WO1999015715A2 - Coated products - Google Patents
Coated products Download PDFInfo
- Publication number
- WO1999015715A2 WO1999015715A2 PCT/US1998/019811 US9819811W WO9915715A2 WO 1999015715 A2 WO1999015715 A2 WO 1999015715A2 US 9819811 W US9819811 W US 9819811W WO 9915715 A2 WO9915715 A2 WO 9915715A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- particles
- catalyst
- product
- coated
- Prior art date
Links
- 238000000576 coating method Methods 0.000 claims abstract description 182
- 239000011248 coating agent Substances 0.000 claims abstract description 174
- 239000002245 particle Substances 0.000 claims abstract description 160
- 239000000463 material Substances 0.000 claims abstract description 121
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 23
- 239000011800 void material Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims description 48
- 230000008569 process Effects 0.000 claims description 27
- 239000003989 dielectric material Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 26
- 239000003292 glue Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 69
- 238000000151 deposition Methods 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000012856 packing Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001652 electrophoretic deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- -1 zeolite X Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
Definitions
- the invention relates to coated products and the production thereof
- the invention also relates to electrophoretic coating and to products produced thereby
- This invention further relates to providing a more uniform coatmg by the use of electrophoretic coating or deposition
- the present invention relates to the production of a coated three-dimensional network of material in which interior and exte ⁇ or portions ot the material are coated
- the invention further relates to a coated catalyst structure wherein the structure is formed from a plurality of layers of fibers that are coated with a paniculate coatmg that includes a catalyst.
- electrophoretic coating Another coatmg procedure which is known in the an is electrophoretic coating Such electrophoretic coating has generally been applied only to dense bodies or surfaces
- a process for depositing particles, as a coating, on a product or support comprised of a three dimensional network of material with the particles being applied to such a product or support by an electrophoretic coating procedure.
- Such porous product or support can be effectively coated with a paniculate coating with or without penetration of the coating into the interior of the porous product or support, preferably with penetration and that the degree of penetration can be controlled.
- Such three dimensional network of material is preferably formed from a plurality of layers of fibers that are randomly onented.
- the invention is not limited to achieving such a uniform coating; i.e., the porous product may have a non-uniform coating over a defined thickness.
- a porous product is coated electrophoretically to produce a product having a paniculate coating in which a defined thickness thereof is uniformly coated (the interior portion of the multilayered product is coated)
- the present invention is also applicable to producing a coated product in which there is no essential penetration into the interior of the product or in which there is a controlled penetration and in which the coating is not uniform.
- an electrophoretic coating procedure may be employed for depositing particles within the interior of a product comprised of a three dimensional network of material. Moreover, Applicant has surprisingly found that an electrophoretic coating procedure may be employed for depositing particles as a uniform coating for a defined thickness of the interior portion of such a three dimensional network.
- a coated porous product which differs from coated porous products produced by procedures previously employed in the art such as spray coating or dipping.
- the use of the technique of the invention provides a more uniform coating, i.e., there is a lower variation in coating thickness over a defined thickness of the product.
- an excess buildup of coating material that blocks or closes pores can be reduced or eliminated.
- “blocking” or “closing” of pores is reduced and/or eliminated.
- "bare" or uncoated portions of material are reduced or eliminated.
- a product comprised of a three dimensional network of materials may be produced in which a defined thickness of the interior portion of the material is coated with the particles in a uniform manner.
- the defined thickness of the three dimensional network of material may be a portion of the overall thickness or may be the entire thickness of such three dimensional network.
- the coating comprised of particles forms a porous coating on both the exterior and the interior portion of the three dimensional network of material, which coating may be comprised of one, two or more layers of the deposited particles.
- a process and coated product wherein a non-particulate support is electrophoretically coated with particles that have an average particle size greater than 0.5 micron wherein such larger particles are electrophoretically coated onto the support in conjunction with smaller particles that have an average particle size less than 150 nanometers (such smaller particles can be in the form of a sol or colloid).
- an electrophoretic coating of larger particles may be applied more effectively if the coating bath employed in such electrophoretic coating process includes particles having an average particle size of less than 150 nanometers in addition to the larger particles.
- the smaller particles function to more effectively bind the larger particles to each other and/or to the support or product that is being coated.
- the smaller particles function as a "glue" to improve the adherence of the larger particles to each other and/or to the coated product or support and increase the mobility of the larger particles in the electric field.
- the larger particles that are to be coated onto the product or support are either a catalyst support, catalyst precursor, a catalyst, or a catalyst or catalyst precursor on a paniculate support.
- the smaller particles may be the same material as the larger particles or may be a different material.
- a catalyst in particle- form (the particle form of the catalyst coated on the non-particulate support may be a paniculate catalyst support coated or impregnated with a catalyst) is present as a coating on a non-particulate support in which the particulate catalyst, when supported on the non-particulate support, has an average particle size greater than 0.5 micron.
- the electrophoretic coating bath that contains such larger particles also includes smaller particles (in the form of a sol or colloid) in an amount that provides for a coating of the larger particles onto the non-particulate support such that the coating of the larger particles effectively adheres to the non- particulate support.
- the smaller particles may be comprised of the same material as the larger particles or may be a different material or materials or may include the material of the larger particle plus a different material. As hereinabove indicated, it is believed that the smaller particles function as a "glue" that improves adherence of the larger particles to each other and/or the non-particulate support.
- the average particle size of the smaller particles is generally less than 150 nanometers.
- the average particle size is at least 2 nanometers.
- the average particle size is from 20-40 nanometers.
- the larger particles that are to be coated onto the non-particulate support generally have an average particle size of at least 0.5 micron for example, at least 1.0 micron. In general, the average particle size does not exceed 20 microns.
- the relative amounts of the larger and smaller particles are selected to achieve in the final coating the desired amount of larger particles and an amount of smaller particles that provides for effective adherence of the coating containing the larger particles to the non-particulate support.
- the amount of smaller particles used in the coating bath is from 0.1 % to 10% by weight.
- the aspect of the present invention wherein larger particles are electrophoretically coated onto a support is applicable to the electrophoretic coating of porous supports (three dimensional supports with a thickness wherein the coating is applied to -both the exterior or interior of the support) as well as to electrophoretic coating of dense or non-porous supports wherein the coating is essentially only applied to the exterior of the support.
- the product or support to which a coating of particles is applied by electrophoretic coating is one which is capable of accepting a charge.
- the product may be formed from only conductive materials or from a mixture of conductive and nonconductive materials, provided that the overall product is capable of accepting a charge.
- conductive materials which may be used alone or in combination for forming all or a portion of the product comprised of a three dimensional network of material
- metals, carbon as well as electrically conducting polymers and/or ceramics.
- of preferred metals there may be mentioned: stainless steel; Fe-Ni or Fe- Cr alloys; Fe-Cr-Al alloys; copper; nickel; brass; etc.
- the product or support which is coated may be of the type described in U.S. Patent Nos. 5,304,330; 5,080,962; 5,102,745 or 5,096,663.
- the three dimensional network of materials may be one which is comprised of fibers or wires, such as a wire or fiber mesh, a metal felt or gauze, metal fiber filter or paper and the like, or may be a porous metal composite for example, formed from sintered porous metal powder.
- the compacted powder and/or wires or fiber define a three dimensional network of material which has a thickness thereto.
- the thickness of the three dimensional network of material which contains the uniform coating is at least 5 microns, and generally does not exceed 10 mm.
- the thickness of the network which contains the uniform coating is at least 50 microns and more preferably at least 100 microns, and generally does not exceed 2 mm.
- the thickness or diameter of the fiber is less than 500 microns, preferably less than 100 microns and more preferably less than 30 microns.
- the product that is coated is preferably comprised of a plurality of layers of fibers that are randomly oriented in the layers, and in accordance with the invention, the fibers in the interior as well on the exterior of the product are coated with a paniculate coating to form a porous coating.
- the particles which are applied to the three-dimensional network of material, as a coating, by an electrophoretic coating process generally have an average particle size which does not exceed 100 microns, and in most cases does not exceed 10 microns. In general, the particle size of such particles is at least 1 nanometer, and preferably at least 2 nanometers.
- the particles may be colloidal particles or mixtures of colloidal particles and/or mixtures of colloidal particles with one or more particles which are not colloidal particles.
- the thickness of the formed coating may vary. In general, the thickness is at least 1 micron and in general no greater than 100 microns.
- the particles that are to be coated onto the support may be comprised of a single material or multiple materials (two, three or more different materials).
- the material may be a complex of two or more materials, such as an ionic or absorbed complex.
- the interior portion of the product that is coated in accordance with the invention has a porosity which is sufficient to allow the particles which comprise the coating to penetrate or migrate into the three dimensional network.
- the pore size of the three dimensional material and the particle size of the particles comprising the coating determine the distance to which the particles penetrate into and coat the interior of the three dimensional network of material and/or the coating thickness in the network.
- the larger the pore sizes the greater the thickness of the coating which can be uniformly coated in accordance with the invention.
- the average void opening of the product which is coated is at least 10 microns and preferably at least 20 microns, preferably the total void volume is 60-90% (void volume percent is the ratio of open volume to total volume multiplied by 100).
- the product or support which is coated may have different pore sizes over the thickness thereof, and within the scope of the invention, it is contemplated that the three dimensional product which is coated will have a uniform porosity throughout or that its porosity will vary and that such product may be a laminated and/or comprised of the same or different materials and/or may have multi-layers.
- the material forming the three-dimensional network which is to be electrophoretically coated may be coated or uncoated and such three-dimensional network may have particles entrapped or contained therein. In general, such particles, if present, have a size of from 1-300 microns.
- the paniculate material which is used as the coating may be comprised of a single material or a mixture of materials and when a mixture is used, the particles may be a composite comprised of smaller particles (a sol) which adheres to larger particles.
- the coating mixture may include an appropriate sol, all or a portion of which adheres to the larger particles to provide a sufficient charge and/or binding properties for producing a paniculate coating in accordance with the invention.
- the paniculate material which is applied as a coating may be particles larger than a sol, which larger particles may be applied as a coating with or without the addition of a sol, preferably with the addition of a sol.
- the particles which are applied to the three dimensional network of porous material may be catalyst particles or a catalyst support and/or a catalyst support containing active catalyst or precursor and/or a catalyst precursor.
- the particles preferably form a uniform coating over a defined thickness of the interior of the three dimensional network of material, with such three-dimensional network of material being porous (having a void volume), and widi the coating of particles on such material also being porous. In this manner, it is possible to provide an overall catalyst structure in which there is a high void volume and wherein catalyst is uniformly distributed through a defined thickness of the interior of the three dimensional network.
- the product after the deposit of the particles, is treated to convert the catalyst precursor to an active catalyst.
- active catalyst or catalyst precursor may then be applied to such support, e.g., by spraying, dipping, or impregnation.
- Catalytically active material or precursors can be many-fold.
- the catalytically active material may comprise one or more of Group VIB, " VTIB, VIII catalytically active metals, metal oxide or sulfides and mixtures thereof and optionally including activators such as phosphorous, halogen or boron or such Group VIB, VIIB, VIII catalytically active metals, metal oxides or metal sulfides or metal nitrides and optionally including activators such as phosphorus, halogen or boron and mixtures thereof deposited on a refractory metal oxide base such as alumina, silica, silica alumina, titania, zirconia, etc.
- alumina-silicate such as natural or synthetic zeolites such as zeolite X, zeolite Y, zeolite beta, ZSM-5, offretite, mordenite, erronite. etc. and mixtures thereof.
- silica, titania-phases, vanadia-phases, transition-aluminas, zinc-phases can be deposited directly from suspensions e.g., as nano- or micrometer particles or from sols of said compounds or from mixtures of both.
- Coated particles may include carbon supports, such as carbon black, oxidized carbon supports, carbon molecular sieves, etc., that are porous or non- porous.
- the concentration of the solid in the suspensions can vary between 0.01 and 80 wt. %
- the particles that are applied to the three dimensional. material are inorganic particles.
- the coating bath in some cases may include additional agents, such as stabilizers, binders, mobility enhancing agents, etc., and in some cases a single material may perform multiple functions in this respect.
- additional agents such as stabilizers, binders, mobility enhancing agents, etc.
- stabilizing agents there may be mentioned: a polymer like polyacrylic acid, acrylamines. organic quarternary ammonium compounds, or other special mixes which are selected based on the particles that are to be coated.
- sols may also act as binders and/or stabilizing agents.
- the advantage of sols is that they are not pyrolyzed during subsequent heat treatment, which is used in most cases to achieve a proper bonding between the coating and the matrix.
- alumina powder is suspended in an aqueous system and alumina sol is added to obtain, for example, a concentration between 1 and 30 wt. % alumina in such aqueous system.
- the article is dried and calcined.
- the dried and calcined sol is a good binder for alumina.
- the sol functions as a stabilizer and gives mobility to the alumina particles.
- the catalyst may be applied to the support in a variety of ways.
- a paniculate catalyst support may be applied to the support by electrophoretic coating in accordance with the invention, followed by application of a catalyst solution to the coated product; e.g., by spraying or impregnation.
- unsupported catalyst particles may be applied to a support in accordance with the invention.
- a particulate catalyst support having catalyst or catalyst precursor applied thereto is coated onto the support in accordance with the invention.
- the electrophoretic coating may be accomplished with or without a binder added to the electrophoretic coating mix.
- a binder may be applied to the three-dimensional network prior or subsequent to coating with a particulate material, with such binder preferably being applied by electrophoretic coating in accordance with the invention.
- multiple coatings may be applied to the same product in multiple coating steps, which coatings may be the same or different from each other.
- a material may also be applied to the non-particulate support in addition to the particulates being applied by electrophoretic coating.
- the product comprised of a mree dimensional network of material has particles applied thereto by use of an electrophoretic coating or deposition process, which electrophoretic process may be of a type known in the art. It is unexpected that such known electrophoretic coating or deposition procedure could be effectively applied to both the interior and exterior of a product or support comprised of a porous three dimensional network of material (a product having a thickness) in that it would have been expected that the particles would be applied only to the exterior surfaces, rather than to the exterior and interior of such three dimensional network.
- the product comprised of a three dimensional network of materials, is connected to the power supply as a positive or negative pole, depending on the charge of the particles which are to be applied to such product.
- the particles are employed in suspension in an appropriate liquid medium for application to the product or support.
- the product to which the particles are to be applied forms one of the poles or electrodes employed in the procedure.
- the rate and amount of particles which is applied to the support and, therefore, the thickness of the coating may be controlled by controlling the current (which is determined by electrophoretic deposition parameters such as voltage and solid content of the suspension of particles employed in the procedure and additives) and the total time of the coating process.
- the coated porous body is usually dried and, if required, one or more treatment steps can be carried out.
- the article to be coated is immersed into the coating suspension.
- the electrodes are positioned.
- the electrodes may be comprised of a metal (e.g., stainless steel).
- the article to be coated is the + or - pole (cathodic or anodic deposition).
- the deposition process is usually made under constant voltage, which depends on the geometry of the entire system (size/distance of the electrodes) and the properties of the suspension. Generally, the correlation is given by:
- a second heating step is performed to achieve a proper bonding of the coating onto the surface and to make the coating itself more stable against abrasion and other influences.
- the specific heating cycles and conditions are dependent on the coating.
- the heating cycle forms the appropriate crystallographic phase.
- An alumina-sol for example, can be dried at 110°C and treated afterwards at 550°C in an inert or oxygen-containing atmosphere to form a transitional-alumina.
- each of the fibers or wires in the defined thickness can be coated with such particles in a uniform manner.
- essentially the entire thickness of the material is coated with the particles, it is within the spirit and scope of the invention to coat less than the entire thickness with such particles. It is also possible within the spirit and scope of the present invention to have various coating thickness within the three dimensional structure.
- the aspect of the present invention wherein larger panicles are more effectively electrophoretically coated onto a support or product by the use of a sol or colloid is applicable to electrophoretic coating of nonporous supports wherein essentially only the exterior is coated as well as to the coating of porous supports wherein both the interior and exterior are coated.
- the invention further relates to a catalytic reactor wherein the reactor contains at least one fixed bed of catalyst comprised of a coated, porous, three- dimensional product in accordance with the present invention.
- the coating of the porous, three-dimensional product includes an appropriate catalyst. All or a portion of the coating is applied to the product or support by an electrophoretic procedure as hereinabove described wherein the coating which is applied electrophoretically is comprised of catalyst alone, or combination of catalyst and support or support and in the case where only the catalyst support is applied by electrophoretic coating, the catalyst is subsequently applied by another procedure, e.g. spray-coating or dipping or impregnation.
- the void volume of the coated product is preferably at least 45%, and is preferably at least 55%, and is more preferably at least 65%. In general, the void volume does not exceed 95%, and preferably does not exceed 90%.
- the term "void volume" as used herein is determined by dividing the volume of the coated product which is open (free of catalyst and material forming the mesh) by the total volume of the coated product (openings, mesh material and coating) and multiply by 100.
- the reactor contains at least one catalyst bed, and such catalyst bed may be formed from one or more layers of coated product in accordance with the invention. In most cases, the catalyst bed is comprised of multi-layers of such coated product.
- the coated product in accordance with the present invention, may be formed into a wide variety of shapes and, therefore, may be employed as a packing element for a catalytic reactor.
- the mesh may be fabricated into corrugated packing elements, wherein each corrugated packing element which forms the fixed catalyst bed is formed of the coated product.
- the catalyst bed can be formed from a plurality of such corrugated elements, and the elements may be arranged in a wide variety of shapes and forms.
- a catalyst structure that is comprised of a plurality of layers of fibers (the layers form a three dimensional network of material), with the fibers being randomly oriented in said layers, with the fibers being coated with a porous particulate coating wherein the particulate coating is applied to the fibers in a particulate form.
- the particulate comprising the catalyst or a catalyst precursor or a catalyst support (the catalyst support may or may not include a catalyst or catalyst precursor) is applied to the fibers during the coating process in the form of particles.
- a process (and resulting product) for producing a catalytic structure that is comprised of a support structure that is coated with a particulate coating comprising a catalyst.
- the support structure is a porous mesh like structure comprised of multiple layers of randomly oriented fibers wherein the fibers in the interior of the mesh like structure and the fibers on the exterior portion of the mesh-like structure are coated with the particulate coating.
- the particles of the particulate coating are in the form of particles when being applied to the fibers.
- a porous non-particulate support comprised of a plurality of layers of fibers, that are preferably randomly oriented, in which the fibers of the multi-layers are coated with a particulate coating comprising a catalyst wherein the particles of the coating are applied to the fibers as particles.
- the particles that are applied as a coating may be (i) a catalyst support that may or may not include a catalyst or catalyst precursor or (ii) a catalyst or (iii) a catalyst precursor.
- catalyst may be added to the support particles coated on the fiber.
- the particles are or include a catalyst precursor or where the particles are a catalyst support that contain a catalyst precursor, the catalyst precursor is converted to a catalyst by procedures known in the art.
- the fibers used in the catalyst structure may be of the type as hereinabove described and the resulting catalyst structure may also have the properties (void volume etc.) as hereinabove described.
- the support structure used in this aspect of the invention is comprised of a plurality of layers of randomly oriented fibers and, therefore, is not and is different from woven mesh structures used in the prior art.
- woven mesh structures include a single layer of material.
- a three-dimensional catalyst support, or packing, for a catalytic reactor wherein the support, or packing, is formed of a coated, porous, three-dimensional product which has the characteristics hereinabove described.
- a catalyst coated packing in a reactor in particular a fixed bed reactor in accordance with the invention can provide one or more of the following improvements: low by-product formation (improved selectivity); higher volumetric activity per unit of reactor volume; enhanced catalyst life, minimization or elimination of back- mixing; lower pressure drop; improved mixing of reactants and/or products as liquids and/or gases; higher geometric surface area to volume ratio of the catalyst; improved mass and heat transfer; etc.
- the catalytic reactor may be employed for a wide variety of chemical reactions.
- chemical reactions there may be mentioned hydrogenation reactions, oxidations, dehydrogenation reactions, catalytic or steam reforming, alkylation reactions, hydrotreating, condensation reactions, hydrocracking, etherification reactions, isomerization reactions, selective catalytic reductions, and catalytic removal of volatile organic compounds, etc.
- the "edge effect" is one in which the material being coated receives a thicker coating around the edges thereof than in other portions thereof; in particular, the center portions.
- the "edge effect" is reduced whereby the difference between the coating thickness around the edges of the coated material and other portions of the coated material is n ⁇ mized; i.e., in the same plane, the coating thickness at the edge of the material is essentially equal to the coating thickness in other portions of the material.
- edge effect is reduced by electrophoretically coating the material in a manner such that the field lines between the electrode comprising the material to be coated, and the electrode or electrodes of opposite plurality which are adjacent to the electrode comprising the material to be coated are disrupted.
- the edge effect can be minimized by disrupting or changing the field lines between the electrode comprising the material to be coated and the adjacent electrodes of opposite polarity such edge effect reduction may be accomplished without the use of a disrupting counter-electrode.
- the electrophoretic coating is accomplished by a procedure that employs non-homogeneous or non-uniform field lines.
- the edge effect in an electrophoretic coating process is minimized by electrophoretically coating a material in a manner such that the cross-section of the electrode comprising the material to be coated, and the electrode or electrodes of opposite polarity adjacent to the material to be coated, as well as the cross-section of the coating bath between such electrodes are essentially equal to each other.
- the shape and outer dimensions of such electrodes, and the shape and outer dimension of the coating bath between such electrodes are essentially equal to each other. Applicant has found that the use of such dimensions reduces the edge effect.
- the distance between the electrode comprising the material to be coated, and the electrodes of opposite polarity adjacent to the electrode comprising the material to be coated is selected to be at a value which minimizes the edge effect during such electrophoretic coating. Applicant has found that by reducing the distance between such electrodes, the edge effect can be reduced. In a preferred embodiment, the distances between the electrode comprising the material to be coated, and the electrodes of opposite polarity adjacent to such electrode, is less than 100 mm and, in general, is no less than one millimeter.
- a dielectric material is placed between the electrode comprising the material to be coated and the electrodes of opposite polarity adjacent thereto.
- Such dielectric material has an opening therein and the dielectric constant thereof is different than that of the suspension in the coating bath.
- the dielectric constant of such dielectric material is at least ten times greater than the dielectric constant of the suspension in the coating bath.
- the opening or openings in the dielectric material generally comprises from 10% to 90% of the area of the dielectric material.
- the size or area of the opening or plurality of the openings is less than the size or cross-sectional area of the material to be coated.
- the electrophoretic coating is effected in a manner such that the electrodes adjacent to the electrode comprising the material to be coated, -and having a polarity opposite thereto, is comprised of a polarity of separately spaced electrodes, each of which is smaller than the electrode(s) comprising the material to be coated.
- the electrodes having a polarity opposite to that of the electrode comprising the material to be coated, which is adjacent to the material to be coated is each comprised of a plurality of pin-like electrodes, anchored or placed in a dielectric material, with the pin electrodes being spaced from each other.
- Such pin electrodes create a non-homogeneous or disrupted electric field which improves the uniformity of the electrophoretic coating; i.e. , reduces edge effects.
- a combination of the hereinabove-described techniques for reducing the edge effect may be employed.
- two or more of such techniques may be employed to improve the uniformity of the coating.
- the distance between the electrodes is selected to minimize the distance between the material to be coated and the electrode of opposite polarity adjacent thereto thereby improving the uniformity of the coating.
- the above two techniques may be combined with the use of a dielectric material between adjacent electrodes having an appropriate opening therein.
- the uniformity of the coating thickness can be manipulated to provide a wide variety of coating thickness differences.
- by appropriately controlling the opening(s) in the dielectric material it is possible to reduce the edge effect and to obtain a uniform coating over the cross-sectional area, in a given plane, of the material which is coated.
- Figure 1 is a simplified schematic of an electrophoretic coating apparatus
- Figure 2 is a simplified schematic of an electrophoretic costing apparatus with means for reducing edge effects
- Figure 3 is a simplified schematic of an electrode for reducing edge effects
- Figure 4 is a simplified schematic of an electrophoretic coating apparatus for reducing edge effects
- Figure 5 is a simplified schematic of an electrophoretic coating apparatus that includes means for locating the material to be coated.
- a deposition apparatus An example for a deposition apparatus is given in Fig. 1.
- the electrodes (1) made of an electronically conducting sheet (e.g. stainless steel) are immersed in the colloidal fluid (10), which is all inserted in a container (15).
- the article to be coated by the colloidal particles is placed between the two electrodes.
- the geometry of the arrangement can be varied, so that one electrode or more than two electrodes are used.
- the article to be coated (20) can be placed between two electrodes (1) or opposite to a single electrode or between an arrangement of more than two electrodes.
- FIG. 2 a schematic representation of a coating unit, which includes a dielectric material between the electrode comprising the product to be coated and the electrode of opposite polarity.
- the product electrode is 21, the electrode of opposite polarity is 22, and the dielectric material is 23, which includes a slit opening 24.
- a dielectric material with a slit opening is shown, as hereinabove indicated, other openings in the dielectric material are possible within the scope of the present invention.
- the opening may be a square or rectangular opening, or a plurality of openings in the dielectric material.
- an electrode wherein the electrode is comprised of a plurality of separate and distinct electrodes, which are used as an electrode having a polarity opposite to the electrode comprising the material to be electrophoretically coated. As shown in Figure 3, such an electrode is comprised of a plurality of pin-like electrodes 31 in a dielectric material 32.
- FIG 4 there is shown a schematic representation of an electrophoretic coating design wherein the electrode comprising the material to be coated, the electrodes of polarity opposite thereto, and the coating bath between the electrodes have essentially the same dimension.
- the electrode comprising the material to be coated is designated as 41
- the two electrodes of opposite polarity are designated as 42 and 43.
- the electrodes 41, 42 and 43 have essentially the same dimensions, and the height and width of the tank 44 for holding the electrophoretic coating material 46 is such that the level of the electrophoretic coating material in the tank may be maintained essentially equal to the height of the electrodes.
- the techniques for reducing edge effect of the present invention has particular applicability to the coating of a porous, three- dimensional network of material by electrophoretic coating in a manner such that in addition to the exterior of the material at least a portion of the interior of such three- dimensional network is coated.
- such techniques may also be employed for coating the surface of non-porous materials.
- electrophoretic coating is effected in a manner such that the distance between the sheet and each electrode of opposite polarity is 50 mm.
- the size of the electrode, the specimen and the cross-section of the bath is 30 x 30 cm.
- such an arrangement may be accomplished by the use of a holder which positions the sheet to be coated the desired distance from the other electrode.
- the sheets are fixed in a container box, which is mobile.
- the container is inserted in coating units and drying units.
- the movable container is equipped with the electrodes with a design that allows a "self-positioning by gravity" (distance holders) of the mesh-sheets.
- the electrical contacts are guided through the distance holders, so that no external electrical contacting is necessary. This makes the process easy to handle, reliable and allows simple automation.
- a container or cell 64 comprised of a first wall in the form of an electrode 62, a second wall in the form of an electrode 63 and a bottom non-conducting wall 66.
- the sheet 60 to be coated is put into the deposition container 64 (Fig 5a); and the sheet 60 rests "unlocated" in the deposition cell or container 64 (Fig. 5b).
- the container 64 is tilted to an angle of 45° (Fig. 5c) and the sheet 60 falls on the distance holders 61 which include an electrode 67 that is of a polarity opposite to both electrodes 62 and 63.
- the electrical current transport during the electrophoretic deposition is governed by the charge transport by the colloidal particles and by ionic transport. The latter is undesired. because this is a current transport without any benefit. Due to this the concentration of ions should be kept on a minimum.
- Example 1 Configuration and process to incorporate gamma alumina onto and into a sheet of metal felt.
- the tank contains an alumina sol with particle size ranging from 1 to 60 ran, preferred 10-30 run.
- the system is stabilized to establish a sufficiently long shelf life by addition of nitric acid or acetic acid.
- Aqueous solutions are preferred because such systems are easy to handle.
- the solid concentration of alumina in the sol is between 1 and 30 wt. %, preferred 5-10 wt. %.
- Positive electrodes of stainless steel plates are preferred while the negatively charged electrode is the article to be coated, which may consist for example of a 1 mm thick metal felt made of 20 micron thick metal fibers with 90% void volume and an average void-opening of 20 micron.
- the article to be coated has a size of 10 by 10 cm.
- a current is applied, a voltage between 10 and 20 V and a current between 0.1 and 100 mA per cm 2 specimen-surface, preferred 10-40 mA per cm 2 surface.
- the specimen is removed from the tank, dried to evaporate water and sintered afterwards (e.g. a temperature of 500° to 550°C for 1 to 3 hours, preferably 500°C for 1 hour) to form gamma aluminum oxide that is properly bonded to the metal surface and has the appropriate active surface between 100 and 300 m /g.
- the current and the deposition time alumina-loads up to 30% can be incorporated in the metallic felt.
- Example 2 Co-deposition of sol and particles
- micrometer-particles exhibit an electrophoretic mobility and the solid particles migrate into the fiber-network of the article to be coated-.
- micrometer sized particles which have a size of preferred 0.5-10 micron can be titania, alumina, zeolite or any other compound.
- the sol acts as an adhesive that connects the particles to the fiber-surface and to each other. The process starts with a stable suspension of micron particles that contains a sol (nano-particles) with a concentration ranging from below 1 % up to 20% or even higher.
- the electrophoretic deposition results in a migration of both, the nano-particles (i.e., sol) and the micrometer particles, towards the fiber-network.
- a co-deposition onto the surface of the fibers takes place.
- the micrometer- particles are more firmly attached onto the metal surface by the sol; after heating to temperatures higher than 100°C, the dried coating begins to solidify and the sol starts to form a crystalline state.
- the micron-particles are embedded in a porous thin film coating and are by this strongly attached to the metal.
- coated products of the present invention may be employed for a wide variety of applications, including, but not limited to, use as a catalyst, separation membranes, packing (non-catalytic or catalytic) for columns, in particular distillation columns; sensors; separation devices other than membranes; adsorbents for adsorption columns.
- a catalyst separation membranes, packing (non-catalytic or catalytic) for columns, in particular distillation columns; sensors; separation devices other than membranes; adsorbents for adsorption columns.
- a coating deposition cell contains two plate like stainless steel electrodes with the same geometry as the cross section of the bath: 30 cm by 30 cm. The distance of the electrodes from each other is 100 mm.
- the amount of sol-binder is governed by the total amount of aluminum oxide ( ⁇ 3 microns) of oxide powder, which is in this example 10 wt.%.
- the amount of sol-binder is 2 wt.% of the amount of the solid powder.
- This mix is vigorously stirred and 1 wt.% (related to the amount of oxide powder) of quaternary amine is added.
- the pH is adjusted by adding diluted nitric acid to pH 4-4.5.
- the aluminum oxide ( ⁇ 3 microns) powder is added step by step while the suspension is stirred further.
- a fiber mesh sheet (30 cm x 30 cm), that has been annealed at 300 C for 1 h is inserted at the middle plane between the two electrodes.
- a potential of 10 V is applied across the electrodes and the fiber mesh.
- a deposition time of 60 seconds is sufficient to load the interior of the fiber mesh structure with 25 wt.% oxide powder.
- the mesh is removed from the bath, the adhering drops are blown off by an air-blower and dried by a hot air stream.
- the final step is the sinte ⁇ ng at 500 C for 1 h in air.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9812384-0A BR9812384A (en) | 1997-09-23 | 1998-09-23 | Coated products |
AU95009/98A AU9500998A (en) | 1997-09-23 | 1998-09-23 | Coated products |
JP2000513001A JP3757373B2 (en) | 1997-09-23 | 1998-09-23 | Coated product |
EP98948436A EP1017885A2 (en) | 1997-09-23 | 1998-09-23 | Coated products |
CA002302749A CA2302749A1 (en) | 1997-09-23 | 1998-09-23 | Process for electrophoretically coating a product comprised of three-dimensional network of material and catalyst prepared by this process |
Applications Claiming Priority (4)
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US5979597P | 1997-09-23 | 1997-09-23 | |
US60/059,795 | 1997-09-23 | ||
US9748398P | 1998-08-21 | 1998-08-21 | |
US60/097,483 | 1998-08-21 |
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WO1999015715A2 true WO1999015715A2 (en) | 1999-04-01 |
WO1999015715A3 WO1999015715A3 (en) | 1999-08-26 |
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PCT/US1998/019811 WO1999015715A2 (en) | 1997-09-23 | 1998-09-23 | Coated products |
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US (2) | US6217732B1 (en) |
EP (1) | EP1017885A2 (en) |
JP (1) | JP3757373B2 (en) |
KR (1) | KR100394513B1 (en) |
CN (1) | CN1271395A (en) |
AR (1) | AR015171A1 (en) |
AU (1) | AU9500998A (en) |
BR (1) | BR9812384A (en) |
CA (1) | CA2302749A1 (en) |
ID (1) | ID24453A (en) |
TW (1) | TW482829B (en) |
WO (1) | WO1999015715A2 (en) |
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- 1998-09-17 US US09/156,023 patent/US6217732B1/en not_active Expired - Fee Related
- 1998-09-22 AR ARP980104742A patent/AR015171A1/en unknown
- 1998-09-23 AU AU95009/98A patent/AU9500998A/en not_active Abandoned
- 1998-09-23 ID IDW20000530A patent/ID24453A/en unknown
- 1998-09-23 WO PCT/US1998/019811 patent/WO1999015715A2/en active IP Right Grant
- 1998-09-23 EP EP98948436A patent/EP1017885A2/en not_active Withdrawn
- 1998-09-23 CA CA002302749A patent/CA2302749A1/en not_active Abandoned
- 1998-09-23 JP JP2000513001A patent/JP3757373B2/en not_active Expired - Lifetime
- 1998-09-23 CN CN98809384A patent/CN1271395A/en active Pending
- 1998-09-23 KR KR10-2000-7003133A patent/KR100394513B1/en not_active IP Right Cessation
- 1998-09-23 BR BR9812384-0A patent/BR9812384A/en not_active Application Discontinuation
- 1998-09-24 TW TW087115824A patent/TW482829B/en not_active IP Right Cessation
-
2001
- 2001-03-01 US US09/797,082 patent/US6624115B2/en not_active Expired - Lifetime
Patent Citations (1)
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WO1997030193A1 (en) * | 1996-02-13 | 1997-08-21 | Engelhard Corporation | Catalyst on metal substrate by simultaneous electrophoretic deposition of catalyst and catalyst adhesion material |
Non-Patent Citations (1)
Title |
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L. GAL-OR: "Deep Electrophoretic Penetration and Deposition of Ceramic Particles inside Porous substrates" J. ELECTROCHEM. SOC, vol. 139, no. 4, 1992, pages 1078-1079, XP002104278 * |
Cited By (9)
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WO2001028665A1 (en) * | 1999-10-15 | 2001-04-26 | Abb Lummus Global, Inc. | Conversion of nitrogen oxides in the presence of a catalyst supported of a mesh-like structure |
US6534022B1 (en) | 1999-10-15 | 2003-03-18 | Abb Lummus Global, Inc. | Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure |
US6667017B2 (en) | 1999-10-15 | 2003-12-23 | Abb Lummus Global, Inc. | Process for removing environmentally harmful compounds |
US6946107B2 (en) | 1999-10-15 | 2005-09-20 | Abb Lummus Global, Inc. | Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure |
EP1754526A1 (en) * | 1999-10-15 | 2007-02-21 | ABB Lummus Global Inc. | Conversion of nitrogen oxides in the presence of catalyst supported on a mesh-like structure |
KR100840812B1 (en) * | 1999-10-15 | 2008-06-23 | 루머스 테크놀로지 인코포레이티드 | Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure |
US7488360B2 (en) * | 2001-02-16 | 2009-02-10 | Battelle Memorial Institute | Catalysts, reactors and methods of producing hydrogen via the water-gas shift reaction |
US7776113B2 (en) * | 2001-02-16 | 2010-08-17 | Battelle Memorial Institute | Catalysts, reactors and methods of producing hydrogen via the water-gas shift reaction |
US7901742B2 (en) | 2006-06-19 | 2011-03-08 | Jgc Catalysts And Chemicals Ltd. | Method for forming metal oxide fine particle layer on conductive substrate |
Also Published As
Publication number | Publication date |
---|---|
US20020005355A1 (en) | 2002-01-17 |
AU9500998A (en) | 1999-04-12 |
AR015171A1 (en) | 2001-04-18 |
JP3757373B2 (en) | 2006-03-22 |
JP2001517738A (en) | 2001-10-09 |
CA2302749A1 (en) | 1999-04-01 |
CN1271395A (en) | 2000-10-25 |
KR100394513B1 (en) | 2003-08-14 |
TW482829B (en) | 2002-04-11 |
EP1017885A2 (en) | 2000-07-12 |
KR20010024257A (en) | 2001-03-26 |
ID24453A (en) | 2000-07-20 |
WO1999015715A3 (en) | 1999-08-26 |
BR9812384A (en) | 2000-09-12 |
US6624115B2 (en) | 2003-09-23 |
US6217732B1 (en) | 2001-04-17 |
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