Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
1998-07-27
2002-11-12
Silverman, Stanley S. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S305000, C502S325000, C502S349000, C502S353000, C502S350000, C502S351000, C502S527120, C502S527130, C502S527150, C502S527240, C427S585000
Reexamination Certificate
active
06479428
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a catalyst useful for hydrocarbon conversion and specifically to a catalyst structure that exhibits longer life especially under high temperature conditions.
BACKGROUND OF THE INVENTION
Hydrogen and hydrocarbon conversion reactions including but not limited to steam reforming, water-gas shift reactions, methanol synthesis and catalytic combustion are well known. These reactions are usually carried out at temperatures between 200 and 1000° C. Currently these reactions are industrially run using catalyst pellets which consist of an active catalytic metal or metal oxide deposited on high surface area ceramic pellets.
Known foam or monolith catalysts are known to have three layers (1) porous support, (2) interfacial layer, and (3) catalyst metal as described in [1]. In making these catalysts, the interfacial layer has been deposited by various methods including solution impregnation techniques. The catalyst layer may be deposited by solution impregnation techniques. The interfacial layer has greater surface area than the porous support whereas the porous support has greater mechanical strength than the interfacial layer.
The porous support may be a metal or ceramic foam. Metal foams are highly thermally conductive and easy to machine. The sponge-like mechanical properties allow convenient sealing in a reaction chamber via mechanical contact. The closely matched thermal expansion between the metal foam and the housing reaction chamber minimizes cracking of the porous support and minimizes gas channeling around the porous support at higher reaction temperatures. Pestryakov et al prepared metal foam supported transition metal oxide catalysts with [1] and without [2] an intermediate gamma-alumina layer for the oxidation of n-butane. Kosak [3] examined several approaches to disperse precious metals on various metal foams where the surface was pre-etched with HCl solution, and reported that electroless deposition provides the best adhesion of precious metals to the foam supports. Podyacheva et al. [4] also synthesized foam metal supported LaCoO
3
perovskite catalyst with a porous alumina intermediate for methane oxidation. Despite all of the potential advantages with metal foam supported catalysts, metal foam has low corrosion resistance and its nonporous and smooth web surfaces have provided poor adhesion to ceramic materials.
In order to increase corrosion resistance, methods such as diffusion alloying with Al, Cr, and Si have been used to fabricate ferritic steels, which are typically used for the manufacturing of high temperature furnace elements (about 1200° C.) [5]. When the aluminum containing ferritic steels are appropriately heat-treated, aluminum migrates to the alloy surface and forms a strongly adhering oxide film which is resistant to oxygen diffusion. Such ferritic steel foils have been used to fabricate metal monoliths with >10 ppi (pores per inch) open cells [6]. However, the search for the similar alloy foams with pores suitable for catalytic applications (<20 ppi, 80 ppi preferred) has been fruitless. This has been attributed to both the immature methods for making the finer Al-ferritic steel foams and the lack of the alloy precursors for making the foams.
Hence, there is a need in the art of supported catalysts for a porous support of a foam that is resistant to corrosion or oxidation and resists cracking of the interfacial layer.
References
1. A. N.Pestryakov, A. A.Fyodorov, V. A.Shurov, M. S.Gaisinovich, and I. V.Fyodorova,
React.Kinet.Catal.Lett
., 53 [2] 347-352 (1994).
2. A. N. Pestryakov, A. A. Fyodorov, M. S. Gaisinovich, V. P. Shurov, I.V. Fyodorova, and T. A. Gubaykulina,
React.Kinet.Catal.Lett
., 54 [1] 167-172 (1995).
3. J. R. Kosak. A Novel Fixed Bed Catalyst for the Direct Combination of H
2
and O
2
to H
2
O
2
, M. G. Scaros and M. L. Prunier, Eds.,
Catalysis of Organic Reactions
, Marcel Dekker, Inc. (1995), p115-124.
4. O. Y. Podyacheva, A. A. Ketov, Z. R. Ismagilov, V. A. Ushakov, A. Bos and H. J. Veringa,
React.Kinet.Catal.Lett
., 60 [2] 243-250 (1997).
5. A. N. Leonov, O. L. Smorygo, and V. K. Sheleg,
React.Kinet.Catal.Lett
., 60 [2] 259-267 (1997).
6. M. V. Twigg and D. E. Webster. Metal and Coated-Metal Catalysts, A Cybulski and J. A. Moulijn, Eds.,
Structured Catalysts and Reactors
, Marcel Dekker, Inc. (1998), p59-90 .
SUMMARY OF THE INVENTION
The present invention includes a catalyst that has at least three layers, (1) porous support, (2) buffer layer, (3) interfacial layer, and optionally (4) catalyst material. The buffer layer provides a transition of thermal expansion coefficient from the porous support to the interfacial layer thereby reducing thermal expansion stress as the catalyst is heated to high operating temperatures. The buffer layer also reduces corrosion and oxidation of the porous support.
The method of the present invention for making the multi-layer catalyst (at least four layers) has the steps of (1) selecting a porous support, (2) solution depositing an interfacial layer thereon, and optionally (3) depositing a catalyst material onto the interfacial layer; wherein the improvement comprises (4) depositing a buffer layer between the porous support and the interfacial layer.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description taken in connection with accompanying drawings wherein like reference characters refer to like elements.
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Adris et al, On t
Gao Yufei
Tonkovich Anna Lee Y.
Wang Yong
Battelle (Memorial Institute)
Ildebrando Christina
May Stephen R.
Rosenberg Frank S.
Silverman Stanley S.
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