KR20170077379A - Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof - Google Patents
Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof Download PDFInfo
- Publication number
- KR20170077379A KR20170077379A KR1020150187210A KR20150187210A KR20170077379A KR 20170077379 A KR20170077379 A KR 20170077379A KR 1020150187210 A KR1020150187210 A KR 1020150187210A KR 20150187210 A KR20150187210 A KR 20150187210A KR 20170077379 A KR20170077379 A KR 20170077379A
- Authority
- KR
- South Korea
- Prior art keywords
- porous metal
- metal foam
- catalyst
- reaction
- foam housing
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 257
- 239000006262 metallic foam Substances 0.000 title claims abstract description 180
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000011148 porous material Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000003825 pressing Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 239000010941 cobalt Substances 0.000 claims description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 35
- 229910017052 cobalt Inorganic materials 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- -1 iron-chromium-aluminum Chemical compound 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 158
- 238000003786 synthesis reaction Methods 0.000 description 75
- 239000000446 fuel Substances 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 239000011324 bead Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 238000001991 steam methane reforming Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006057 reforming reaction Methods 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012684 catalyst carrier precursor Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000696 methanogenic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product 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
- B01J23/745—Iron
-
- 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
- B01J23/75—Cobalt
-
- 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
-
- B01J32/00—
-
- B01J35/026—
-
- B01J35/08—
-
- B01J35/1057—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method of manufacturing a unit porous metal foam housing catalyst structure by pressing a catalyst formed into a predetermined shape into pores of a sheet-shaped porous metal foam structure by pressurizing means and filling the unit porous metal foam housing catalyst structure, The present invention relates to a method of manufacturing a porous metal foam housing catalyst structure and a porous metal foam housing catalyst structure produced by the above method.
The pores of the porous metal foam housing catalyst structure according to the present invention are filled with a part of the surface of the catalyst so as to be in direct contact with the porous metal foam structure so that stable and highly reactive There are advantages.
Description
The present invention relates to a porous metal foam housing catalyst structure for exothermic and endothermic reactions for the production of synthetic liquid fuels or syngas, and a process for its preparation. And more particularly, to a porous metal foam housing catalyst structure for use in a synthetic liquid fuel or syngas production technology which is low in damage to a catalyst and high in stability and efficiency in exothermic and endothermic reaction, and a method for producing the same.
Various alternative energy sources are being developed in preparation for depletion of fossil fuels. There is growing interest in the development of alternative energy using biomass. Biomass refers to the amount of living matter on earth as a quantity of energy. Biomass is important because the amount of biomass produced per year does not have to be exhausted as much as the total amount of petroleum reserves.
Biogas energy technology, which is generated from biomass waste landfill, wastewater treatment plant, and anaerobic fermentation tank of food waste, is getting attention from the viewpoint of recycling and practical use. However, the biogas has a low calorific value when burned directly, and has a problem of contamination due to impurities such as ammonia (NH 3 ). In addition, since the composition of the biogas is not uniform, direct combustion causes boiler fluctuation, which makes it difficult to supply heat uniformly.
In addition, when biomethane generated from biomass is applied as an automobile fuel, it is difficult to apply it directly like gasoline, diesel or natural gas, which is a fossil fuel, because there is insufficient research on engine, vehicle parts and exhaust gas. A separate device must be installed in the vehicle to apply the biomethane, which has not undergone a separate reforming process or concentration process, to the vehicle, resulting in economical problems.
On the other hand, when biomethane is replaced with alternative natural gas, there is no case in which biomethane is injected into the natural gas supply network in the country, and there is a problem that it is necessary to examine the stability of human health and combustibility. .
Even if a biogas plant is built and produced in a landfill or near a landfill, it is difficult to deliver it to consumers. The reason for this is that it is difficult to mass-produce biogas yet and it is not economical to provide a new supply chain. Also, there is a problem that a tanker that is proposed as an alternative has to prepare a dedicated vehicle to maintain the pressure and temperature to maintain liquefaction.
Therefore, the most realistic solution to date is to convert biogas to synthetic fuels for use as general industrial fuels. Among the various methods for the synthesis fuel conversion, there is the Fischer-Tropsch synthesis method which is an indirect liquefaction method. This is a method of producing gasoline, diesel, wax and the like by synthesizing and liquefying the supplied gas. The maximum tubing of the Fischer-Tropsch synthesis method is difficult to control the temperature in the reactor due to the severe exothermic reaction.
Therefore, various studies have been conducted on an efficient reactor and a catalyst structure for controlling the reaction temperature of the Fischer-Tropsch synthesis reaction. In addition, since the Fischer-Tropsch synthesis reaction proceeds on a large scale, it is impossible to use biogas as a small-scale dispersed raw material. Accordingly, it is possible to obtain a large amount of biomass raw material for economical operation of the Fischer- It is regarded as a big challenge of the technology to produce.
The Fischer-Tropsch synthesis reaction for producing a liquid fuel from a syngas composed of carbon monoxide and hydrogen uses a slurry reactor using a powder catalyst and a particle catalyst in the form of spheres or pellets, or a fixed bed reactor technology.
US Pat. No. 4,605,680, prior art of the Fischer-Tropsch synthesis reaction using a cobalt catalyst, is a technique for preparing cobalt catalysts supported on gamma-alumina and ita-alumina and activated with group B or B metal oxides, US Pat. No. 4,717,702 A technique for producing a cobalt catalyst having a high dispersibility of cobalt particles and a small particle size using an impregnation solution made of an organic solvent.
U.S. Patent No. 6,130,184 relates to the development of highly active cobalt catalysts through catalyst precursor and carrier precursor modifications, and U.S. Patent Nos. 6,537,945 and 6,740,621 describe techniques for developing catalysts with improved thermal stability and abrasion resistance, respectively. Recently, U.S. Patent No. 7,084,180 discloses an effective reaction heat control technique using a cobalt catalyst in a microchannel reactor.
Hereinafter, the entire process of producing the synthetic fuel using the Fischer-Tropsch synthesis reactor will be described.
Generally, in order to obtain a synthetic fuel from a natural gas using a steam methane reforming reactor and a Fischer-Tropsch synthesis reactor, synthesis gas (H 2 / CO ratio of 3 or more) obtained in the reaction process is used As a reactant of the Fischer-Tropsch synthesis reaction, a conversion process is required to a suitable synthesis gas (H 2 / CO ratio is 2).
1) a method of merging with a partial oxidation (POX) reaction process for producing synthesis gas (ratio of H 2 / CO is 1) using oxygen separated from air,
2) a method in which excess hydrogen obtained in steam methane reforming is separated and used for combustion for use in reaction heat supply, or used in a refinery process of the produced synthetic fuel,
3) Recently, three methods such as a method of merging with a dry methane reforming reaction process for producing syngas (ratio of H 2 / CO 1) using CO 2 are representative.
FIG. 12 is a process diagram showing a production method according to an embodiment of a conventional synthetic fuel production method using Fischer-Tropsch synthesis. The illustrated process shows a method of merging with a partial oxidation (POX) reaction process for producing a syngas (H 2 / CO ratio is 1). The natural gas is supplied through a steam methane reforming reaction process A synthesis gas having a H 2 / CO ratio of 3: 1 is produced and, at the same time, a synthesis gas having a H 2 / CO ratio of 1:11 is produced through partial oxidation (POX) of H 2 / CO is obtained via the steam methane reformer ratio of 3: 1 synthesis gas and merged with the
13 is a view showing a production method according to another embodiment of the method for producing a synthetic fuel by the conventional Fischer-Tropsch synthesis, wherein a synthesis gas is produced using one reaction process and one separation process, And supplying it to the reactor to produce a synthetic fuel. That is, the supply of natural gas steam methane reforming through the reaction process ratio of 3 in the H 2 / CO: used in combustion for then generating a synthesis gas more than 1, excess (excess) heat of reaction supplied by the hydrogen is separated, and H 2 /
The greatest problem in the production of synthetic fuel using the conventional Fischer-Tropsch synthesis reaction is that since the catalyst charged in the Fischer-Tropsch synthesis reactor is easily damaged due to a high exothermic reaction or endothermic reaction, It is not possible to express it.
Generally, cobalt or iron metal powder and pellet type catalysts are used in the Fischer-Tropsch synthesis reaction. Due to the severe reaction heat inside the reactor, the operation of the reactor has been seriously limited. In order to control this amount of heat, Expensive heat exchange cooling equipment was required.
Recently, a cobalt catalyst coated on a porous metal foam structure was used to control the high heat of reaction in the reactor during the Fischer-Tropsch synthesis reaction. However, due to the high temperature byproduct produced by the reaction, the cobalt catalyst is removed from the porous metal foam structure, which serves as a support, and thus does not function as a catalyst. As a result, the synthesis gas composed of carbon monoxide and hydrogen supplied to the inside of the reactor can not effectively contact the cobalt catalyst, so that the Fischer-Tropsch synthesis reaction can not be performed with high efficiency.
As described above, there is a structural problem that the conventional coating type catalyst can not withstand the Fischer-Tropsch synthesis reaction under a high temperature and vigorous condition.
In order to solve such a problem, U.S. Patent No. 4,027,476 discloses a catalyst structure in which a plurality of catalyst particles are filled in a metal matrix of Pom et al. However, since a plurality of catalysts are filled in the pores of each metal matrix, the heat generated in the catalyst is not directly transferred to the structure, thereby raising the temperature inside the catalyst filler. In addition, since the structure of the matrix is in the form of a pipe and the contact area with the catalyst is not wide, there still remains a problem that the heat transfer is insufficient at the contacting portion.
In order to solve the above-mentioned problems, the present invention provides a porous metal foam structure having a pore formed in a porous metal foil structure, wherein the pores are directly filled with the catalyst so that stable and high reactivity can be obtained without desorbing the catalyst even during severe heat and endothermic reactions. A method of manufacturing a porous metal foam housing catalyst structure, and a porous metal foam housing catalyst structure.
In order to accomplish the above objects and to solve the conventional problems, the present invention provides a method of manufacturing a catalyst structure for use in an exothermic or endothermic reaction,
A unit porous metal foam housing catalyst structure is manufactured by pressing a catalyst having a predetermined shape in the pores of a sheet-shaped porous metal foam structure by pressurizing and pressing to form a unit porous metal foam housing catalyst structure.
It is apparent to those skilled in the art that the porous metal foam housing catalyst structure may take the form of a cylinder or a polygonal column and that the shape thereof may be modified according to the shape of the interior of the reactor.
In addition, in the above manufacturing method, a porous metal foam structure, which is not filled with a catalyst for gas circulation, is inserted between upper and lower unit porous metal foam housing catalyst structures when stacking the porous metal foam housing catalyst structure. A method for manufacturing a porous metal foam housing catalyst structure for endothermic reaction is provided.
According to another aspect of the present invention, there is provided a method of manufacturing a catalyst structure for use in an exothermic or endothermic reaction, comprising the steps of: providing a porous metal foam structure in the form of a sheet; The processed catalyst is compressed by pressing means and filled, and then the porous metal foam structure is rolled and formed into a cylindrical shape and provided.
In a preferred embodiment, the catalyst may be in the form of spheres or pellets having a diameter of 0.1 to 10 mm.
In a preferred embodiment, the sheet-like porous metal structure has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm. In each pore, a part of the catalyst surface can be in direct contact with the porous metal foam structure And the porosity of the porous metal foam housing catalyst structure filled with the catalyst may be 10 to 75%.
In a more preferred embodiment, the porosity of the porous metal foam housing catalyst structure packed with the catalyst may be 20 to 55%.
In a preferred embodiment, the pores of the porous metal foam structure are closed, but the cross section of the porous metal foam structure can be made thin so that the material can pass through the upper and lower surfaces of the porous metal foam structure.
In a preferred embodiment, the material of the porous metal foam structure is one or more thermoelectric materials selected from among aluminum, iron, stainless steel, nickel, iron-chrome-aluminum alloys (Fecralloy), nickel-chromium alloys, copper, The metal can be made of. Also, the porous metal foil structure itself may be constructed such that the interior is not hollow.
In a preferred embodiment, the catalyst may be at least one selected from a cobalt-based catalyst, an iron-based catalyst, and a nickel-based catalyst.
According to another aspect of the present invention, there is provided a porous metal foam housing catalyst structure for an exothermic or endothermic reaction, comprising: a porous metal foam structure which is prepared according to a method for producing a catalyst structure used in the exothermic or endothermic reaction, And a catalyst packed in pores formed in the porous metal foam structure. The porous metal foam housing catalyst structure for a heating or endothermic reaction is provided.
In a preferred embodiment, the catalyst may be in the form of spheres or pellets having a diameter of 0.1 to 10 mm.
In a preferred embodiment, the sheet-like porous metal structure has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm. In each pore, a part of the catalyst surface can be in direct contact with the porous metal foam structure And the porosity of the porous metal foam housing catalyst structure filled with the catalyst may be 10 to 75%.
In a more preferred embodiment, the porosity of the porous metal foam housing catalyst structure packed with the catalyst may be 20 to 55%.
In a preferred embodiment, the pores of the porous metal foam structure are closed, but the cross section of the porous metal foam structure can be made thin so that the material can pass through the upper and lower surfaces of the porous metal foam structure.
In a preferred embodiment, the material of the porous metal foam structure is one or more thermoelectric materials selected from among aluminum, iron, stainless steel, nickel, iron-chrome-aluminum alloys (Fecralloy), nickel-chromium alloys, copper, The metal can be made of. Also, the porous metal foil structure itself may be constructed such that the interior is not hollow.
In a preferred embodiment, the catalyst may be at least one selected from a cobalt-based catalyst, an iron-based catalyst, and a nickel-based catalyst.
The present invention having such characteristics as described above is characterized in that when producing a synthetic liquid fuel using biogas, a porous metal foam housing catalyst structure having a cobalt-based, iron-based or nickel-based catalyst is directly filled in a porous metal foam structure, (DME) synthesis reaction, steam methane reforming reaction, carbon dioxide methane reforming reaction, carbon dioxide steam methane reforming reaction, methane partial oxidation reaction, ethane partial oxidation reaction, propane partial oxidation reaction, It is advantageous in that durability is improved due to no significant damage to the catalyst desorption during the endothermic reaction and the endothermic reaction such as the reforming reaction,
As a result, it is possible to economically produce the synthetic liquid fuel with a high efficiency and stable and high reactivity in the endothermic and endothermic reactions, thereby lowering the production cost. .
FIG. 1 is an exemplary view showing a porous metal foam housing catalyst structure manufactured according to an embodiment of the present invention,
FIG. 2 is an exemplary view showing a porous metal foam housing catalyst structure according to another embodiment of the present invention,
FIG. 3 is an exemplary view showing a method of manufacturing the porous metal foam housing catalyst structure of FIG. 2. FIG.
FIG. 4 is a view illustrating a porous metal foam housing catalyst structure manufactured according to another embodiment of the present invention.
FIG. 5 is an exemplary view showing a method of manufacturing the porous metal foam housing catalyst structure of FIG. 4,
FIG. 6 is a graph showing a reaction temperature change in the Fischer-Tropsch synthesis reaction according to Example 2 of the present invention,
7 is a graph showing a sharp increase in reaction temperature due to the reaction heat and a rapid decrease in reaction temperature according to the inactivation of the catalyst in the Fischer-Tropsch synthesis reaction according to Comparative Example 1,
8 is a graph showing an increase in the reaction temperature and a decrease in the reaction temperature with the inactivation of the catalyst in the Fischer-Tropsch synthesis reaction according to Comparative Example 2,
9 is a graph showing a temperature change in a Fischer-Tropsch synthesis reaction according to Example 4 of the present invention,
10 is a graph showing a reaction temperature change in the Fischer-Tropsch synthesis reaction according to Example 6 of the present invention,
11 is a graph showing the reaction temperature change in the Fischer-Tropsch synthesis reaction according to Example 9 of the present invention,
FIG. 12 is a process diagram showing a production method according to one embodiment of a conventional oil production method by the Fischer-Tropsch synthesis reaction,
13 is a process diagram showing a production method according to another embodiment of the conventional oil production method by the Fischer-Tropsch synthesis reaction,
Figure 14 is an illustration of an actual product of a unit porous metal foam housing catalyst structure according to the present invention.
FIG. 15 is a view showing a laminated structure for measuring the porosity of the porous metal foam housing catalyst structure according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
FIG. 1 is an exemplary view showing a porous metal foam housing catalyst structure manufactured according to an embodiment of the present invention.
As shown in the figure, the porous metal foam housing catalyst structure according to the present invention comprises a porous
The catalyst (2) may be subjected to various reactions such as a Fischer-Tropsch synthesis reaction, a methanol synthesis reaction, a dimethyl ether (DME) synthesis reaction, a steam methane reforming reaction, a carbon dioxide methane reforming reaction, a carbon dioxide steam methane reforming reaction, It is a catalyst (2) which is used for an exothermic reaction or an endothermic reaction in severe high temperature such as partial oxidation reaction, propane partial oxidation reaction and autothermal reforming reaction. These reactions are reactions that can be used in the production of synthetic liquid fuel using biogas, and may be prepared by selecting the catalyst (2) to be used in the porous metal foam housing catalyst structure according to the required reaction.
The porous metal foam structure is a porous metal foam structure having a woof shape, and is formed as a plurality of strands of wire for the sake of convenience, but is actually a metal structure having irregular pores. The shape of the porous
The metal foam structure may have open pores or closed pores depending on the porosity. However, in the case of the open pores, since the metal foam is in the form of a net having a thread-like shape, There may be restrictions. Therefore, it is preferable to use a closed pore having a wide surface of the metal foam itself so that heat transfer can be performed well for the fuming reaction or the endothermic reaction of a severe high temperature. However, in the case of the closed pores, there may be restrictions on the movement of the material. Therefore, in the method of manufacturing the porous metal foam housing catalyst structure, the cross-sectional area of the porous metal foam structure is changed so that the material can pass through the upper and lower surfaces of the porous metal foam structure. Should be adjusted.
In manufacturing, the material must be able to pass through the cross-section and have a porosity to such an extent that sufficient heat exchange can proceed through contact with the cross-section and the catalyst.
The material of the porous
Particularly, the porous
That is, the porous
At this time, each of the pores is filled in a quantity such that a part of the surface of the catalyst can be in direct contact with the porous metal foam structure, and the porosity of the porous metal foam housing catalyst structure filled with the catalyst is 10 to 75% May be 20 to 55%.
As the catalyst (2), a catalyst (2) which requires a cobalt-based catalyst, an iron-based catalyst, and a nickel-based catalyst in a reaction selected from the above reactions may be selectively used.
For reference, it means that cobalt catalysts such as cobalt or cobalt-based alloys are suitably supported on gamma-alumina and ita-alumina. Since this definition is a general expression of the catalyst, descriptions of iron-based and nickel-based catalysts are omitted.
The unit porous metal foam housing catalyst structure having such a shape is laminated to produce a cylindrical porous metal foam housing catalyst structure. As a result, a single cylindrical shape is provided. The unit porous metal foam housing catalyst structure may be bonded between the porous metal foam structures by a welding method or may be integrated by inserting the unit porous metal foam housing catalyst structure into the porous case.
The inner pore size of the porous
If the lower limit of the pore size is smaller than the lower limit of the pore size, the pore size of the porous metal foam structure is too small to fill the pores of the porous metal foam structure with the catalyst of spherical or pellet shaped particles having a predetermined size. If the upper limit of the pore size is larger than the upper limit of the pore size, the porous metal foam pores are too large to make surface contact with the charged catalyst particles, making it difficult to effectively transfer the reaction heat. Therefore, it is difficult to realize the technique of controlling the reaction heat by using the porous metal foam. It limits.
If the thickness is smaller than the thickness of the porous metal foam sheet, it is impossible to form a porous metal foam structure having a three-dimensional structure. If the porous metal foam sheet is larger than the upper limit value, spherical or pellet- ), It is limited in this way.
The spherical or pellet type catalyst is injected into the pores in the porous metal foams when the load is applied by sprinkling or laying on the porous metal foams and pressing using a pressing means such as a press or the like.
The catalyst may be spherical or pellet-shaped particles having a diameter of 0.1 to 10 mm or less, and may be a Fischer-Tropsch synthesis reaction, a steam methane reforming reaction, a carbon dioxide methane reforming reaction, a carbon dioxide steam methane reforming reaction, It is an active catalyst for severe exothermic reaction or endothermic reaction such as partial oxidation reaction, propane partial oxidation reaction, and methanogenic reforming reaction.
If the lower limit of the catalyst particle diameter is smaller than the lower limit of the catalyst particle diameter, the catalyst particles are too small to be fixed in the pores of the porous metal foam structure of a predetermined size and are difficult to be housed. If the upper limit of the catalyst particle diameter is too large, It can not be charged into the internal pores and the amount to be charged is small.
If the upper limit of the catalyst particle diameter is larger than the upper limit of the catalyst particle diameter, the above-mentioned size is preferable because the reaction activity per catalyst unit weight is low.
Preferably, one pore is filled with one catalyst. Because most of the catalysts are disposed on the surface of the carrier, the heat generated in the reaction also occurs on the surface of the carrier. Therefore, it is preferable for the heat transfer that the filled catalyst directly contacts the pores, that is, the catalyst structure. In the conventional patent (patent document 10), the porous metal foams are filled with the catalyst. However, in this document, after the catalysts having a size much smaller than that of the pores are charged so that the plurality of catalysts can be filled in the pores, Lt; / RTI > In this case, when one or two catalysts out of the pores are out of the pores due to physical or thermal impact, all the other catalysts in the pores can escape, and many catalysts in the pores do not directly contact the catalyst structure, There is a drawback that the contact surface temperature can rise.
In addition, the present invention has a separate advantage in that the pressure drop in the reactor is almost zero because of high porosity, whereas in Patent Document 10, a high pressure drop occurs due to the catalyst particles filled in the reactor.
FIG. 2 is a view illustrating a porous metal foam housing catalyst structure according to another embodiment of the present invention. FIG. 3 is a view illustrating a method of manufacturing the porous metal foam housing catalyst structure of FIG. Metal foam housing A circular porous metal foam without a catalyst is placed between the catalyst structures to secure the flow path of the synthesis gas. It is possible to improve the gas flow due to the lamination of the unit porous metal foam housing catalyst structure, .
FIG. 4 is a view illustrating a porous metal foam housing catalyst structure manufactured according to another embodiment of the present invention, and FIG. 5 is a view illustrating a method of manufacturing the porous metal foam housing catalyst structure of FIG.
The porous metal foam housing catalyst structure according to the above embodiment is similar to the cylindrical porous metal foam housing catalyst structure obtained by laminating the unit porous metal foam housing catalyst structure shown in FIG. The method is slightly different.
The basic structure of the porous metal foam housing catalyst structure is composed of a porous metal foam sheet serving as a support of the present invention and filled with a spherical or pellet shaped catalyst.
The porous metal foam sheet constituting the porous metal foam sheet has an inner pore size of 0.1 to 10 mm and a thickness of 1 to 10 mm and a spherical or pellet-shaped particle having a diameter of 0.1 to 10 mm or less same.
In the manufacturing method, a spherical or pellet-shaped catalyst is poured into pores in a sheet-shaped porous metal foam structure by a method such as squeezing and then rolled in a roll form to form a long rod-like porous metal foam housing catalyst structure .
A method for producing liquid hydrocarbons using the Fischer-Tropsch synthesis reaction using the porous metal foam housing catalyst structure produced according to the above method is as follows.
After the porous metal foam housing catalyst structure is filled in the reactor, synthesis gas is supplied. The synthesis gas may be a material composed of carbon monoxide, hydrogen, or other inert gas, methane, or carbon dioxide. More preferably, the ratio of the volume ratio of hydrogen and carbon monoxide is used in a certain ratio in accordance with the catalyst used, which is preferably 2: 1 in the case of the cobalt catalyst and 0.7: 1 to 1.3 : 1 is preferable.
The synthesis gas also has a space velocity of 0.1 to 10.0 NL / g cat / hr Lt; / RTI > to the fixed bed reactor.
If the space velocity is less than the space velocity, the reaction mass transfer rate on the catalyst surface active site is too low to proceed the Fischer-Tropsch synthesis reaction for producing the synthetic liquid fuel. If the synthesis gas is injected at a higher space velocity than the space velocity, The conversion rate of carbon monoxide can be greatly reduced.
The reaction temperature can be used in the range of 180 to 260 ° C. However, if the high temperature stability of the catalyst is secured, the reaction may be suitably performed at 210 to 240 ° C. in order to increase the conversion of carbon monoxide and increase the productivity of the synthetic liquid fuel.
Such a reaction occurs stably and continuously because there is no deformation of the catalyst packed in the porous metal foam housing catalyst structure.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
[ Example 1] Catalyst lamination
A porous metal foam sheet (pore
A porous metal foam housing catalyst structure was prepared by charging 0.4 g on average of cobalt alumina (Co / γ-Al 2 O 3 ) catalyst beads (diameter of 1 to 1.5 mm) in pores formed in one porous metal foam structure. do.
Then, a plurality of the porous metal foam housing catalyst structures were stacked and then stacked to form cobalt alumina (Co / γ-Al 2 O 3 (pore size: ) A porous metal foam housing catalyst structure (pore
[ Example 2] Preparation of reaction and reaction temperature (FTS 10 g )
A porous metal foam housing catalyst structure (pore
In order to activate the Co / γ-Al 2 O 3 catalyst in the Fischer-Tropsch synthesis reaction, the catalyst was reduced for 16 hours at 350 ° C. at a flow rate of
When the internal temperature of the reaction tube of the heat exchange reactor is increased to 190 ° C or more by circulating the heating oil heated to 230 ° C in the heating oil storage by using a pump, a Fischer-Tropsch synthesis reaction, which is a severe exothermic reaction, occurs in the reaction tube, The temperature suddenly increases.
However, when the Fischer-Tropsch synthesis reaction as a severe exothermic reaction proceeds, the exothermic reaction heat generated in the catalyst layer is effectively removed by the porous metal foam structure filled in the reaction tube and transferred to the shell portion of the heat exchange reactor, Is recovered by the heat medium oil circulating through the shell portion and the temperature of the heat medium oil is regulated constantly by the second heat exchanger controlled by the cooling water so that the reaction temperature is kept constant at 226 캜. The reaction temperature was constantly obtained without an abrupt temperature increase as shown in FIG.
[ Comparative Example One]
4.5 g of cobalt alumina pellet catalyst is charged into a 2-inch diameter reaction tube of a fixed bed reactor. In order to activate the cobalt alumina catalyst in the Fischer-Tropsch synthesis reaction, the catalyst was reduced for 16 hours at a temperature of 350 ° C. at a flow rate of 300 ml / min of H 2 before the reaction.
H 2 67 ml / min of reactant and 33 ml / min of CO are fed to the fixed bed reactor to maintain the reaction pressure at 20 atm.
When the internal temperature of the reaction tube of the fixed bed reactor is increased to 190 ° C or higher, the Fischer-Tropsch synthesis reaction occurs and the reaction temperature suddenly increases. However, since the porous metal foam structure capable of controlling the heat of the exothermic reaction is not present in the catalyst layer, The reaction temperature rapidly increases to 280 ° C, which causes carbon deposition on the surface of the cobalt alumina catalyst, deactivating the catalyst, and rapidly reducing the reaction temperature.
FIG. 7 shows a drastic increase in the reaction temperature due to the severe exothermic reaction heat and a drastic decrease in the reaction temperature with the inactivation of the catalyst.
[ Comparative Example 2]
A 1-inch diameter reaction tube of the fixed-bed reactor is charged with 8.0 g of a cobalt alumina pellet catalyst. In order to activate the cobalt alumina catalyst in the Fischer-Tropsch synthesis reaction, the catalyst was reduced for 16 hours at a temperature of 350 ° C. at a flow rate of 500 ml / min of H 2 before the reaction.
When the internal temperature of the reaction tube of the fixed bed reactor is increased to 190 ° C or higher, the Fischer-Tropsch synthesis reaction occurs and the reaction temperature suddenly increases. However, since the porous metal foam structure capable of controlling the heat of the exothermic reaction is not present in the catalyst layer, And then reaches 273 ° C., after which the activity of the catalyst is lost, so that the reaction does not proceed any more, and the reaction temperature decreases again to the initial reaction temperature. 8 shows the increase of the reaction temperature and the decrease of the reaction temperature with the inactivation of the catalyst.
[ Example 3] Reaction result (FTS 10 g )
A porous metal foam housing catalyst structure (pore
In order to activate the Co / γ-Al 2 O 3 catalyst in the Fischer-Tropsch synthesis reaction, the catalyst was reduced for 16 hours at 350 ° C. at a flow rate of
As a result of the Fischer-Tropsch synthesis reaction with the porous metal foam housing catalyst structure and the heat exchange reactor at a reaction temperature of 226 ° C, the CO conversion of the reactant was 35% and the synthesis product fuel (C 5 H 12 Or more of hydrocarbons) was 75.3%, and the amount of synthesized fuel produced was 5.9 g.
Finally, the conversion of the reactant carbon monoxide obtained from the Fischer-Tropsch synthesis reaction using the porous metal foam housing catalyst structure and the heat exchange reactor was 35.0% and the synthesis fuel production was 91.0 ml oil / (kg cat h).
Example 4 Catalyst and Reaction Preparation, Reaction Temperature and Reaction Result (Copper Foam FTS)
(Co / γ-Al 2 O 3 ) catalyst beads (having a diameter of 1 to 1.5 mm) in pores formed inside a porous metal foam sheet (pore
After the porous metal foam housing catalyst structure was filled in the reaction tube of the heat exchange reactor, the catalyst was reduced for 16 hours at a temperature of 400 ° C at a flow rate of 400 ml / min of H 2 before the reaction in order to activate the catalyst. 100 ml / min of H 2 and 50 ml / min of CO 2 are supplied to the heat exchange reactor to maintain the reaction pressure at 20 atm.
When the internal temperature of the reaction tube of the heat exchange reactor is increased to 190 ° C or more by circulating a heating medium oil heated to 250 ° C in a heating medium oil reservoir using a pump, a Fischer-Tropsch synthesis reaction, which is a severe exothermic reaction, occurs in the reaction tube, Temperature increases. However, when the Fischer-Tropsch synthesis reaction, which is a severe exothermic reaction, proceeds, the reaction heat generated in the catalyst layer is effectively removed by the porous metal foam structure filled in the reaction tube and transferred to the shell portion of the heat exchange reactor. The temperature of the heat medium oil is constantly controlled by the second heat exchanger which is recovered by the heat medium oil circulating the shell portion and regulated by the cooling water, so that the reaction temperature is kept constant at 249 deg.
FIG. 9 shows the reaction temperature change of the Fischer-Tropsch synthesis reaction according to the reaction time. As a result of the Fischer-Tropsch synthesis reaction with the porous metal foam housing catalyst structure and the heat exchange reactor at a reaction temperature of 249 ° C, the CO conversion of the reactant during the reaction time of 24 hours was 40%, the synthesis product of the liquid product, C 5 H 12 Or more of hydrocarbons) was 51.3%, and the produced amount of synthesized fuel was 9.72 g. Therefore, the final yield of the synthetic fuel obtained from the Fischer-Tropsch synthesis reaction using the porous metal foam housing catalyst structure and the heat exchange reactor was 168.7 ml oil / (kg cat h).
[ Example 5] A catalyst (FTS 30 g)
A porous metal foam sheet (pore
The porous metal foam housing catalyst structure was manufactured by charging 0.3 g on average of cobalt alumina (Co / γ-Al 2 O 3 ) catalyst beads (diameter of 1 to 1.5 mm) in the pores formed in one porous metal foam structure. do.
103 porous metal foam housing catalyst structures were prepared and laminated and packed in a reaction tube of 1 inch to prepare cobalt alumina (pore size: 3000 탆, diameter 22 mm, height 413 mm) (Pore size: 3 mm, diameter: 22 mm, height: 413 mm, cobalt alumina bead catalyst: 30.16 g) in the form of a Co / γ-Al 2 O 3 catalyst beads filled therein.
[ Example 6] Preparation of reaction experiment, temperature result (FTS 30 g )
After filling the porous metal foam housing catalyst structure (pore
400 ml / min of H 2 and 200 ml / min of
When the internal temperature of the reaction tube of the heat exchange reactor is increased to 190 ° C or more by circulating the heating oil heated to 230 ° C in the heating oil storage by using a pump, a Fischer-Tropsch synthesis reaction, which is a severe exothermic reaction, occurs in the reaction tube, Temperature increases.
However, when the Fischer-Tropsch synthesis reaction, which is a severe exothermic reaction, proceeds, the reaction heat generated in the catalyst layer is effectively removed by the porous metal foam filled in the reaction tube and transferred to the shell portion of the heat exchange reactor. The temperature of the heating oil is constantly controlled by the second heat exchanger which is regulated by the cooling water, and the reaction temperature is kept constant at 226 ° C.
FIG. 10 shows the reaction temperature change of the Fischer-Tropsch synthesis reaction according to the reaction time.
[ Example 7] Test results (FTS 30 g )
A porous metal foam housing catalyst structure (pore
In order to activate the Co / γ-Al 2 O 3 catalyst in the Fischer-Tropsch synthesis reaction, the catalyst was reduced for 16 hours at a temperature of 450 ° C. with a flow rate of H 2 1200 ml / min before the reaction.
400 ml / min of H 2 and 200 ml / min of
As a result of the Fischer-Tropsch synthesis reaction with the porous metal foam housing catalyst structure and the heat exchange reactor at a reaction temperature of 226 ° C., the CO conversion of the reactant was 39% and the synthesis product fuel (C 5 H 12 Or more of hydrocarbons) was 78.2%, and the amount of synthesized fuel produced was 16.5 g.
Therefore, the final yield of synthetic fuel obtained from the Fischer-Tropsch synthesis reaction using a porous metal foam housing catalyst structure and a heat exchange reactor was 57.0 ml oil / (kg cat h).
[ Example 8] Catalyst preparation (SMR 180 g )
A porous metal foam sheet (pore
About 1.0 g of nickel bead (Ni / γ-Al 2 O 3 ) catalyst beads (0.5 to 1.0 mm in diameter) was poured into the pores formed in one porous metal foam structure to manufacture a porous metal foam housing catalyst structure do.
133 of the porous metal foam housing catalyst structures were prepared and stacked and packed in a reaction tube of 1 inch to obtain nickel alumina (pore size: 3000 탆, diameter: 22 mm, height: 534 mm) (
[ Example 9] Reaction preparation, temperature result (SMR 180 g )
A porous metal foam housing catalyst structure (pore
To activate the nickel alumina (Ni / γ-Al 2 O 3 ) catalyst in the steam methane reforming reaction, the catalyst was reduced for 4 hours at a temperature of 800 ° C. at a H 2 5.14 L / min flow rate prior to the reaction.
Reforming reaction was carried out at 800 ° C and 1 atm by supplying reactants, CH 4 6.17 L / min and H 2 O 18.51 L / min, to the fixed bed reactor. The reaction temperature decreases at the early stage of the reaction due to the progressive steam methane reforming reaction. However, even at high reactant flow rates for the reformer operation of 1 Nm 3 / h of hydrogen production, the porous metal foam- The reaction was properly performed at a reaction temperature of about 735 ° C.
FIG. 11 shows the reaction temperature change of the steam methane reforming reaction according to the reaction time.
[ Example 10] Reaction result (SMR 180 g )
Steam methane reforming reaction was carried out by supplying CH 4 6.17 L / min and H 2 O 18.51 L / min, which are reactants, using a fixed bed reactor and a porous metal foam housing catalyst structure. In the endothermic reaction of the reforming reaction, the CH 4 conversion of 97.8%, the H 2 concentration of 74.9% (dry basis) and the 1.22 Nm 3 / h H 2 productivity was obtained.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents. Of course, such modifications are within the scope of the claims.
(1): Porous metal foam
(2) Catalyst
Claims (10)
A unit porous metal foam housing catalyst structure is manufactured by pressing a catalyst formed into a predetermined shape on the pores of a sheet-shaped porous metal foam structure by pressing means to form a unit porous metal foam housing catalyst structure,
Wherein the catalyst is in the form of a spherical or pellet having a diameter of 0.1 to 10 mm, the porous metal foil structure in sheet form has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm, Wherein the porous metal foam housing catalyst structure is filled in a quantity such that it can be in direct contact with the porous metal foam structure and the porosity of the porous metal foam housing catalyst structure filled with the catalyst is 10 to 75% .
Wherein the unit porous metal foam housing catalyst structure is inserted between the upper and lower unit porous metal foam housing catalyst structures at the time of laminating the unit porous metal foam housing catalyst structure.
A porous metal foam structure having a sheet-like porous metal foil structure, a porous metal foam housing catalyst structure having a plurality of pores formed in the porous metal foam structure, And,
Wherein the catalyst is in the form of a spherical or pellet having a diameter of 0.1 to 10 mm, the porous metal foil structure in sheet form has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm, Characterized in that the porous metal foam housing catalyst structure is filled in a quantity such that it can be in direct contact with the porous metal foam structure and the porosity of the porous metal foam housing catalyst structure filled with the catalyst is 10 to 75% .
Wherein the pores of the porous metal foam structure are closed but the cross section of the porous metal foam structure is thinned so that the porous material passes through the upper and lower surfaces of the porous metal foam structure. Gt;
The material of the porous metal foam structure is at least one thermally conductive metal selected from the group consisting of aluminum, iron, stainless steel, nickel, iron-chromium-aluminum alloy (Fecralloy), nickel-chromium alloy, copper, Wherein the interior of the porous metal foil housing catalyst structure is not hollow.
Wherein the catalyst is at least one selected from the group consisting of cobalt-based catalysts, iron-based catalysts, and nickel-based catalysts.
A porous metal foam housing catalyst structure, comprising: a porous metal foam structure made by the method according to any one of claims 1 to 3 and serving as a support; and a catalyst packed in pores formed in the porous metal foam structure .
Wherein the pores of the porous metal foam structure are closed but the cross section of the porous metal foam structure is thinned so that the porous material passes through the upper and lower surfaces of the porous metal foam structure.
The material of the porous metal foam structure is at least one thermally conductive metal selected from the group consisting of aluminum, iron, stainless steel, nickel, iron-chromium-aluminum alloy (Fecralloy), nickel-chromium alloy, copper, Wherein the interior of the porous metal foam housing catalyst structure is not hollow.
Wherein the catalyst is at least one selected from the group consisting of cobalt-based catalysts, iron-based catalysts, and nickel-based catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150187210A KR101766451B1 (en) | 2015-12-28 | 2015-12-28 | Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150187210A KR101766451B1 (en) | 2015-12-28 | 2015-12-28 | Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170077379A true KR20170077379A (en) | 2017-07-06 |
| KR101766451B1 KR101766451B1 (en) | 2017-08-08 |
Family
ID=59354019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150187210A KR101766451B1 (en) | 2015-12-28 | 2015-12-28 | Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101766451B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200060615A (en) * | 2018-11-22 | 2020-06-01 | 한국에너지기술연구원 | Electric-field assisted catalytic reactor system for biogas upgrading |
| KR102153130B1 (en) * | 2020-04-14 | 2020-09-08 | 국방과학연구소 | Methanol Reformer with enhanced heat transfer ability and Method for manufacturing the same |
| KR102280650B1 (en) * | 2021-01-21 | 2021-07-22 | 국방과학연구소 | Methanol reformer comprising pellet catalyst and method for manufacturing the same |
-
2015
- 2015-12-28 KR KR1020150187210A patent/KR101766451B1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200060615A (en) * | 2018-11-22 | 2020-06-01 | 한국에너지기술연구원 | Electric-field assisted catalytic reactor system for biogas upgrading |
| KR102153130B1 (en) * | 2020-04-14 | 2020-09-08 | 국방과학연구소 | Methanol Reformer with enhanced heat transfer ability and Method for manufacturing the same |
| KR102280650B1 (en) * | 2021-01-21 | 2021-07-22 | 국방과학연구소 | Methanol reformer comprising pellet catalyst and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101766451B1 (en) | 2017-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Ru-based catalysts for ammonia decomposition: a mini-review | |
| Alves et al. | Catalytic methane decomposition to boost the energy transition: Scientific and technological advancements | |
| Wang et al. | Nickel nanoparticles decorated nitrogen-doped carbon nanotubes (Ni/N-CNT); a robust catalyst for the efficient and selective CO2 methanation | |
| Yolcular et al. | Ni/Al2O3 catalysts and their activity in dehydrogenation of methylcyclohexane for hydrogen production | |
| Muradov | Thermocatalytic CO2-free production of hydrogen from hydrocarbon fuels | |
| De la Osa et al. | Fischer–Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions | |
| Fasanya et al. | Copper zinc oxide nanocatalysts grown on cordierite substrate for hydrogen production using methanol steam reforming | |
| Frey et al. | Optimization of structured cellular foam-based catalysts for low-temperature carbon dioxide methanation in a platelet milli-reactor | |
| KR101766451B1 (en) | Manufacturing method of porous metallic foam housing structured catalysts and porous metallic foam housing structured catalysts thereof | |
| Kechagiopoulos et al. | Sustainable hydrogen production via reforming of ethylene glycol using a novel spouted bed reactor | |
| Banu et al. | Review on COx-free hydrogen from methane cracking: Catalysts, solar energy integration and applications | |
| Byun et al. | Conceptual feasibility studies for cost-efficient and bi-functional methylcyclohexane dehydrogenation in a membrane reactor for H2 storage and production | |
| Yadav et al. | Kinetic investigation on butanol steam reforming over Ru/Al2O3 catalyst | |
| Badmaev et al. | Syngas production via partial oxidation of dimethyl ether over Rh/Ce0. 75Zr0. 25O2 catalyst and its application for SOFC feeding | |
| Jiao et al. | n-decane steam reforming for hydrogen production over mono-and bi-metallic Co-Ni/Ce-Al2O3 catalysts: Structure-activity correlations | |
| KR101308405B1 (en) | Apparatus for production of synthetic fuel with biomethane and method thereof | |
| Mehariya et al. | Fischer–Tropsch synthesis of syngas to liquid hydrocarbons | |
| Yang et al. | Review on developments of catalytic system for methanol steam reforming from the perspective of energy-mass conversion | |
| CA3197009A1 (en) | Electrically heated reforming reactor for reforming of methane and other hydrocarbons | |
| Dubey et al. | Kinetics of steam reforming of acetol over a Pt/C catalyst | |
| Iftikhar et al. | LaNi x Fe1–x O3− δ as a Robust Redox Catalyst for CO2 Splitting and Methane Partial Oxidation | |
| Kim et al. | The active phase of NaCo/ZnO catalyst for ethanol steam reforming: EXAFS and in situ XANES studies | |
| Lim et al. | Optimization of methanol synthesis reaction on Cu/ZnO/Al 2 O 3/ZrO 2 catalyst using genetic algorithm: Maximization of the synergetic effect by the optimal CO 2 fraction | |
| Pan et al. | Enhanced low-temperature CO2 methanation over bimetallic Ni–Ru catalysts | |
| Yusuf et al. | Recent Advances in Bimetallic Catalysts for Methane Steam Reforming in Hydrogen Production: Current Trends, Challenges, and Future Prospects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |