Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
2001-01-10
2004-02-24
Nguyen, Cam N. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S074000, C502S084000, C502S104000, C502S110000, C502S113000, C502S117000, C502S183000, C502S184000, C502S185000, C502S208000, C502S209000, C502S210000, C502S211000, C502S212000, C502S213000, C502S219000, C502S220000, C502S221000, C502S222000, C502S223000, C502S241000, C502S242000, C502S243000, C502S244000, C502S245000, C502S246000, C502S247000, C502S248000, C502S249000, C502S250000, C502S251000, C502S252000, C502S253000, C502S254000, C502S255000, C502S256000, C502S257000, C502S258000, C501S117000
Reexamination Certificate
active
06696388
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a novel composition comprising a gel that has utility as a catalyst or as a catalyst support. Also disclosed are methods of preparing the compositions and processes for using the compositions for the dehydrogenation of C
2-10
hydrocarbons.
BACKGROUND OF THE INVENTION
The dehydrogenation of paraffins to olefins is commercially significant because of the need for olefins for the manufacture of high octane gasolines, elastomers, detergents, plastics, ion-exchange resins and pharmaceuticals. Important hydrocarbon dehydrocyclization reactions include the conversion of diisobutylene and isooctane to p-xylene.
Processes for the conversion of paraffin hydrocarbons to less saturated hydrocarbons are known. For examples, see U.S. Pat. No. 4,513,162, U.S. Pat. No. 5,378,350 and European Pat. Application EP 947,247 (published). Nonetheless, there is a continuing need to develop new compositions that are more effective catalysts than those currently available in dehydrogenation processes.
SUMMARY OF THE INVENTION
The present invention discloses a composition of matter, comprising: (i) a solid material having pores; (ii) a gel, said gel being substantially contained within the pores of said solid material and comprising at least one catalytically active element, and optionally when said catalytically active element is other than Cr, comprising chromium in addition to said element.
Another disclosure of the present invention is a process for preparing a composition of matter comprising: a solid material having pores; a gel, said gel being substantially contained within the pores of said solid material and comprising at least one catalytically active element, and optionally when said catalytically active element is other than Cr, comprising Cr in addition to said element, said process comprising: contacting in the presence of a solid material having pores, in any order a protic solution with a non-aqueous solution wherein said non-aqueous solution comprises a gel-forming precursor and wherein one of either the protic solution or the non-aqueous solution comprises at least one soluble compound comprising an inorganic element selected from the group consisting of Group 1 through Group 16 and the lanthanides of the Periodic Table, under conditions such that the solution added first is at incipient wetness, whereby gel formation occurs substantially within the pores of said solid material.
A further disclosure of the present invention is a composition of matter prepared by the process described immediately above.
The present invention also discloses an improved gel composition, wherein said improvement comprises: said gel is substantially contained within the pores of a solid material.
Yet another disclosure of the present invention is a method of using the composition disclosed wherein said method comprises contacting in a reactor said composition with a hydrocarbon feed in a dehydrogenation or dehydrocyclization process, said hydrocarbon being from C
2
to C
10
.
DETAILED DESCRIPTION OF THE INVENTION
The solid material having pores is selected from the group consisting of alumina, silica, titania, zirconia, carbon, molecular sieves (for example, zeolites), porous minerals (such as bentonite), microporous, mesoporous and macroporous materials, montmorillonites, aluminosilicate clays (for example, bentonite), binary ternary, quaternary and higher order oxides such as e.g., Fe
2
O
3
, NiO, CaO and CeO
2
(binary oxides), FeNbO
4
, NiWO
4
and Sr
2
TiO
4
(ternary oxides) and Ca
2
MgSi
2
O
7
(quaternary oxide), carbides, nitrides, phosphates, and sulfides. These materials are used as supports for the gels.
Higher order oxides are oxides beyond quaternary that contain more than four elements, including oxygen. Some examples of higher order oxides include ganomalite (Pb
9
Ca
5
MnSi
9
O
33
), a lead calcium magnesium silicate, sodium calcium nickel arsenate (NaCa
2
Ni
2
As
3
O
12
) and barium copper europium lanthanum thorium oxide (Ba
1.33
La
0.67
Eu
1.5
Th
0.5
Cu
3
O
8.89
).
Catalytically active elements, which can be present as oxides, reduced metals, and in some cases phosphates of Group 1 (Li, Na, K, Rb, Cs), Group 2 (Be, Mg, Ca, Sr and Ba), Group 3 (Y, La) and the lanthanides (Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm Yb and Lu) of the Periodic Table can be used in C—H activation catalytic chemistries. Examples include methane coupling reactions to produce ethane and ethylene. In combination with other oxides of Groups 5, 6, 7, 8, 9, 10 of the Periodic Table, Groups 1, 2, 3 and the lanthanides can also be used for other oxidation chemistries. Alkane and olefin oxidation are two examples. Group 5 (V, Nb, Ta), Group 6 (Cr, Mo, W), Group 7 (Mn, and Re), and Group 9 (Fe, Ru, Os), can be used for oxidation reactions of alkanes and olefins. Two examples are the oxidation of butane to maleic anhydride and propylene oxidation to form acrolein. Elements of Group 10 (Ni, Pd, Pt) and Group (11, Cu. Ag, and Au) can be used for alkane and olefin oxidation reactions, CO abatement, and for Pd, Pt, hydrogenation chemistries such as hydrogenation of ethylene to ethane. Ag and its oxides can be used in epoxidation reactions, such as the epoxidation of ethylene to produce ethylene oxide. Elements of Group 15, especially P, As, Sb Bi can be used for oxidation reaction chemistries, such as the ammoxidation of propylene to acrylonitrile, especially when combined with elements of Group 6 (Cr, Mo, and W) to form various oxide combinations. Elements and their oxides of Group 16 (S, Se and Te) can be used for dehydrosulfurization chemistries, which are used to treat sulfur containing streams from petroleum distillates.
The gel is prepared from at least one soluble compound comprising an inorganic element precursor wherein at least one element is selected from the group consisting of Group 1 (i.e., Li, Na, K, Rb and Cs); Group 2 (i.e., Be, Mg, Ca, Sr and Ba); Group 3 (i.e., Y and La); Group 4 (i.e., Ti, Zr and Hf); Group 5 (i.e., V, Nb and Ta); Group 6 (i.e., Cr, Mo and W); Group 7, (i.e., Mn and Re); Group 8 (i.e., Fe, Ru and Os); Group 9 (i.e., Co, Rh and Ir); Group 10 (Ni, Pd and Pt); Group 11 (Cu, Ag and Au); Group 12 (i.e., Zn and Cd); Group 13 (i.e., B, Al and In); Group 14 (i.e.; Si, Ge, Sn and Pb); Group 15 (i.e.; P, As, Sb and Bi); Group 16 (i.e., S, Se and Te) and lanthanides (i.e.; Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) of the Periodic Table.
In the present invention one or more inorganic alkoxides or salts thereof is used as starting material, or precursors, for preparing the gels. The gel-forming precursor comprises at least one soluble compound comprising an inorganic element wherein the element is selected from the group consisting of aluminum, silicon, titanium zirconium, niobium, tantalum, vanadium, molybdenum and chromium. The alkoxides are the preferred compounds, and metal alkoxides are most preferred.
The inorganic metal alkoxides used in this invention may include any alkoxide which contains from 1 to 20 carbon atoms and preferably 1 to 5 carbon atoms in the alkoxide group, which preferably are soluble in the liquid reaction medium. Examples include, but are not limited to, tantalum n-butoxide, titanium isopropoxide, aluminum isopropoxide and zirconium isopropoxide. These alkoxides are preferred.
Inorganic materials have a range of pore sizes. Pore dimensions for some inorganic materials are relatively small. The present invention discloses gel-forming precursors that fit within the pore structure of the solid materials that are used. Commercially available alkoxides can be used. However, inorganic alkoxides can be prepared by other routes.
Inorganic alkoxides can be prepared in various ways. One method of preparation includes direct reaction of zero valent metals with alcohols in the presence of a catalyst. Many alkoxides can be formed by reaction of metal halides with alcohols. Also, alkoxy derivatives can be synthesized by the reaction of the alkoxide with alcohol in a ligand interchange reaction. Direct reactions of metal
Kourtakis Kostantinos
Manzer Leo E.
E. I. du Pont de Nemours and Company
Nguyen Cam N.
LandOfFree
Gel catalysts and process for preparing thereof does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Gel catalysts and process for preparing thereof, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Gel catalysts and process for preparing thereof will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3344656