d 2 =0.00 to 0.2.
7. The catalyst of claim 1 , wherein the metal oxide is selected from the group consisting of alumina, silica, titania, zirconia, and combinations thereof.
8. The catalyst of claim 1 , wherein the metal oxide is a porous metal oxide.
9. The catalyst of claim 8 , wherein the porous metal oxide has a pore volume greater than 0.01 cc/g; and the catalyst has a surface area greater than 10 m 2 /g.
10. The catalyst of claim 1 , wherein the catalyst further comprises at least one transition metal element selected from Mo, W, Cr, V, Mn, Sn, Fe, Co, Ni, Pd, Ru, Ir, Rh, Ag and Pt.
11. The catalyst of claim 1 , wherein the metal oxide is at least 10 wt % based on the total weight of the integrated metal oxide layer and iMeH.
12. A method of making a catalyst, comprising:
a) combining an iMeH, a metal alkoxide and an alcohol;
b) adding an acid to initiate a condensation reaction to form a metal oxide-containing gel; and
c) drying the gel to form an integrated metal oxide layer and iMeH having a surface,
wherein an interfacial compound containing at least one element from each the metal oxide layer and the iMeH is formed between the metal oxide layer and the iMeH.
13. The method of claim 12 , further comprising at least one of the following steps:
d) calcining the catalyst under an inert atmosphere;
e) charging the catalyst under hydrogen.
14. The method of claim 12 , wherein the metal alkoxide is selected from the group consisting of an aluminum alkoxide, a silicon alkoxide, a titanium alkoxide, a zirconium alkoxide, and combinations thereof.
15. The method of claim 14 , wherein the metal alkoxide is selected from the group consisting of titanium(IV) tert-butoxide, zirconium(IV) tert-butoxide, tetrabutyl orthosilicate and aluminum isopropoxide.
16. The method of claim 15 , wherein the metal oxide-containing gel comprises alumina, silica, titania, zirconia, and combinations thereof.
17. The method of claim 12 , wherein step a) further comprises combining a mixed valence metal dopant selected from vanadium, cerium, tin, antimony, and combinations thereof.
18. The method of claim 12 , wherein step a) further comprises combining at least one transition metal element selected from Mo, W, Fe, Co, Ni, Pd, and Pt.
19. A process for upgrading a hydrocarbon feedstream, comprising contacting a hydrocarbon feedstream with a catalyst to yield an upgraded hydrocarbon product stream wherein the catalyst is comprised of:
a metal oxide layer;
an interstitial metal hydride; and
an interfacial compound containing at least one element from each the metal oxide layer and the iMeH wherein the interfacial compound is formed between the metal layer support and the iMeH.
20. The process of claim 19 , wherein the process is performed in the presence of a hydrogen-rich gas containing at least 50 mol % hydrogen.
21. The process of claim 19 , wherein the hydrocarbon feedstream and catalyst are further subjected to radio frequency energy or microwave frequency energy.
22. The process of claim 19 , wherein the hydrocarbon feedstream is a heavy hydrocarbon feedstream with an API gravity of less than 20 and a sulfur content of at least 1 wt % sulfur.
23. The process of claim 19 , wherein the hydrocarbon feedstream comprises a biofuel.
24. The process of claim 19 , wherein the process is a hydroprocessing process selected from hydrogenation, hydrocracking, hydrodesulfurization, hydrodenitrogenation, hydrodemetalization, and catalytic hydrodewaxing processes.
25. The process of claim 24 , wherein the catalyst is further comprised of at least one transition metal element selected from Mo, W, Fe, Co, Ni, Pd, and Pt.
26. The process of claim 19 , wherein the process is a reforming process selected from catalytic reforming and catalytic isomerization.
27. The process of claim 26 , wherein the catalyst is further comprised of a noble metal selected from Pd and Pt.
28. The process of claim 19 , wherein the hydrocarbon feedstream contains at least 10 ppm nitrogen.