WO2012002283A1 - メタンガスを水素に改質する触媒とその合成方法、および同触媒を用いたメタンガスの改質方法 - Google Patents
メタンガスを水素に改質する触媒とその合成方法、および同触媒を用いたメタンガスの改質方法 Download PDFInfo
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- WO2012002283A1 WO2012002283A1 PCT/JP2011/064573 JP2011064573W WO2012002283A1 WO 2012002283 A1 WO2012002283 A1 WO 2012002283A1 JP 2011064573 W JP2011064573 W JP 2011064573W WO 2012002283 A1 WO2012002283 A1 WO 2012002283A1
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- Prior art keywords
- methane gas
- gas
- palladium
- catalyst
- reforming
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000007789 gas Substances 0.000 title claims abstract description 149
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000002407 reforming Methods 0.000 title claims description 58
- 230000015572 biosynthetic process Effects 0.000 title claims description 13
- 238000003786 synthesis reaction Methods 0.000 title claims description 13
- 239000001257 hydrogen Substances 0.000 title description 36
- 229910052739 hydrogen Inorganic materials 0.000 title description 36
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 186
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 71
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000013078 crystal Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052786 argon Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 9
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 150000002697 manganese compounds Chemical class 0.000 claims description 5
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000011521 glass Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 235000002867 manganese chloride Nutrition 0.000 description 9
- 239000011565 manganese chloride Substances 0.000 description 9
- 229940099607 manganese chloride Drugs 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/16—Reducing
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- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- 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
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- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- 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
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- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- 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
- the present invention relates to a catalyst for reforming methane gas into hydrogen, a method for synthesizing the catalyst, and a method for reforming methane gas using the catalyst.
- Hydrogen is a typical clean energy, and it is indispensable that the market needs for its inexpensive manufacturing method will increase in the future.
- a method steam reforming method in which methane gas, which is a main component of natural gas, is brought into contact with steam at 700 to 800 ° C. to reform hydrogen is employed.
- this steam reforming method a high conversion efficiency of 80% or more from methane gas to hydrogen is obtained, but about 10 to 20% of methane gas remains unconverted.
- various studies have been attempted to use the residual heat of this steam reforming method to reform the unconverted residual methane gas to hydrogen. For example, Rodeng et al.
- Non-Patent Document 1 the natural gas mainly composed of methane gas that erupts from the underground contains not only water vapor but also corrosive gas such as hydrogen sulfide, so its water solubility becomes a problem with cobalt. Then, as the oxidation proceeds, the catalytic properties decrease. For this reason, when nickel, iron, or the like is used as a reforming catalyst metal, the nickel oxide or iron oxide oxidized by supplying hydrogen while heating to several hundred degrees Celsius is reduced and metallized again.
- the substance used as a support for the noble metal catalyst fine particles does not simply have a role for supporting the noble metal catalyst fine particles.
- alumina when used as a carrier, it is stable chemically and crystallographically even at a high temperature such as 700 ° C., but it is toxic as a by-product when hydrogen gas is produced by reforming methane gas. Some carbon monoxide CO is generated.
- a carbon material such as activated carbon is used as the carrier, if oxygen is mixed in the methane gas, the carbon itself can not withstand a temperature of several hundred degrees C and is ashed.
- the most inexpensive palladium catalyst fine particle that is effective for reforming methane gas to obtain hydrogen is used as a support material that is heat resistant and does not generate carbon monoxide as a byproduct.
- the present inventor has proposed that palladium catalyst fine particles are chemically deposited on the surface of manganese dioxide having a ramsdelite type crystal structure and used as a reforming catalyst (Patent Document 1).
- the present invention provides a catalyst that can efficiently convert methane gas to hydrogen gas at a relatively low temperature, a synthesis method thereof, and a methane gas reforming method that reforms methane gas into hydrogen gas.
- the issue is to provide.
- the present invention is characterized by the following.
- the method for synthesizing a methane gas reforming catalyst according to the present invention is a method for synthesizing a catalyst for reforming methane gas to hydrogen gas, wherein manganese dioxide having a ramsdelite type crystal structure is immersed in a palladium-containing aqueous solution, and the manganese dioxide is synthesized.
- the heat treatment step is performed by using manganese dioxide on which palladium is deposited, a mixed gas of methane gas and argon gas, a mixed gas of hydrogen gas and argon gas, or hydrogen gas and It is preferable to heat in a reducing atmosphere of a mixed gas with nitrogen gas.
- the heat treatment step heats the manganese dioxide on which the palladium is deposited at a temperature of 150 ° C. or more and 700 ° C. or less in a reducing atmosphere.
- manganese dioxide having a ramsdelite type crystal structure used in the palladium deposition step is prepared by adding an alkaline reagent to an aqueous solution of a manganese compound containing divalent manganese ions. It is preferable that the manganese oxide be converted into manganese oxide by adding hydrogen peroxide water and then recovering the manganese oxide and bringing it into contact with a dilute acid.
- the methane gas reforming catalyst of the present invention is a catalyst for reforming methane gas into hydrogen gas synthesized by any one of the methods described above, and that palladium is supported on manganese oxide Mn 3 O 4.
- the particle size of palladium supported on manganese oxide Mn 3 O 4 is preferably 10 nm or less.
- the methane gas reforming method of the present invention is characterized in that methane gas is brought into contact with a methane gas reforming catalyst synthesized by any of the above-described methods in an atmosphere at a temperature of 200 ° C. or more to generate hydrogen gas. To do.
- the methane gas is brought into contact with the methane gas reforming catalyst in a humid atmosphere.
- the methane gas is brought into contact with the methane gas reforming catalyst in an atmosphere substantially free of oxygen.
- the methane gas is brought into contact with the methane gas reforming catalyst at a temperature of 300 to 600 ° C.
- a catalyst capable of efficiently converting methane gas to hydrogen gas at a relatively low temperature can be synthesized.
- Pd (MnO 2 ) is a transmission electron micrograph of Pd (MnO 2 ) obtained by chemically depositing palladium catalyst fine particles on manganese dioxide having Ramsdelite type crystals in Examples.
- Pd (MnO 2 ) obtained by chemically depositing palladium catalyst fine particles on manganese dioxide having ramsdelite type crystals in the examples was heated to 300 ° C. in a mixed gas atmosphere of methane gas having a concentration of 10% and argon gas having a concentration of 90%. It is an X-ray diffraction pattern of Pd (Mn 3 O 4 ) obtained by maintaining for 4 hours. It is a transmission electron micrograph of Pd (Mn 3 O 4 ).
- Pd (Mn 3 O 4 ) is measured with an element mapping system attached to the transmission electron microscope. It is a transmission electron micrograph of metal manganese PdMn carrying palladium. This is an example in which PdMn was measured by an element mapping system attached to a transmission electron microscope.
- manganese dioxide having a ramsdelite type crystal structure (hereinafter also referred to as R-type manganese dioxide) is immersed in a palladium-containing aqueous solution to deposit palladium on the surface of the R-type manganese dioxide (palladium precipitation step).
- R-type manganese dioxide is immersed in a palladium-containing aqueous solution to deposit palladium on the surface of the R-type manganese dioxide (palladium precipitation step).
- the R-type manganese dioxide on which palladium is deposited is heated in a reducing atmosphere to change the manganese dioxide to manganese oxide Mn 3 O 4 (heat treatment step).
- a methane gas reforming catalyst Pd (Mn 3 O 4 ) is obtained.
- an aqueous solution containing metal palladium Pd such as palladium hydroxide Pd (OH) 2 (hereinafter also referred to as palladium aqueous solution) is prepared.
- the palladium aqueous solution preferably contains palladium at a concentration of 1000 ppm to 10000 ppm. Moreover, it is desirable to adjust to pH 4.8 or more and 10 or less.
- R-type manganese dioxide is added and suspended in this palladium aqueous solution. At that time, an alkaline reagent such as a sodium hydroxide aqueous solution is dropped while stirring the aqueous palladium solution so that the pH is kept at 4.8 or more for about 24 hours.
- the deposited metal palladium has a particle size (diameter) of 10 nm or less, especially 0.1 nm to 5 nm, particularly about 1 nm to 5 nm.
- R-type manganese dioxide may be previously dried at about 130 ° C., and then the R-type manganese dioxide may be suspended in an aqueous palladium solution. Further, R-type manganese dioxide immersed in distilled water may be collected by filtration and suspended in an aqueous palladium solution.
- reaction formula The reaction in which palladium is deposited on the surface of R-type manganese dioxide in the palladium deposition step is represented by the following reaction formula.
- Manganese dioxide Pd (MnO 2 ) having a ramsdelite type crystal structure on which palladium is precipitated is recovered by filtering an aqueous palladium solution in which R-type manganese dioxide is suspended. After the recovery, Pd (MnO 2 ) may be dried at about 130 ° C. in the atmosphere.
- R-type manganese dioxide suspended in an aqueous palladium solution can be synthesized according to the following steps.
- an aqueous solution of a manganese compound containing divalent manganese ions having high water solubility such as manganese chloride and manganese sulfate is prepared, and an alkali reagent such as sodium hydroxide is added to the aqueous solution to convert the manganese ions to manganese hydroxide Mn (OH ) Convert to 2 .
- an alkali reagent such as sodium hydroxide is added to the aqueous solution to convert the manganese ions to manganese hydroxide Mn (OH ) Convert to 2 .
- This is step 1 As the aqueous solution of the manganese compound containing divalent manganese, for example, an aqueous solution having a manganese ion concentration of 0.05 to 1.0 wt%, preferably 0.08 to 0.2 wt% is used.
- step 2 hydrogen peroxide water is added to an aqueous solution of a divalent manganese compound to which an alkali reagent is added to convert manganese hydroxide into manganese oxide Mn 3 O 4 having a manganese valence of 2.67.
- step 3 manganese oxide Mn 3 O 4 is diluted with a dilute acid (the dilute acid is a low concentration solution of acid such as hydrochloric acid, sulfuric acid, nitric acid, for example, an acid aqueous solution having a concentration of 0.1M to 1M. ) Is added and stirred to synthesize nano manganese dioxide having a ramsdelite type crystal structure.
- the dilute acid is a low concentration solution of acid such as hydrochloric acid, sulfuric acid, nitric acid, for example, an acid aqueous solution having a concentration of 0.1M to 1M.
- the nano manganese dioxide is a nano particle of manganese dioxide, and the nano particle is a nanometer order particle, for example, a particle having a diameter (particle diameter) of 1 to 100 nm.
- nano manganese dioxide having a ramsdelite type crystal structure has a shape such as a rod shape or a needle shape.
- step 2 maintaining the synthesis water temperature at 25 ° C. or lower is important for finally obtaining R-type manganese dioxide.
- the nano manganese dioxide having a ramsdelite-type crystal structure is immersed in an aqueous solution containing divalent manganese ions, thereby promoting nano manganese dioxide crystal growth.
- this process is also referred to as a crystal growth process. It is effective for promoting crystal growth that the pH of the aqueous solution at that time is, for example, less than 3, specifically, a strong acidity such as pH 1. The effect is particularly remarkable when sulfuric acid is used. Further, when crystal growth of nano manganese dioxide is performed, the aqueous solution is heated for a long time (for example, a time exceeding 100 hours), and finally a mixed crystal of manganese oxide having another crystal structure is obtained in the R-type crystal structure.
- the heating time for promoting the R-type crystal growth is preferably 100 hours or less, more preferably 10 to 80 hours, particularly about 60 hours.
- the heating temperature of the aqueous solution is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
- the crystal structure and size of the R-type manganese dioxide in this embodiment can be confirmed, for example, by analyzing an X-ray diffraction pattern with a general laboratory X-ray diffraction analyzer.
- Pd (MnO 2 ) is heated in a reducing atmosphere to change manganese dioxide to manganese oxide Mn 3 O 4 .
- the heat treatment is performed, for example, with the apparatus shown in FIG.
- Pd (MnO 2 ) is pressed and placed in a Pyrex (registered trademark) glass tube.
- the glass tube is heated by a heater.
- a gas cylinder for supplying gas into the glass tube and a flow meter are connected to the glass tube, and a bubbler containing distilled water is provided between the glass tube and the gas cylinder.
- a gas chromatograph for quantifying the concentration of the product gas is connected to the glass tube.
- the heat treatment is performed by supplying a mixed gas, which will be described later, into the glass tube with a gas cylinder to form a reducing atmosphere, and heating Pd (MnO 2 ) in the glass tube with a heater.
- Examples of the reducing atmosphere include a mixed gas of methane gas and argon gas, a mixed gas of hydrogen gas and argon gas, or a mixed gas of hydrogen gas and nitrogen gas.
- the mixed gas of methane gas and argon gas when the concentration of methane gas is 10% and the concentration of argon gas is 90%, the flow rate ratio (methane gas / argon gas) is preferably about 1/20 to 1/4, for example. . In particular, 1/10 to 1/5, particularly 1/9 is preferable.
- the concentration of hydrogen gas is preferably about 1 to 10%.
- the temperature of the heat treatment is, for example, preferably 150 ° C. or higher and 700 ° C. or lower, particularly 180 ° C. or higher and 600 ° C. or lower, particularly about 300 ° C.
- Pd (MnO 2 ) By heating Pd (MnO 2 ) in this temperature range, manganese dioxide carrying palladium can be effectively changed to manganese oxide Mn 3 O 4 .
- the catalyst Pd (Mn 3 O 4 ) synthesized as described above is excellent in heat resistance.
- methane gas can be efficiently converted to hydrogen gas at a relatively low temperature.
- methane gas can be supplied into a glass tube with a gas cylinder and brought into contact with the catalyst Pd (Mn 3 O 4 ), and heated at a temperature of 200 ° C. or more with a heater to generate hydrogen.
- concentration of methane gas brought into contact with the catalyst Pd (Mn 3 O 4 ) can be set to 1 to 99.9%, for example.
- methane gas is brought into contact with the catalyst Pd (Mn 3 O 4 ) in a wet (humidified) atmosphere.
- the degree of wetting (humidification) is, for example, 70% RH or more, preferably 80% RH or more.
- methane gas is passed through a bubbler containing distilled water in order to obtain a humid (humidified) atmosphere.
- methane gas is humidified, and water is contained in the methane gas in the glass tube.
- the reason why such a moist (humidified) atmosphere is used is that it is effective in reacting carbon monoxide with water and manganese oxide to decompose them into hydrogen ions and electrons.
- methane gas is brought into contact with the reforming catalyst Pd (Mn 3 O 4 ) in an atmosphere that does not substantially contain oxygen.
- substantially free of oxygen means that the oxygen concentration in the reaction system is so low that a decrease in reforming of methane gas due to the promotion of combustion of methane gas as an auxiliary combustor is not observed. . Specifically, it refers to a state where the oxygen concentration in the reaction system is 100 ppm or less, and further 20 ppm or less.
- methane gas is brought into contact with the catalyst Pd (Mn 3 O 4 ) in an atmosphere of 200 ° C. or higher, preferably 300 ° C. to 600 ° C., particularly about 300 ° C. . If the temperature exceeds 600 ° C., the cost is high, and hydrogen may not be produced at a low cost. In addition, the catalyst Pd (Mn 3 O 4 ) may deteriorate, and the reforming effect of methane gas may decrease.
- the methane gas reforming method using the catalyst Pd (Mn 3 O 4 ) is relatively low compared to the conventional method using steam at a temperature of 700 to 800 ° C. in the steam reforming method of methane gas.
- the reforming can be performed at a temperature, for example, 200 ° C. to 600 ° C., and hydrogen can be produced at low cost.
- the conversion efficiency of hydrogen is high.
- the hydrogen concentration when reforming methane gas at 300 ° C. using the catalyst Pd (Mn 3 O 4 ) is 700 times higher than the hydrogen concentration when Pd (MnO 2 ) is used at 200 ° C. It has been confirmed that.
- the reforming method of methane gas using the catalyst Pd (Mn 3 O 4 ) has an advantage that carbon monoxide is not generated as a by-product.
- Example 1 Method for synthesizing methane gas reforming catalyst Pd (Mn 3 O 4 ) (1-1) Method for synthesizing R-type manganese dioxide MnO 2 having a ramsdellite-type crystal as an initial carrier of palladium catalyst metal fine particles (1-1-1) Method for synthesizing manganese oxide Mn 3 O 4 by hydrothermal synthesis using manganese chloride as a raw material and R-type manganese dioxide MnO 2 Three steps described below using manganese chloride as a raw material R-type manganese dioxide nanoparticles were hydrothermally synthesized.
- Step 1 90 mL of ion-exchanged pure water in which 10.8 g of sodium hydroxide NaOH (special grade 99% manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in water (pH 4.6) in which manganese chloride was dissolved was added, and a magnetic stirrer was added. Stir. Manganese chloride was immediately changed to a milky white compound (manganese hydroxide Mn (OH) 2 ) by the addition of sodium hydroxide. The pH at that time was about 12.
- Step 2 54 mL of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise thereto, and when the stirring was continued, the milky white compound changed to a brown compound.
- the beaker as a reaction vessel was cooled with ice water to suppress heat generation due to the addition of hydrogen peroxide solution, and the water temperature of the reaction solution containing the brown compound was kept at 25 ° C. or lower.
- the pH of the final reaction solution was about 7.5.
- the brown compound in the reaction solution was collected on the glass filter paper using a 0.2 micro mesh glass filter paper (Advantech GS-25) and a vacuum filter.
- the compound collected on the filter paper was suspended in 500 mL of ion-exchanged pure water and washed for 1 hour by stirring with a magnetic stirrer made of Teflon (registered trademark) to obtain sample A.
- Step 3 sample B is suspended in 1 L of dilute hydrochloric acid having a concentration of 0.5 M, stirred for 8 hours, collected by filtration, and washed in 500 mL of ion-exchanged pure water for 1 hour.
- Step 3 as a crystal growth treatment, an appropriate amount of Sample B is suspended in 100 mL of a solution obtained by dissolving 18 g of manganese chloride in 500 mL of dilute hydrochloric acid having a concentration of 0.5 M, and sealed in a stoppered Erlenmeyer flask having a capacity of 100 mL. Maintained at 90 ° C. for 12 hours. Thereafter, the Erlenmeyer flask was naturally cooled to room temperature, sample B was collected by filtration, stirred and washed in 1 L of ion-exchanged pure water for 1 hour, and then dried at 110 ° C. for 12 hours at atmospheric pressure to obtain Sample C. .
- FIG. 2 shows the results of analyzing the crystal structure using a powder X-ray diffraction analyzer (RINT-2000 RINT-2000, CuK ⁇ ).
- RINT-2000 RINT-2000, CuK ⁇ powder X-ray diffraction analyzer
- step 2 when the synthesis is continued at 30 ° C. or higher without controlling the water temperature to 25 ° C. or lower, as shown in the upper pattern in FIG. 4, another type of manganese oxide Mn 2 O indicated by * mark A peak indicating the mixture of 3 appeared mixed with the peak of Mn 3 O 4 .
- the water temperature is controlled to 25 ° C. or lower (the lower pattern in FIG. 4)
- only the peak of Mn 3 O 4 is observed, which has an adverse effect on the purity of ramsdelite-type manganese dioxide obtained in the next step 3. Does not reach.
- FIG. 5 shows the influence of the heating time on the crystal growth and purity of ramsdelite-type manganese dioxide that is finally obtained in the crystal growth treatment after the completion of the synthesis step 3.
- This figure is an X-ray diffraction pattern obtained by heating the dilute hydrochloric acid to 90 ° C. for 4, 16, 24, and 40 hours instead of maintaining the dilute hydrochloric acid at 90 ° C. for 12 hours in the crystal growth treatment described above. Crystals grow as the heating time increases. When heated for 16 hours, 24 hours, and 40 hours, it can be seen from the intensity of each peak of the X-ray diffraction pattern, the sharpness of the peak, and the like that a slight crystal growth occurs compared to Sample C in FIG. However, as shown in FIG.
- FIG. 6 shows an X-ray diffraction pattern in the case of heating at 90 ° C. for 64 hours using dilute hydrochloric acid in the crystal growth treatment, and for 130 hours and 64 hours at 90 ° C. using water. From the results of FIGS. 5 and 6, the optimum heating time for promoting crystal growth under this condition is less than 100 hours.
- Step 3 the compound obtained after the completion of Step 3 was collected by filtration, and 1.6 g each was taken into three stoppered volumetric flasks and suspended in 100 mL of ion-exchanged pure water in which manganese sulfate was dissolved at a manganese ion concentration of 0.1 wt%. It was made turbid and the state was maintained at 90 ° C. for 48 hours to promote crystal growth. At that time, the pH of the suspension of each stoppered volumetric flask was adjusted to 5.2, 3, and 1, respectively. Sulfuric acid was used for this adjustment. Thereafter, the mixture was naturally cooled to room temperature, and then the compound was collected by filtration and the X-ray diffraction pattern was measured. The results are shown in FIG.
- the R-type manganese dioxide suspended in the palladium aqueous solution may be suspended in the palladium aqueous solution in advance at a temperature of about 130 ° C., or the one immersed in distilled water may be recovered by filtration and suspended in the palladium aqueous solution. You may make it cloudy.
- the pH of the suspension was kept at 6 to 7 by dropping 0.1 mol / L sodium hydroxide aqueous solution. After the lapse of 24 hours, the suspension was filtered to obtain a solid-liquid separation, and the pasty solid collected on the filter paper was dried at 130 ° C. in the atmosphere for 24 hours using a dryer.
- Pd (MnO 2 ) obtained by depositing palladium catalyst fine particles as shown in the transmission electron micrograph of FIG. 8 can be synthesized.
- a reaction system as shown in FIG. 1 0.2 gram of Pd (MnO 2 ) was pressed and placed in a Pyrex (registered trademark) glass tube having an inner diameter of 6 mm.
- Pd (MnO 2 ) in the glass tube was heated to 300 ° C. with a heater, and while maintaining the temperature, methane gas (concentration 10%) and argon gas (concentration) were passed through a bubbler filled with 30 mL of distilled water. 90%) was continuously introduced at a flow rate of 20 mL / min and heated for 4 hours.
- the change was compared and proved by measuring the X-ray diffraction patterns before and after heating at 300 ° C.
- the X-ray diffraction pattern after heating mainly shows a pattern attributed to manganese oxide Mn 3 O 4 , and clearly changed from a pattern attributed to ramsdelite type manganese dioxide.
- FIG. 10 is a transmission electron micrograph of Pd (Mn 3 O 4 ) obtained by heating Pd (MnO 2 ) in a glass tube at 300 ° C. From FIG. 10, Pd metal catalyst fine particles having a particle diameter of 5 nm or less, particularly 1 nm to 5 nm or less, can be observed on the surfaces of the rods of Mn 3 O 4 entangled.
- FIG. 11 shows an example in which Pd (Mn 3 O 4 ) is measured by an element mapping system attached to a transmission electron microscope. FIG. 11 shows that manganese and oxygen are concentrated at the position of the rod. It can also be seen that palladium is distributed on the surface of the rod.
- the composition is heated with a heater under the following conditions, and while maintaining the temperature, a mixed gas of methane gas (concentration 10%) and argon gas (concentration 90%) is flowed at a flow rate of 20 mL / min using a stainless steel pipe.
- a mixed gas of methane gas (concentration 10%) and argon gas (concentration 90%) is flowed at a flow rate of 20 mL / min using a stainless steel pipe.
- the catalyst was passed through and contacted with the catalyst in the glass tube.
- the gas after passing through and contacting the catalyst in the glass tube is introduced into Shimadzu gas chromatograph (GC-8APT, molecular sieves 5A, column oven temperature 60 ° C) to quantify the generated hydrogen concentration and carbon monoxide concentration. did.
- the heating temperature was raised from room temperature to 150 ° C. and maintained for 3 hours. No hydrogen concentration was detected at this temperature.
- the heating temperature was raised to 300 ° C. and maintained for 4 hours. At this temperature, a hydrogen concentration of 3.6% was always detected in the gas after passing and contacting the catalyst in the glass tube. In addition, the carbon monoxide concentration was hardly generated below the detection limit and could not be measured.
- the heating temperature was lowered to 200 ° C. and maintained for 1 hour. At this time, a hydrogen concentration of 1200 ppm was constantly detected. The carbon monoxide concentration was below the detection limit and could not be measured.
- the heating temperature was again raised to 300 ° C. After reaching 300 ° C., a hydrogen concentration of 2.8% was continuously detected for 1 hour. At this time, the carbon monoxide concentration was hardly generated below the detection limit, and measurement was impossible.
- a mixed gas of methane gas (concentration 10%) and argon gas (concentration 90%) was wetted by passing through a bubbler filled with 30 mL of distilled water at a flow rate of 20 mL / min, and passed through the catalyst in the glass tube. Made contact. Passing the mixed gas through a bubbler containing distilled water is effective for reacting carbon monoxide with water and manganese oxide to decompose them into hydrogen ions and electrons.
- a mixed gas of oxygen (concentration 20%) and argon gas (concentration 80%) (flow rate 32 mL / min)
- a mixed gas of methane gas (concentration 10%) and argon gas (concentration 90%) (flow rate 8 mL / min)
- Hydrogen gas is not detected under heating conditions at 300 ° C when the mixed gas is passed through a bubbler filled with distilled water and passed through and contacted with the catalyst in the glass tube at a total flow rate of 40 mL / min. It was. This is because oxygen gas promotes the combustion of methane gas as a combustion aid, and carbon dioxide is generated by carbon derived from methane, and as a result, the effect of hindering the reforming from methane to hydrogen is considered to have occurred.
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Abstract
Description
(1-1) パラジウム触媒金属微粒子の初期担体となるラムズデライト型結晶を有するR型の二酸化マンガンMnO2を合成する方法
(1-1-1) 原料に塩化マンガンを用いた水熱合成による酸化マンガンMn3O4、およびR型二酸化マンガンMnO2の合成方法
原料に塩化マンガンを用いて、以下に記述した3つのステップを通じてR型二酸化マンガンナノ粒子を水熱合成した。原料である塩化マンガンMnCl2・4H2O(和光純薬製試薬特級99%)26.7gをビーカー中のイオン交換純水225mLに溶解させた。
(1-1-2) 原料に硫酸マンガンを用いた水熱合成による酸化マンガンMn3O4、およびR型二酸化マンガンナノ粒子を合成する方法
上述した(1-1-1)の実験において、原料として塩化マンガンの代わりに硫酸マンガンMnSO4・5H2O(和光純薬製試薬特級99%)32.51gをビーカー中のイオン交換純水225mLに溶解させた。その後、各ステップにおける処理および試薬の添加量は実施例1と同様とした。ただし、ステップ3における酸処理時には濃度0.25Mの希硫酸を用いた。最後に、ステップ3終了後に得られた化合物を濾過回収し、有栓メスフラスコ3つに1.6gずつとり、マンガンイオン濃度0.1wt%で硫酸マンガンを溶解させたイオン交換純水100mLに懸濁させ、その状態を90℃、48時間保つことで結晶成長を促進させた。その際、各有栓メスフラスコの懸濁液のpHをそれぞれ5.2、3、および1に調整した。この調整には硫酸を用いた。その後、室温まで自然冷却し、次いで、化合物を濾過回収してX線回折パターンを計測した。図7にその結果を示した。
(1-2) パラジウム触媒金属微粒子を担持したラムズデライト型結晶を有するR型の二酸化マンガンMnO2からパラジウム触媒金属微粒子を担持した酸化マンガンPd(Mn3O4)を合成する方法
上述した(1-1-1)、および(1-1-2)の手法によって得られたラムズデライト型結晶を有する二酸化マンガンを、パラジウムを1000ppm、または10000ppmの濃度で含む水溶液に懸濁させて24時間攪拌した。その際、パラジウム水溶液に懸濁させるR型二酸化マンガンは予め130℃程度で乾燥処理にパラジウム水溶液に懸濁させても構わないし、蒸留水に浸しておいたものを濾過回収してパラジウム水溶液に懸濁させても構わない。次に、0.1moL/Lの水酸化ナトリウム水溶液を滴下することで同懸濁液のpHを6から7に保った。24時間経過後に同懸濁液を濾過する事で固液分離し、ろ紙上に回収されたペースト状の固体を乾燥器を使って大気中で130℃で24時間乾燥した。これらの手順によって、図8の透過型電子顕微鏡写真に示した様なパラジウム触媒微粒子を金属析出させたPd(MnO2)を合成することができる。
<実施例2>メタンガス改質触媒Pd(Mn3O4)を用いたメタンガスの水素への改質方法
上記(1-2)に記述した、Pd(Mn3O4)を主成分とする触媒(PdMnも含む)0.2グラムを、図1に示した反応系において内径6mmのパイレックス(登録商標)ガラス製チューブ内に押し固めて配置した。押し固めた触媒の両端にはグラスウールを配置し、触媒の粉末の飛散を防止した。このガラスチューブ内で合成物をヒーターで下記の条件で加熱し、その温度を維持しながらメタンガス(濃度10%)とアルゴンガス(濃度90%)の混合ガスをステンレス配管を使って流量20mL/minで蒸留水30mLを満たしたバブラーを通過させて湿潤させた後に、同ガラスチューブ内の触媒に通過・接触させた。ガラスチューブ内の触媒に通過・接触した後の気体を島津製作所製ガスクロマトグラフ(GC―8APT、モレキュラーシーブス5A、カラムオーブン温度60℃)に導入することで発生水素濃度、および一酸化炭素濃度を定量した。
Claims (10)
- メタンガスを水素ガスに改質する触媒の合成方法であって、ラムズデライト型結晶構造を有する二酸化マンガンをパラジウム含有水溶液に浸漬して前記二酸化マンガンの表面にパラジウムを析出させるパラジウム析出工程と、前記パラジウムを析出させた二酸化マンガンを還元雰囲気下で加熱して前記二酸化マンガンからパラジウムを担持した酸化マンガンMn3O4に変化させる加熱処理工程と、を含むことを特徴とするメタンガス改質触媒の合成方法。
- 前記加熱処理工程は、前記パラジウムを析出させた二酸化マンガンを、メタンガスとアルゴンガスとの混合ガス、水素ガスとアルゴンガスとの混合ガス、または、水素ガスと窒素ガスとの混合ガスの還元雰囲気下で加熱することを特徴とする請求項1に記載のメタンガス改質触媒の合成方法。
- 前記加熱処理工程は、前記パラジウムを析出させた二酸化マンガンを、還元雰囲気下で150℃以上700℃以下の温度で加熱することを特徴とする請求項1または2に記載のメタンガス改質触媒の合成方法。
- 前記パラジウム析出工程に使用されるラムズデライト型結晶構造を有する二酸化マンガンは、2価のマンガンイオンを含むマンガン化合物の水溶液にアルカリ試薬を添加して水酸化マンガンを析出させ、さらに過酸化水素水を添加して前記水酸化マンガンを酸化マンガンに変換した後、この酸化マンガンを回収して希酸と接触させて得ることを特徴とする請求項1から3のいずれか一項に記載のメタンガス改質触媒の合成方法。
- 請求項1から4のいずれかの方法によって合成された、メタンガスを水素ガスに改質する触媒であって、酸化マンガンMn3O4にパラジウムが担持されていることを特徴とするメタンガス改質触媒。
- 酸化マンガンMn3O4に担持されているパラジウムの粒径が10nm以下であることを特徴とする請求項5に記載のメタンガス改質触媒。
- 請求項1から4のいずれかの方法によって合成されたメタンガス改質触媒に、温度200℃以上の雰囲気下でメタンガスを接触させて水素ガスを生成させることを特徴とするメタンガスの改質方法。
- 湿潤雰囲気下で前記メタンガスを前記メタンガス改質触媒に接触させることを特徴とする請求項7に記載のメタンガスの改質方法。
- 実質的に酸素を含まない雰囲気下で前記メタンガスを前記メタンガス改質触媒に接触させることを特徴とする請求項7または8に記載のメタンガスの改質方法。
- 温度300~600℃で前記メタンガスを前記メタンガス改質触媒に接触させることを特徴とする請求項7から9のいずれか一項に記載のメタンガスの改質方法。
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US13/807,178 US9295975B2 (en) | 2010-06-28 | 2011-06-24 | Catalysts reforming methane gases into hydrogen and methods for synthesizing the same, and methods for reforming methane gases using said catalysts |
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WO2002078840A1 (fr) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyseur de reformage d'hydrocarbures et procede de preparation du catalyseur, et procede de reformage d'hydrocarbures mettant en oeuvre ledit catalyseur |
JP2007090342A (ja) * | 2005-09-05 | 2007-04-12 | Hideki Koyanaka | 炭化水素ガスから水素ガスを製造するための触媒材料とその製造方法、並びにその触媒材料を用いた水素ガスの製造方法 |
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JP2007090342A (ja) * | 2005-09-05 | 2007-04-12 | Hideki Koyanaka | 炭化水素ガスから水素ガスを製造するための触媒材料とその製造方法、並びにその触媒材料を用いた水素ガスの製造方法 |
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