EP1127029A1 - Production of hydrogen-containing gas streams - Google Patents
Production of hydrogen-containing gas streamsInfo
- Publication number
- EP1127029A1 EP1127029A1 EP99971397A EP99971397A EP1127029A1 EP 1127029 A1 EP1127029 A1 EP 1127029A1 EP 99971397 A EP99971397 A EP 99971397A EP 99971397 A EP99971397 A EP 99971397A EP 1127029 A1 EP1127029 A1 EP 1127029A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mesh
- catalyst
- steam
- reforming
- support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000007789 gas Substances 0.000 title description 14
- 229910052739 hydrogen Inorganic materials 0.000 title description 8
- 239000001257 hydrogen Substances 0.000 title description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 111
- 238000000629 steam reforming Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000011800 void material Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 39
- 239000000463 material Substances 0.000 description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000008199 coating composition Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 208000021017 Weight Gain Diseases 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000021053 average weight gain Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This application claims the priority of United States Provisional Application 60/107,127, filed November 5, 1998.
- This invention relates to the production of a hydrogen-containing gas by catalytic reforming of a hydrocarbon feedstock.
- a reforming gas such as steam and/or carbon dioxide; in particular, steam, in the presence of a suitable reforming catalyst.
- a feedstock comprises methane and the hydrogen-containing gas contains hydrogen and carbon monoxide, with such gas often being referred to in the art as a "synthesis gas.”
- the steam-reforming reaction is endothermic and is operated at high temperature in order that the equilibrium favors production of hydrogen.
- the heat required for the endothermic reforming reaction is supplied by preheating the feed and by heating during the reforming process; in particular, the reforming reaction is accomplished in a reactor often referred to in the art as a steam reformer.
- the steam reforming reactor is a tubular reactor where the tubes are heated in a fired furnace.
- other reactor configurations are also possible, e.g. non-fired tubular reactors or pre heated adiabatic packed beds.
- the present invention is directed to improving the steam-reforming process for conversion of a hydrocarbon feedstock to a synthesis gas.
- a synthesis gas (a gas that contains hydrogen, and also generally contains carbon monoxide), is produced by reacting steam and a hydrocarbon, with the hydrocarbon preferably being methane, in the presence of a steam-reforming catalyst, wherein the steam- reforming catalyst is supported on a mesh or mesh-like material, or the catalyst is in the form of a mesh i.e., the mesh is formed from a catalytic material.
- the term "supported on the mesh” includes coating the catalyst on the mesh as well as entrapping the catalyst in the interstices of the mesh.
- the catalyst that is supported on the mesh in a preferred embodiment, is comprised of a steam- reforming catalyst supported on a particulate support with the supported steam- reforming catalyst being supported on the mesh.
- the mesh like material is comprised of fibers or wires, such as a wire or fiber mesh, a metal felt or gauze, metal fiber filter or the like.
- the mesh like structure may be comprised of a single layer, e.g. a knitted wire structure or a woven wire structure, or may include more than one layer of wires; and is preferably comprised of a plurality of layers of wires or fibers to form a three dimensional network of materials.
- the support structure is comprised of a plurality of layers of fibers that are randomly oriented in the layers.
- One or more metals may be used in producing a metal mesh.
- the mesh fibers may be formed from or include materials other than metals alone or in combination with metals; e.g. carbon or metal oxides or a ceramic.
- the mesh includes a metal.
- the material forming the mesh is preferably non-catalytic with respect to steam reforming. As hereinabove indicated, in one embodiment, the material forming the mesh is a steam-reforming catalyst.
- the thickness of such support is at least five microns, and generally does not exceed ten millimeters. In accordance with a preferred embodiment, the thickness of the network is at least 50 microns and more preferably at least 100 microns and generally does not exceed 2 millimeters.
- the thickness or diameter of the fibers which form the plurality of layers of fibers is less than about 500 microns, preferably less than about 150 microns and more preferably less than about 30 microns. In a preferred embodiment the thickness or diameter of the fibers is from about 8 to about 25 microns.
- the three dimensional mesh like structure may be produced as described in U.S. Patent Number 5,304,330; 5,080,962; 5,102,745 or 5, 096,663. It is to be understood, however, that such mesh like structure may be formed by procedures other than as described in the aforementioned patents.
- the particulate catalyst support is a porous support and in a preferred embodiment, has a surface area that is greater than lm 2 /g , and preferably a surface area greater than 5m 2 /g. In most cases, the surface area does not exceed 100m 2 /g.
- the surface area is measured by the Brunauer Emmett and Teller (BET) method.
- BET Brunauer Emmett and Teller
- the support is a porous support that is heat resistant, and as representative examples of such supports there may be mentioned alumina, silicon carbide, silica, zirconia, titania, calcium aluminate, calcium aluminum titanate, a silica/alumina support etc.
- the catalyst support on which the steam-reforming catalyst is supported is a support that is in particulate form (with such supported catalyst being supported on the mesh-like structure).
- particulate as used herein includes and encompasses spherical particles, elongated particles, fibers, etc.
- the particulate support has an average particle size of at least 0.5 micron and no greater then 20 microns although larger particles may be employed. In some cases, the particle size may be as low as 0.002 micron.
- the particulates are no greater than 300 ⁇ m. preferably no greater than 200 ⁇ m and most preferably no greater than 100 ⁇ m.
- the steam catalyst reforming may be of a type known in the art.
- such catalyst includes nickel, ruthenium or rhodium, with or without promoters such as alkali metals.
- the steam-reforming catalyst (with or without a support) is supported on the mesh like structure in an amount of at least 5%, and preferably at least 10%, with the amount of catalyst generally not exceeding 60% and more generally not exceeding 50%, all by weight, based on mesh, catalyst, and, if present, particulate support.
- the mesh like structure that is formed from a steam reforming catalyst and/or functions as a support for the steam- reforming catalyst is in the form of a shaped structured packing to provide for turbulence of the gas phase flowing over the catalyst in the steam-reforming tubes.
- the mesh structure may be provided with suitable corrugations in order to provide for increased turbulence.
- the mesh like structure may include tabs or vortex generators to provide for turbulence. The presence of turbulence generators permits mixing in the radial (and longitudinal) direction and permits improved heat transfer at the wall compared to the processes know in the art.
- the structural packing can be in the form of a module such as a roll of one or more sheets that is placed into the tubes of the reactor such that the channels in the module follow the longitudinal direction of the tube.
- the roll can consist of sheets that are flat, corrugated or wavy or a combination thereof and the sheets can contain fins or holes to promote mixing.
- the sheets can also be shaped into corrugated strips that are separated from each other by a flat sheet that exactly fit the size of the tube and are held together by welds, wires, a cylindrical flat sheet or combinations thereof.
- the mesh that is formed from a steam reforming catalyst or that supports the steam-reforming catalyst may be employed in a form other than as a structured sheet.
- the mesh may be formed as rings, particles, ribbons, etc. and employed in the tubes as a packed bed. In one embodiment the particle dimensions are smaller than those of packed bed particles that are known in the prior art.
- the supported catalyst on the mesh (whether or not used as a structured packing is preferably employed as a packed bed.
- the steam-reforming catalyst which is supported on the mesh like structure may be present on the mesh like support as a coating on the wires or fibers that form the mesh like structure and/or may be present and retained in the interstices of the mesh like structure.
- the mesh may be initially coated with the particulate support, followed by addition of the steam-reforming catalyst to the particulate support present as a coating on the mesh.
- the catalyst supported on a particulate support may be coated onto the mesh.
- the particulate support with or without catalyst may be coated on the mesh by a variety of techniques, e.g., dipping or spraying.
- the supported catalyst particles may be applied to the mesh-like structure by contacting the mesh-like structure with a liquid coating composition (preferably in the form of a coating bath) that includes the particles dispersed in a liquid under conditions such that the coating composition enters or wicks into the mesh-like structure and forms a porous coating on both the interior and exterior portions of the mesh-like structure.
- a liquid coating composition preferably in the form of a coating bath
- the coating composition enters or wicks into the mesh-like structure and forms a porous coating on both the interior and exterior portions of the mesh-like structure.
- the mesh-like structure is coated with a particulate support containing active catalyst or the mesh-like structure may be coated with particles of a catalyst precursor.
- the liquid coating composition has a kinematic viscosity of no greater than 175 centistokes and a surface tension of no greater than 300 dynes/cm.
- the supported catalyst or catalyst support is coated onto the mesh by dip-coating.
- the three-dimensional mesh- like material is oxidized before coating; e.g., heating in air at a temperature of from 300°C up to 700°C.
- the mesh-like material is cleaned prior to oxidation; for example, by washing with an organic solvent such as acetone.
- the coating bath is preferably a mixed solvent system of organic solvents and water in which the particles are dispersed.
- the polarity of the solvent system is preferably lower than that of water in order to prevent high solubility of the catalyst and to obtain a good quality slurry for coating.
- the solvent system may be a mixture of water, amides, esters, and alcohols.
- the kinematic viscosity of the coating bath is preferably less than 175 centistokes and the surface tension thereof is preferably less than 300 dynes/cm.
- the mesh-like structure that is coated includes metal wires or fibers and the metal wires or fibers that are coated are selected or treated in a manner such that the surface tension thereof is higher than 50 dynes/cm, as determined by the method described in "Advances in Chemistry. 43. Contact Angle. Wettability and Adhesion. American Chemical Society. 1964.”
- the liquid coating composition preferably has a surface tension from about 50 to 300 dynes/cm, and more preferably from about 50 to 150 dynes/cm, as measured by the capillary tube method, as described in T.C.
- the liquid coating composition has a kinematic viscosity of no greater than 175 centistokes, as measured by a capillary viscometer and described in P.C. Hiemenz, “Principles of colloid and Surface Chemistry", 2 nd Ed., Marcel Dekker Inc., 1986, p. 182.
- the surface tension of the metal being coated is coordinated with the viscosity and surface tension of the liquid coating composition such that the liquid coating composition is drawn into the interior of the structure to produce a particulate coating on the mesh-like structure.
- the metal to be coated preferably has a surface tension which is greater than 50 dynes/cm and preferably is higher than the surface tension of the liquid coating composition to obtain spontaneous wetting and penetration of the liquid into the interior of the mesh.
- the structure may be heat-treated to produce the desired surface tension.
- the liquid coating composition can be prepared without any binders or adhesives for causing adherence of the particulate coating to the structure.
- the surface of the structure to be coated may also be chemically or physically modified to increase the attraction between the surface and the particles that form the coating; e j., heat treatment or chemical modification of the surface.
- the solids content of the coating bath generally is from about 2 % to about 50%, preferably from about 5% to about 30%.
- the bath may also contain additives such as surfactants, dispersants etc.
- additives such as surfactants, dispersants etc.
- the weight ratio of additives to particles in the coating bath is from 0.0001 to 0.4 and more preferably from 0.001 to 0.1.
- the mesh-like material preferably is coated by dipping the mesh-like material into a coating bath one or more times while drying or calcining in between dippings.
- the temperature of the bath is preferably at room temperature, but has to be sufficiently below the boiling point of the liquid in the bath.
- the mesh-like material that includes a porous coating comprised of a plurality of particles is dried, preferably with the material in a vertical position.
- the drying is preferably accomplished by contact with a flowing gas (such as air) at a temperature of from 20°C to 150°C more preferably from 100°C to 150°C.
- the coated mesh-like material is preferably calcined, for example, at a temperature of from 250°C to 800°C, preferably 300°C to 500°C, most preferably at about 400°C.
- the temperature and air flow are coordinated in order to produce a drying rate that does not affect adversely the catalyst coating, e ⁇ g,, cracking, blocking of pores, etc. In many cases, a slower rate of drying is preferred.
- 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. Typically, the coating thickness does not exceed 50 microns and more typically does not exceed 30 microns.
- the interior portion of the mesh material that is coated 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 in effect, determine the amount and uniformity of the coating that can be deposited in the interior of the 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 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.
- the coating bath in some cases may include additives.
- stabilizing agents there may be mentioned: a polymer like polyacrylic acid, acrylamines, organic quaternary ammonium compounds, or other special mixes which are selected based on the particles.
- an organic solvent can be used for the same purpose. Examples of such solvents are alcohols or liquid paraffins.
- Control of the pH of the slurry, for example, by addition of HNO 3 is another method of changing the viscosity and surface tension of the coating slurry.
- the particulate support with or without catalyst may be coated onto the mesh by an electrophoretic coating procedure, as described in U.S. Application Serial Number 09/156,023, filed on September 17, 1998.
- the wire mesh is employed as one of the electrodes, and the particulate support, such as an alumina support of the requisite particle size, with or without catalyst, (which preferably also includes alumina in the form of a sol to promote the adherence of larger particles to the wire mesh) is suspended in a coating bath.
- a potential is applied across the electrodes, one of which is the mesh formed from a plurality of layers of fibers, and the mesh is electrophoretically coated with the alumina support with or without catalyst.
- the steam-reforming catalyst which is preferably comprised of nickel particles with or without one or more promoters, is then added to the catalyst structure by dipping the structure (which contains the alumina coating) into or impregnating the structure with an appropriate solution that contains the nickel catalyst and preferably one or more promoters.
- the Example illustrates preparation of a catalyst by electrophoretic coating.
- the steam-reforming catalyst (with or without a particulate support) may be supported on the mesh material by entrapping or retaining the catalyst in the interstices of the mesh.
- a particulate support may be included in the mix that is used for producing the mesh whereby the mesh is produced with the particulate support retained in the interstices of the mesh.
- such mesh may be produced as described in the aforementioned patents, and with an appropriate alumina support being added to the mesh that contains the fibers and a binder, such as cellulose.
- the thus produced mesh includes the alumina particles retained in the mesh.
- the particulate support retained in the mesh is then impregnated with nickel by procedures known in the art.
- bed void volume means the open space in the portion of the reaction zone (for example the tubes of a steam reforming catalyst) that is not occupied by the mesh wherein the openings or pores in the mesh and the openings or pores in any catalyst or particulate support on the mesh is considered as being occupied by the mesh.
- the mesh is considered to be a closed sheet and any catalyst and particulate support on the mesh is considered to be free of pores.
- the term “mesh catalyst void volume” means the total of open space in the mesh and the open space in any particulate support and catalyst on the mesh.
- the “bed void volume percent” is the ratio of the bed void volume to the total volume of the portion of the reaction zone in which the mesh is placed multiplied by 100.
- the "mesh catalyst void volume percent" is the ratio of open volume in the mesh, particulate support and catalyst divided by the total volume of mesh, particulate support and catalyst (including pores or openings) multiplied by 100.
- the "mesh void volume percent” is the ratio of void volume in the mesh without catalyst or particulate support to the total volume of the mesh structure (openings and mesh material) multiplied by 100.
- the mesh like structure that is employed in the present invention has a mesh void volume percent that is at least 45%, and is preferably at least 55% and is more preferably at least 65% and still more preferably is at least about 85% or 90%.
- the mesh void volume percent does not exceed about 98%.
- the average void opening is at least 10 microns and preferably at least 20 microns.
- the steam-reforming reaction is generally effected in a tubular furnace, often referred to as a steam-reformer or a steam-reforming furnace, which furnace includes a plurality of tubes that are appropriately heated in the furnace.
- the mesh catalyst in the form of a wire mesh that is the steam-reforming catalyst or in the form of a mesh that supports the steam-reforming catalyst with or without a particulate support
- the reaction zone for example, the tubes in the furnace
- the bed void volume percent is at least 70%.
- the bed void volume percent is no greater than 97%.
- the bed void volume percent is generally between 70% and 97%.
- the bed is generally from 70% to 97% void volume percent and.
- the mesh catalyst void volume percent is at least 50% preferably at least 60% and generally does not exceed 90%.
- the catalyst is generally present on the particulate support in an amount from 3 to 20%, by weight, based on catalyst and particulate support.
- the steam reforming is generally accomplished at outlet temperatures of at least 700°C, with the outlet temperature in most cases not exceeding 900°C.
- the inlet temperature to the steam-reforming is generally in the order of at least 500°C, and generally does not exceed 600°C.
- the outlet pressure of the tubes that contain the steam-reforming catalyst is generally in the order of from about 15 to 60 bar with the pressure drop through the tubes generally not exceeding 0.42 bar/meter of tube length, and preferably not exceeding 0.31 bar/m.
- the steam- reforming feed is generally comprised of a hydrocarbon (preferably methane) and steam, with the steam-to-hydrocarbon ratios generally being at least 1.5, and generally not exceeding 6:1.
- the steam-reforming reaction may be accomplished in any one of a wide variety of steam-reforming furnaces, and may be combined with other processes; for example, a shift reaction to increase the content of hydrogen and to reduce the carbon monoxide content.
- steam reforming is effected in multiple stages where the heat is generated in one of the stages is used to provide or supplement the heat required for other stages. This can be done either in tubular reactors heated by hot gases or by using hot gases to preheat the feed to an adiabatic reactor.
- the support of 5 x 5 cm is a metal mesh with a thickness of 0.8mm.
- the metal mesh is composed of a plurality of layers of metal fibers.
- the mesh is placed vertically in a bath containing a slurry.
- the aqueous slurry contains 10 wt% alumina catalyst support with a surface area of about 10 m 2 /g, 0.11 wt% NyacolTM 20% alumina sol and 0.055 wt% of a commercial quaternary ammonium chloride agent.
- the pH of the slurry was adjusted with diluted HNO 3 to 5.5.
- the mesh is connected to the negative pole of a power supply and is placed between and parallel to two vertical metal electrodes, which are connected to the positive pole of a power supply. A potential of 5 V is applied for 2 minutes, during which the alumina is deposited into the mesh.
- the sample is calcined in air at 500°C for 60 minutes.
- the amount of catalyst support that is deposited on the mesh is 25.1% by weight of the combined mesh support and catalyst.
- the coated wire mesh is impregnated to the incipient wetness point with 1.10 g of a 20 wt% Ni(NO 3 ) 2 6H2O containing aqueous solution.
- the impregnated sample is heated in air at 525°C for 60 minutes to convert the Ni(NO 3 ) 2 to NiO. After calcination the alumina on the support contains about 15 wt% of NiO.
- EXAMPLE 2 Twenty weight percent of Nickel oxide on calcium aluminate in distilled water slurry was further milled in an Eiger Mill to obtain a slurry with a mean particle size of ⁇ 3 microns. One tenth of one percent of Stockhausen, a
- the average weight gains after each dipping were 6.1, 11.4, 16.1, 21.1, and 24.7 wt %, respectively. These coated monolith were finally subjected to calcining at
- Example 2 The same procedures for slurry and monolith preparation as Example 1 and 2 were used. Dip-coating procedures were also the same except that two additional successive coatings were carried out for three monolith structures to achieved higher catalyst loading.
- the weight gains after each dipping were 6.5, 12.2, 17.4, 22.3, 25.7, 29.1, and 31.8 wt %, respectively.
- the catalyst loading was
- the present invention is particularly advantageous in that mass transfer limitations in the catalyst are reduced by applying a thin coating of catalyst on the surface of a highly porous fibrous metal mesh. Consequently a volumetric activity can be obtained that is higher than or similar to processes of the prior art with a reduced amount of steam reforming catalyst. As a result of the high void volume of the catalyst bed and of the mesh catalyst it is possible to effect the steam reforming at a lower pressure drop than in processes of the prior art.
- the present invention permits the reaction to be effected with an improved heat transfer at the wall, e.g. by employing the mesh as a structured packing, preferably with turbulence generators that contact the wall, or as a packed bed with smaller dimensions compared to those applied in processes known in the art.
- the improved heat transfer per pressure drop and improved mass transfer allow the steam reforming process to be operated at a lower wall temperature which extends tube life.
- the lower temperature reduces coke formation on the catalyst and consequently allows the use of lower steam/carbon ratios (typically lower than 3) than in processes of the prior art. This results in a reduction of the separation costs downstream.
- the higher volumetric activity and improved heat transfer also allow a higher heat flux through the wall, which is particularly useful if a high methane conversion is required.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10712798P | 1998-11-05 | 1998-11-05 | |
US107127P | 1998-11-05 | ||
US43273799A | 1999-11-02 | 1999-11-02 | |
US432737 | 1999-11-02 | ||
PCT/US1999/026148 WO2000026137A1 (en) | 1998-11-05 | 1999-11-04 | Production of hydrogen-containing gas streams |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1127029A1 true EP1127029A1 (en) | 2001-08-29 |
Family
ID=26804424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99971397A Ceased EP1127029A1 (en) | 1998-11-05 | 1999-11-04 | Production of hydrogen-containing gas streams |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1127029A1 (pt) |
JP (1) | JP2003526590A (pt) |
KR (1) | KR20010080393A (pt) |
CN (1) | CN1350507A (pt) |
AR (1) | AR021084A1 (pt) |
AU (1) | AU1468800A (pt) |
BR (1) | BR9914728A (pt) |
CA (1) | CA2348625A1 (pt) |
WO (1) | WO2000026137A1 (pt) |
ZA (1) | ZA200103122B (pt) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6797244B1 (en) * | 1999-05-27 | 2004-09-28 | Dtc Fuel Cells Llc | Compact light weight autothermal reformer assembly |
US6746650B1 (en) * | 1999-06-14 | 2004-06-08 | Utc Fuel Cells, Llc | Compact, light weight methanol fuel gas autothermal reformer assembly |
WO2001000323A1 (en) * | 1999-06-29 | 2001-01-04 | Abb Lummus Global, Inc. | Process for coating metal fibrous material |
JP4551538B2 (ja) * | 2000-07-13 | 2010-09-29 | 株式会社フルヤ金属 | 水蒸気改質触媒の製造方法 |
ZA200306075B (en) * | 2001-02-16 | 2004-09-08 | Battelle Memorial Institute | Integrated reactors, methods of making same, and methods of conducting simultaneous exothermic and endothermic reactions. |
US7901662B2 (en) * | 2005-11-01 | 2011-03-08 | Celanese International Corporation | Steam generation apparatus and method |
WO2010089265A2 (de) * | 2009-02-09 | 2010-08-12 | Basf Se | Hydrierkatalysatoren, deren herstellung und verwendung |
WO2016080551A1 (en) * | 2014-11-20 | 2016-05-26 | Kao Corporation | Method for producing catalyst fibrous structure |
CN105663319A (zh) * | 2016-03-16 | 2016-06-15 | 石药集团河北永丰药业有限公司 | 一种治疗贫血的中药组合物、颗粒制剂及其制备方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3068525D1 (en) * | 1979-09-06 | 1984-08-16 | Ici Plc | A process and apparatus for catalytically reacting steam with a hydrocarbon in endothermic conditions |
GB8514344D0 (en) * | 1985-06-06 | 1985-07-10 | Ici Plc | Catalyst support |
US4716023A (en) * | 1986-11-13 | 1987-12-29 | Energy Research Corporation | Composite partial oxidizer and reformer |
DE3714262A1 (de) * | 1987-04-29 | 1988-11-10 | Huels Chemische Werke Ag | Plattenfoermiger katalysator zur entfernung von stickstoffoxiden aus abgasen |
DE69322129T2 (de) * | 1992-06-24 | 1999-05-12 | Shell Internationale Research Maatschappij B.V., Den Haag/S'gravenhage | Verfahren zur katalytischen Kohlenwasserstoffteiloxidation |
JPH1017303A (ja) * | 1996-06-28 | 1998-01-20 | Daikin Ind Ltd | 燃料電池用改質器 |
US20020068026A1 (en) * | 1997-08-08 | 2002-06-06 | Lawrence L. Murrell | Reactor |
-
1999
- 1999-11-04 CN CN99815103A patent/CN1350507A/zh active Pending
- 1999-11-04 AU AU14688/00A patent/AU1468800A/en not_active Abandoned
- 1999-11-04 WO PCT/US1999/026148 patent/WO2000026137A1/en not_active Application Discontinuation
- 1999-11-04 KR KR1020017005646A patent/KR20010080393A/ko not_active Application Discontinuation
- 1999-11-04 EP EP99971397A patent/EP1127029A1/en not_active Ceased
- 1999-11-04 CA CA002348625A patent/CA2348625A1/en not_active Abandoned
- 1999-11-04 AR ARP990105582A patent/AR021084A1/es not_active Application Discontinuation
- 1999-11-04 BR BR9914728-9A patent/BR9914728A/pt not_active IP Right Cessation
- 1999-11-04 JP JP2000579529A patent/JP2003526590A/ja not_active Withdrawn
-
2001
- 2001-04-17 ZA ZA2001/03122A patent/ZA200103122B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0026137A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2000026137A1 (en) | 2000-05-11 |
JP2003526590A (ja) | 2003-09-09 |
AR021084A1 (es) | 2002-06-12 |
ZA200103122B (en) | 2002-06-26 |
AU1468800A (en) | 2000-05-22 |
KR20010080393A (ko) | 2001-08-22 |
CN1350507A (zh) | 2002-05-22 |
CA2348625A1 (en) | 2000-05-11 |
BR9914728A (pt) | 2001-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2002367020B2 (en) | Structures containing carbon nanotubes and a porous support, methods of making the same, and related uses | |
US7288576B2 (en) | Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts | |
KR100362624B1 (ko) | 반응기와 촉매 구조물을 포함하는 장치, 당해 장치를 사용하는 공정 및 당해 장치에 사용하기 위한 촉매 구조물 | |
WO2010122855A1 (ja) | 一酸化炭素の選択的メタン化触媒、その製造方法及びそれを用いた装置 | |
US6388150B1 (en) | Selective hydrogenation process and catalyst therefor | |
CA2483942A1 (en) | Catalyst for partial oxidation of hydrocarbon, process for producing the catalyst, process for producing hydrogen-containing gas with a use of the catalyst, and method of using hydrogen-containing gas produced with the use of the catalyst | |
JP2008542018A (ja) | 白金、銅および鉄を含有する改善された高選択酸化触媒 | |
KR20130014364A (ko) | 금속 구조체 촉매 및 이의 제조방법 | |
EP1127029A1 (en) | Production of hydrogen-containing gas streams | |
AU689996B2 (en) | Process for preparation of supports | |
KR101511363B1 (ko) | 수증기-이산화탄소 복합개질을 위한 고내구성 금속폼 지지 촉매 및 그 제조방법 | |
MXPA01003980A (en) | Production of hydrogen-containing gas streams | |
JP2616043B2 (ja) | 触媒および触媒担体 | |
KR102141105B1 (ko) | 촉매 담지량 및 열충격시 박리 내구성이 향상된 촉매 담지용 금속 또는 세라믹 지지체의 제조 방법 | |
WO2001000323A1 (en) | Process for coating metal fibrous material | |
JP2017128818A (ja) | 金属粒子担持繊維および金属粒子担持繊維の製造方法 | |
RU2638831C1 (ru) | Способ приготовления катализатора для получения синтез-газа из метана, катализатор, приготовленный по этому способу, и способ получения синтез-газа из метана с его использованием | |
Wang et al. | Carbon nanotube-containing structures, methods of making, and processes using same | |
MXPA01007318A (es) | Procedimiento de hidrogenacion selectiva y catalizador para el mismo | |
MXPA00001359A (es) | Reactor que incluye una estructura de malla para sostener particulas cataliticas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20010417 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17Q | First examination report despatched |
Effective date: 20010828 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 20021123 |