JP2016165664A - STEAM MODIFICATION CATALYST HAVING Ru ON CARRIER CONTAINING 12SrO 7Al2O3 COMPOUND HAVING MAYENITE STRUCTURE, PREFERABLY CARRIER MAINLY CONTAINING THE COMPOUND - Google Patents
STEAM MODIFICATION CATALYST HAVING Ru ON CARRIER CONTAINING 12SrO 7Al2O3 COMPOUND HAVING MAYENITE STRUCTURE, PREFERABLY CARRIER MAINLY CONTAINING THE COMPOUND Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
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- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 title 1
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 54
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000003350 kerosene Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000629 steam reforming Methods 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 238000011068 loading method Methods 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 239000003502 gasoline Substances 0.000 claims description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052799 carbon Inorganic materials 0.000 abstract description 32
- 230000008021 deposition Effects 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 29
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000010304 firing Methods 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 238000002407 reforming Methods 0.000 description 11
- 239000012018 catalyst precursor Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- -1 oxygen radical Chemical class 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004868 gas analysis Methods 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- Combustion & Propulsion (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、炭化水素の水蒸気改質触媒に関する。さらに詳しくは、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体上、好ましくは当該化合物を主成分とする担体上にＲｕが担持された炭化水素の水蒸気改質触媒に関する。 The present invention relates to a hydrocarbon steam reforming catalyst. More specifically, the present invention relates to a hydrocarbon steam reforming catalyst in which Ru is supported on a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure, and preferably on a support containing the compound as a main component.
近年、水素は燃焼すると水しか発生せず、地球環境の保全という観点からクリーンなエネルギー媒体として期待されており、最近では、燃料電池の燃料として注目されている。このような燃料としての水素の製造方法としてはこれまでに様々なものが知られている。そのうちの最も重要な方法として、メタンなどの炭化水素（ＣｎＨｍ）と水蒸気との反応により水素及び一酸化炭素を製造する方法がある。その反応式は次の式で示され、水蒸気改質反応と呼ばれている。 In recent years, hydrogen generates only water when combusted, and is expected as a clean energy medium from the viewpoint of conservation of the global environment, and has recently attracted attention as a fuel for fuel cells. Various methods for producing hydrogen as such a fuel have been known so far. Among them, the most important method is a method of producing hydrogen and carbon monoxide by a reaction between a hydrocarbon such as methane (C n H m ) and water vapor. The reaction formula is shown by the following formula and is called a steam reforming reaction.
その水蒸気改質用触媒としてＮｉ／Ａｌ２Ｏ３触媒などが工業的に利用されている。ただし、Ｎｉ触媒上では水蒸気改質反応中に未改質の炭化水素に由来する炭素析出が生じやすく、大量の水蒸気（スチーム）を触媒に導入して炭素析出を抑制し活性劣化を防いでいる。一方で、大量のスチームを改質器に投入することはエネルギー効率の観点からも、また、経済性の観点からも望ましくない。この問題を回避するために、低スチーム／カーボン比でも炭素析出が少なく、優れた活性と寿命を示すＮｉに白金族元素を共存させた触媒（特許文献１）、Ｒｈ（特許文献２）やＲｕ（特許文献３）を活性点とした触媒の研究が行われている。これらは、活性点側から性能向上を目指したものであるが、担体側から性能向上を図った試みもなされている。例えば、酸素ラジカル発現物質である１２ＣａＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ）化合物やＭａｙｅｎｉｔｅ構造を持つ１２ＳｒＯ・７Ａｌ２Ｏ３化合物を担体としたＮｉ触媒（非特許文献１）である。非特許文献１では、Ｎｉ担持量を５重量％とした場合のトルエンの水蒸気改質活性は、Ｎｉ／１２ＳｒＯ・７Ａｌ２Ｏ３ ＞ Ｎｉ／１２ＣａＯ・７Ａｌ２Ｏ３と報告されている。 A Ni / Al 2 O 3 catalyst or the like is industrially used as the steam reforming catalyst. However, on the Ni catalyst, carbon deposition derived from unreformed hydrocarbons is likely to occur during the steam reforming reaction, and a large amount of steam (steam) is introduced into the catalyst to suppress carbon deposition and prevent activity deterioration. . On the other hand, charging a large amount of steam into the reformer is not desirable from the viewpoint of energy efficiency and from the viewpoint of economy. In order to avoid this problem, a catalyst in which a platinum group element coexists with Ni, which exhibits low activity and a long life even at a low steam / carbon ratio, and has excellent activity and lifetime (Patent Document 1), Rh (Patent Document 2) and Ru. Research on catalysts using (Patent Document 3) as active sites has been conducted. These are intended to improve performance from the active site side, but attempts have been made to improve performance from the carrier side. For example, it is a Ni catalyst (Non-patent Document 1) using a 12CaO · 7Al 2 O 3 (Mayenite) compound that is an oxygen radical-expressing substance or a 12SrO · 7Al 2 O 3 compound having a Mayenite structure as a carrier. Non-Patent Document 1 reports that the steam reforming activity of toluene when the Ni loading is 5 wt% is Ni / 12SrO.7Al 2 O 3 > Ni / 12CaO.7Al 2 O 3 .
上記の様に様々な触媒が検討されているが、未だ炭素析出が少なく、かつ、優れた活性と寿命を持つ炭化水素の水蒸気改質触媒は存在しない。本発明は、この問題を鑑みてなされたものであって、その目的は炭素析出が少なく、かつ、優れた活性と寿命を持つ炭化水素の水蒸気改質触媒を提供することにある。 As described above, various catalysts have been studied. However, there is no hydrocarbon steam reforming catalyst with little carbon deposition and excellent activity and lifetime. The present invention has been made in view of this problem, and an object of the present invention is to provide a hydrocarbon steam reforming catalyst with less carbon deposition and excellent activity and life.
本発明の他の目的は、水蒸気改質により水素を製造するための原料として、重質炭化水素および／または芳香族炭化水素を含む炭化水素、例えば灯油を使用した場合であっても、炭素析出を抑制し、優れた活性を達成できる水蒸気改質触媒を提供することである。 Another object of the present invention is to deposit carbon even when hydrocarbons containing heavy hydrocarbons and / or aromatic hydrocarbons, such as kerosene, are used as raw materials for producing hydrogen by steam reforming. Is to provide a steam reforming catalyst that can achieve excellent activity.
本発明の他の目的は、以下の記載から明らかとなろう。 Other objects of the present invention will become clear from the following description.
本発明者らは、上記の目的を達成すべく鋭意検討を重ねた結果、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体上、好ましくは当該化合物を主成分とする担体上にＲｕ（ルテニウム）を担持し触媒とすることで、上記課題が達成できることを見出し、本発明を完成するに至った。すなわち、本発明の水蒸気改質触媒は、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体上、好ましくは当該化合物を主成分とする担体上にＲｕが担持されていることを特徴とする。 As a result of intensive studies to achieve the above object, the present inventors have found that Ru (on a carrier containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure, preferably on a carrier containing the compound as a main component. The present inventors have found that the above-mentioned problems can be achieved by supporting ruthenium) as a catalyst, and have completed the present invention. That is, the steam reforming catalyst of the present invention is characterized in that Ru is supported on a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure, preferably on a support mainly composed of the compound. .
すなわち本発明は、以下に関する：
１．Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と、前記担体に担持されたＲｕとを含む、炭化水素の水蒸気改質触媒。
２．上記担体が、上記１２ＳｒＯ・７Ａｌ２Ｏ３と３ＳｒＯ・Ａｌ２Ｏ３またはＳｒＣＯ３との混晶であるか、あるいは上記１２ＳｒＯ・７Ａｌ２Ｏ３と３ＳｒＯ・Ａｌ２Ｏ３およびＳｒＣＯ３との混晶である、上記１に記載の触媒。
３．上記１２ＳｒＯ・７Ａｌ２Ｏ３化合物の含有量が、担体の全重量を基準として５０重量％より大きい、上記１または２に記載の触媒。
４．上記１２ＳｒＯ・７Ａｌ２Ｏ３化合物の含有量が、担体の全重量を基準として８０重量％より大きい、上記１または２に記載の触媒。
５．Ｒｕ担持量が、担体の全重量を基準として金属換算で、０．１〜５．０重量％である、上記１〜４のいずれか１つに記載の触媒。
６．担体に担持されたＲｕの原料が、Ｒｕ塩またはＲｕ錯体である、上記１〜５のいずれか１つに記載の触媒。
７．ナフサ、ガソリン、灯油または軽油を水蒸気改質するための、上記１〜６のいずれか１つに記載の触媒。
８．炭化水素を水蒸気改質するための、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と前記担体に担持されたＲｕとを含む触媒の使用。
９．Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と前記担体に担持されたＲｕとを含む触媒に、炭化水素およびスチームを接触させることを含む、水素を製造する方法。
That is, the present invention relates to:
1. A hydrocarbon steam reforming catalyst comprising a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure and Ru supported on the support.
2. The support is a mixed crystal of 12SrO · 7Al 2 O 3 and 3SrO · Al 2 O 3 or SrCO 3 , or a mixture of 12SrO · 7Al 2 O 3 and 3SrO · Al 2 O 3 and SrCO 3. 2. The catalyst according to 1 above, which is a crystal.
3. 3. The catalyst according to 1 or 2 above, wherein the content of the 12SrO.7Al 2 O 3 compound is greater than 50% by weight based on the total weight of the support.
4). 3. The catalyst according to 1 or 2 above, wherein the content of the 12SrO.7Al 2 O 3 compound is greater than 80% by weight based on the total weight of the support.
5. 5. The catalyst according to any one of the above 1 to 4, wherein the Ru loading is 0.1 to 5.0% by weight in terms of metal based on the total weight of the support.
6). 6. The catalyst according to any one of 1 to 5 above, wherein the Ru raw material supported on the support is a Ru salt or a Ru complex.
7). The catalyst as described in any one of 1 to 6 above, for steam reforming naphtha, gasoline, kerosene or light oil.
8). Use of a catalyst comprising a 12SrO.7Al 2 O 3 compound having a Mayenite structure and Ru supported on the carrier for steam reforming a hydrocarbon.
9. A method for producing hydrogen, comprising bringing a hydrocarbon and steam into contact with a catalyst comprising a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure and Ru supported on the support.
本発明によれば、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体上、好ましくは当該化合物を主成分とする担体上にＲｕを担持し触媒とすることで、炭化水素の水蒸気改質反応において炭素析出を抑制し、優れた活性と寿命を得ることが出来る。 According to the present invention, steam reforming of hydrocarbons is carried out by supporting Ru on a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure, preferably on a support containing the compound as a main component. In the reaction, carbon deposition can be suppressed, and excellent activity and life can be obtained.
また、当該触媒により、水蒸気改質反応において、重質炭化水素および／または芳香族炭化水素を含む炭化水素、例えば灯油を原料として使用した場合であっても、炭素析出を抑制し、優れた活性を達成することができる。 In addition, the catalyst suppresses carbon deposition and has excellent activity even when a hydrocarbon containing heavy hydrocarbon and / or aromatic hydrocarbon, for example, kerosene, is used as a raw material in the steam reforming reaction. Can be achieved.
本発明による炭化水素の水蒸気改質触媒は、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を有する担体上、好ましくは当該化合物を主成分とする担体上にＲｕを担持し触媒とすることで、炭化水素の水蒸気改質反応において炭素析出を抑制し、優れた活性と寿命を得ることが出来る。 The hydrocarbon steam reforming catalyst according to the present invention comprises Ru on a carrier having a 12SrO.7Al 2 O 3 compound having a Mayenite structure, preferably a carrier containing the compound as a main component. In the hydrocarbon steam reforming reaction, carbon deposition can be suppressed, and excellent activity and life can be obtained.
すなわち、本発明の水蒸気改質触媒は、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と、前記担体に担持されたＲｕとを含む。 That is, the steam reforming catalyst of the present invention includes a support containing a 12SrO.7Al 2 O 3 compound having a Maynite structure and Ru supported on the support.
ここで、Ｍａｙｅｎｉｔｅ（マイエナイト）構造とは、Ｍａｙｅｎｉｔｅ（１２ＣａＯ・７Ａｌ２Ｏ３：Ｃ１２Ａ７）の結晶と同形の結晶構造を指すものとして広く知られており、当該構造は、Ｍａｙｅｎｉｔｅと同じく、正電荷を帯びたケージ構造を有し、このケージ内に酸素陰イオンラジカルを包接している。このようなＭａｙｅｎｉｔｅ構造を有する化合物はまた、Ｍａｙｅｎｉｔｅ型化合物（マイエナイト型化合物）とも呼ばれる。 Here, the Mayenite structure is widely known to refer to a crystal structure of the same shape as the Mayenite (12CaO.7Al 2 O 3 : C12A7) crystal, and the structure has a positive charge like the Mayenite. It has a cage structure, and oxygen anion radicals are included in the cage. A compound having such a Mayenite structure is also called a Mayenite type compound (mayenite type compound).
本発明の改質触媒で使用される担体は、このようなＭａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物（Ｓ１２Ａ７）を含み、当該化合物がＭａｙｅｎｉｔｅ構造を有することは、Ｘ線回折法（使用Ｘ線 ＣｕＫα）によって確認することができる。 The support used in the reforming catalyst of the present invention includes a 12SrO.7Al 2 O 3 compound (S12A7) having such a Maynite structure, and the fact that the compound has a Maynite structure indicates that the X-ray diffraction method (use X Line CuKα).
図１に、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物に関して３つの異なる純度を有する本発明の担体のＸＲＤプロファイルを示す。 FIG. 1 shows the XRD profiles of the inventive support having three different purities for a 12SrO.7Al 2 O 3 compound having the Mayenite structure.
上記のＭａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物は、細野等の合成方法（特許文献４）に従って製造することができ、当該方法に従って製造することが好適であるが、上記化合物の製造方法はこれに限定されるものではない。 The 12SrO.7Al 2 O 3 compound having the above Mayenite structure can be produced according to a synthesis method such as Hosono (Patent Document 4) and is preferably produced according to the method. It is not limited to this.
簡単に説明すると、上記１２ＳｒＯ・７Ａｌ２Ｏ３化合物は、例えば、特許文献４の記載に従い、出発原料としてＳｒ（ストロンチウム）含有化合物とＡｌ（アルミニウム）含有化合物をＳｒとＡｌの原子当量比で１２：１４に含む混合物を用い、焼成温度５００℃以上で、水蒸気圧を１０−３気圧以下しか含まず、酸素分圧０．２気圧以上の雰囲気下で固相反応させることによって、製造することができる。 Briefly, the 12SrO · 7Al 2 O 3 compound is obtained by using, for example, a Sr (strontium) -containing compound and an Al (aluminum) -containing compound as starting materials in an atomic equivalent ratio of Sr and Al as described in Patent Document 4. : Using the mixture contained in 14, it can be produced by subjecting it to a solid phase reaction in an atmosphere having a firing temperature of 500 ° C. or higher, a water vapor pressure of only 10 −3 atm or less, and an oxygen partial pressure of 0.2 atm or more. it can.
ここで、ストロンチウム含有化合物としては、例えば炭酸ストロンチウムまたは水酸化ストロンチウムを、アルミニウム含有化合物としては、例えばγ−アルミナまたは水酸化アルミニウムを出発原料とすることができる。 Here, as the strontium-containing compound, for example, strontium carbonate or strontium hydroxide can be used as a starting material, and as the aluminum-containing compound, for example, γ-alumina or aluminum hydroxide can be used as a starting material.
本発明では、例えばこのようにして製造した化合物を担体として使用するが、１２ＳｒＯ・７Ａｌ２Ｏ３担体合成時にその生成物は、上記化合物単独での結晶ともなり得るが、通常、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３（以後、これを「１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）」とも呼ぶ）と３ＳｒＯ・Ａｌ２Ｏ３（Ｓ３Ａ）またはＳｒＣＯ３との２種類の混晶、あるいは、それら３種類の混晶となる。本発明では、この混晶中の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）の存在割合が高い場合、例えば、５０重量％より大きい場合、好ましくは７０重量％以上、より好ましくは８０重量％以上、例えば９０重量％以上である場合に、高い活性と高い炭素析出抑制効果が得られ、本発明の担体として好適であることが見出された。 In the present invention, for example, the compound produced in this way is used as a carrier, and the product can be a crystal of the above compound alone when synthesizing a 12SrO.7Al 2 O 3 carrier, but usually has a Maynite structure. 12SrO · 7Al 2 O 3 (hereinafter, this "12SrO · 7Al 2 O 3 (Mayenite phase)" is also referred to as a) two mixed crystal of the 3SrO · Al 2 O 3 (S3A ) or SrCO 3, or, they Three types of mixed crystals are formed. In the present invention, when the presence ratio of 12SrO.7Al 2 O 3 (Mayenite phase) in the mixed crystal is high, for example, when it is larger than 50% by weight, preferably 70% by weight or more, more preferably 80% by weight or more, For example, when the content is 90% by weight or more, it has been found that high activity and a high carbon deposition inhibiting effect are obtained, which is suitable as the carrier of the present invention.
従って、本発明の１つの実施態様において、上記担体はＭａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を主成分とし、すなわち、上記担体におけるＭａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物の含有量は、担体の全重量を基準として５０重量％より大きい。また、本発明の他の好ましい実施態様において、上記担体におけるＭａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物の含有量は、担体の全重量を基準として、好ましくは７０重量％以上、より好ましくは８０重量％以上、例えば９０重量％以上である。 Accordingly, in one embodiment of the present invention, the carrier is a main component 12SrO · 7Al 2 O 3 compound having the Mayenite structure, i.e., the content of 12SrO · 7Al 2 O 3 compound having the Mayenite structure in the carrier Greater than 50% by weight, based on the total weight of the carrier. In another preferred embodiment of the present invention, the content of the 12SrO.7Al 2 O 3 compound having the Maynite structure in the carrier is preferably 70% by weight or more, more preferably 80%, based on the total weight of the carrier. % By weight or more, for example 90% by weight or more.
本発明の水蒸気改質触媒は、活性金属としてＲｕ（ルテニウム）を含み、これは上記担体に担持されている。 The steam reforming catalyst of the present invention contains Ru (ruthenium) as an active metal, which is supported on the carrier.
なお、本発明の改質触媒は、本発明の効果を損なわない限り、Ｒｕ以外の活性金属を含むことができる。そのような金属としては白金族元素、遷移金属元素などが挙げられ、例えばＲｈ（ロジウム）、Ｃｏ（コバルト）などが例示される。しかしながら、Ｒｕ以外の他の活性金属を含む場合、当該他の活性金属によっては炭素析出やアンモニア発生等の副作用を伴うおそれがあるため、そのような場合にはその量は少量であることが好ましい。従って、本発明の１つの実施態様において、Ｒｕ以外の活性金属の含有量は、金属換算で活性金属全重量の１０重量％未満、より好ましくは５重量％未満、特に好ましくは１重量％未満であること、例えばＲｕ以外の金属は実質的に含まれないことが好ましい。本発明の他の好ましい実施態様において、本発明の改質触媒は、活性金属としてＲｕのみを含む。 The reforming catalyst of the present invention can contain an active metal other than Ru as long as the effects of the present invention are not impaired. Examples of such metals include platinum group elements and transition metal elements, and examples thereof include Rh (rhodium) and Co (cobalt). However, when other active metals other than Ru are included, side effects such as carbon deposition and ammonia generation may occur depending on the other active metals. In such a case, the amount is preferably small. . Therefore, in one embodiment of the present invention, the content of the active metal other than Ru is less than 10% by weight, more preferably less than 5% by weight, particularly preferably less than 1% by weight of the total weight of the active metal in terms of metal. It is preferable that a metal other than Ru, for example, is not substantially contained. In another preferred embodiment of the invention, the reforming catalyst of the invention contains only Ru as the active metal.
また、本発明の１つの好ましい実施態様において、本発明の改質触媒は、炭素析出増加防止等の観点から、Ｎｉを実質的に含まないか、触媒に含まれるＮｉの量が、担体の全重量を基準として金属換算で５重量部未満、好ましくは０．５重量部未満、より好ましくは０．２重量部未満、特に好ましくは０．１重量部未満である。 Further, in one preferred embodiment of the present invention, the reforming catalyst of the present invention is substantially free from Ni or the amount of Ni contained in the catalyst is the entire amount of the support from the viewpoint of preventing carbon deposition increase. Based on the weight, it is less than 5 parts by weight, preferably less than 0.5 parts by weight, more preferably less than 0.2 parts by weight, particularly preferably less than 0.1 parts by weight in terms of metal.
本発明の１つの実施態様において、Ｒｕ担持量は、担体の全重量を基準として金属換算で、０．１〜１０．０重量％であることができ、例えば０．２〜８．０重量％、０．３〜６．０重量％、０．４〜４．０重量％、０．５〜３．０重量％であることができる。本発明の改質触媒におけるＲｕ担持量は、特に、担体の全重量を基準として金属換算で０．１〜５．０重量％、より好ましくは０．１〜３．０重量％であることが好ましい。これは、０．１重量％以上の担持量において特に十分な水蒸気改質活性を得ることができ、３．０重量％以下の担持量において触媒活性が減少することなく、かつ触媒としての価格も高くなりすぎずに経済性を維持できるためである。 In one embodiment of the present invention, the Ru loading can be 0.1 to 10.0% by weight, for example 0.2 to 8.0% by weight, in terms of metal based on the total weight of the support. 0.3-6.0 wt%, 0.4-4.0 wt%, 0.5-3.0 wt%. The amount of Ru supported in the reforming catalyst of the present invention is particularly 0.1 to 5.0% by weight, more preferably 0.1 to 3.0% by weight in terms of metal based on the total weight of the support. preferable. This is because particularly sufficient steam reforming activity can be obtained at a loading amount of 0.1% by weight or more, and the catalytic activity does not decrease at a loading amount of 3.0% by weight or less, and the price as a catalyst is also high. This is because the economy can be maintained without becoming too high.
また、本発明においては、改質触媒におけるＲｕ担持量が小さくても十分な触媒活性を発揮できること、および、このような小さい担持量の中でも、Ｒｕ担持量が２．０重量％のときに最大活性が得られることも見出された。従って、本発明の１つの態様において、上記のＲｕ担持量は、担体の全重量を基準として金属換算で０．５〜３．０重量％、好ましくは１．０〜２．５重量％、例えば１．５〜２．５重量％であることができる。 Further, in the present invention, sufficient catalytic activity can be exhibited even if the Ru loading amount in the reforming catalyst is small, and among these small loading amounts, the maximum is obtained when the Ru loading amount is 2.0% by weight. It has also been found that activity is obtained. Therefore, in one embodiment of the present invention, the Ru loading is 0.5 to 3.0% by weight, preferably 1.0 to 2.5% by weight in terms of metal based on the total weight of the support, for example, It can be from 1.5 to 2.5% by weight.
なお、上記改質触媒は、上記担体と上記活性金属のみからなることができるが、本発明の効果を損なわない範囲で、上記担体および活性金属の他に例えばバインダー、シリカ等を含むこともできる。 The reforming catalyst can be composed only of the support and the active metal, but can also contain, for example, a binder, silica, etc. in addition to the support and the active metal as long as the effects of the present invention are not impaired. .
本発明における上記水蒸気改質触媒は、例えば、以下の方法によって製造することができる。 The steam reforming catalyst in the present invention can be produced, for example, by the following method.
上記改質用触媒は、上記担体にＲｕを担持させることにより得られる。上記担体にＲｕを担持する方法としては、例えば、通常の含浸法、ポアフィリング（ｐｏｒｅ−ｆｉｌｌｉｎｇ）法、物理混合法などを採用できる。ここでポアフィリング法とは、予め担体の細孔容積を測定しておき、これと同じ容積分の金属塩溶液を含浸する事で金属を担持する手法である。また、物理混合法とは、担体と金属前駆体の粉末をメノウ乳鉢などですり潰しながら混合することで金属を担持する手法である。含浸法またはポアフィリング法では、Ｒｕ前駆体としてのＲｕ化合物を、例えばエタノールまたはアセトンの溶媒に溶解させた溶液を用いることができる。いずれのＲｕの担持方法においても、Ｒｕ前駆体、すなわち、担体に担持されるＲｕが由来する原料としては、ＲｕＣｌ３等に代表される塩類、Ｒｕ（ＮＯ３）３に代表される硝酸塩類、（ＮＨ４）４ＲｕＣｌ２に代表されるアンミン錯体、Ｒｕ（ＰＰｈ３）３Ｃｌ２に代表されるフォスフィン錯体類などが好適である。担持回数は１回であってもよいし、２回以上であってもよい。Ｒｕを担持した後、得られた触媒前駆体を乾燥工程に付すことができる。当該乾燥工程では、加熱乾燥や真空乾燥を適用することができる。一例としては、空気雰囲気下、あるいは窒素やアルゴン等の不活性ガス雰囲気下、温度１００℃以上で２時間以上乾燥する方法が挙げられる。乾燥後に、必要に応じて、還元処理や金属固定化処理あるいは焼成を施すことにより、本発明の触媒を得ることができる。例えば、焼成方法としては、４００℃以上８００℃以下であれば担体に充分に固定化できる。焼成時間は、３０分以上が好ましく、１時間以上がより好ましい。 The reforming catalyst can be obtained by supporting Ru on the support. As a method for supporting Ru on the carrier, for example, a normal impregnation method, a pore-filling method, a physical mixing method, and the like can be employed. Here, the pore filling method is a method for supporting a metal by measuring the pore volume of the carrier in advance and impregnating the same volume of the metal salt solution. The physical mixing method is a method for supporting a metal by mixing a carrier and a metal precursor powder while grinding with an agate mortar or the like. In the impregnation method or the pore filling method, a solution in which a Ru compound as a Ru precursor is dissolved in, for example, a solvent of ethanol or acetone can be used. In any Ru loading method, Ru precursors, that is, raw materials from which Ru supported on a carrier is derived include salts typified by RuCl 3 and the like, nitrates typified by Ru (NO 3 ) 3 , Ammine complexes represented by (NH 4 ) 4 RuCl 2 and phosphine complexes represented by Ru (PPh 3 ) 3 Cl 2 are suitable. The number of times of carrying may be one time or two or more times. After loading Ru, the resulting catalyst precursor can be subjected to a drying step. In the drying step, heat drying or vacuum drying can be applied. As an example, a method of drying at a temperature of 100 ° C. or more for 2 hours or more in an air atmosphere or an inert gas atmosphere such as nitrogen or argon can be cited. After drying, the catalyst of the present invention can be obtained by performing reduction treatment, metal immobilization treatment or firing as necessary. For example, as a baking method, if it is 400 degreeC or more and 800 degrees C or less, it can fully fix | immobilize to a support | carrier. The firing time is preferably 30 minutes or more, and more preferably 1 hour or more.
なお、本発明においては、上記担体製造時の焼成温度によって、得られる担体中の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）の含有量が変わること、具体的には、焼成温度が８００℃の場合に比べて、焼成温度が７００℃の場合に上記含有量が増加し、焼成温度が６００℃の場合にはさらに上記含有量が増加することが見出された。 In the present invention, the content of 12SrO.7Al 2 O 3 (Mayenite phase) in the obtained carrier varies depending on the firing temperature at the time of producing the carrier. Specifically, when the firing temperature is 800 ° C. It was found that the content increases when the firing temperature is 700 ° C., and the content further increases when the firing temperature is 600 ° C.
従って、本発明の１つの実施態様において、本発明は、以下の工程：
（ａ）出発原料としてＳｒ（ストロンチウム）含有化合物とＡｌ（アルミニウム）含有化合物を含む混合物を用い、８５０℃以下の焼成温度、好ましくは７５０℃以下、より好ましくは６５０℃以下の焼成温度で固相反応させることによって、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体を得ること、および
（ｂ）得られた上記担体に、Ｒｕを担持させること、
を含む、上記水蒸気改質触媒を製造する方法に関する。なお、当該方法の工程（ａ）における焼成温度の下限については、焼成が可能な温度であれば特に限定はされないが、例えば５００℃であることができる。
Thus, in one embodiment of the invention, the invention comprises the following steps:
(A) Using a mixture containing a Sr (strontium) -containing compound and an Al (aluminum) -containing compound as a starting material, a solid phase at a firing temperature of 850 ° C. or lower, preferably 750 ° C. or lower, more preferably 650 ° C. or lower. Obtaining a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure by reacting, and (b) supporting Ru on the obtained support,
A process for producing the steam reforming catalyst. The lower limit of the firing temperature in step (a) of the method is not particularly limited as long as it is a temperature at which firing is possible, and can be, for example, 500 ° C.
本発明の触媒を用いて、炭化水素を改質し、水素や合成ガスを製造することができる。 The catalyst of the present invention can be used to reform hydrocarbons and produce hydrogen and synthesis gas.
具体的には、上記改質用触媒を有する水蒸気改質器において、上記改質用触媒に炭化水素およびスチームを接触させることにより、水素ガス（典型的には、水素および一酸化炭素を含む合成ガス）を製造することができる。 Specifically, in a steam reformer having the reforming catalyst, hydrogen gas (typically synthesis containing hydrogen and carbon monoxide) is obtained by bringing hydrocarbon and steam into contact with the reforming catalyst. Gas).
上記の水蒸気改質器としては、例えば、固定床流通反応器、流動床反応器等を用いることができる。反応器の形状は、適宜選択することができ、例えば、円筒状、平板状のものが用いられる。 As said steam reformer, a fixed bed flow reactor, a fluidized bed reactor, etc. can be used, for example. The shape of the reactor can be appropriately selected. For example, a cylindrical shape or a flat shape is used.
従って、本発明の１つの態様において、本発明は、炭化水素を水蒸気改質するための、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と前記担体に担持されたＲｕとを含む触媒の使用に関する。 Therefore, in one aspect of the present invention, the present invention provides a catalyst comprising a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure and Ru supported on the support for steam reforming a hydrocarbon. About the use of.
また、本発明の他の実施態様において、本発明は、Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体と前記担体に担持されたＲｕとを含む触媒に、炭化水素およびスチームを接触させることを含む、水素を製造する方法に関する。 Further, in another embodiment of the present invention, the present invention is to contact hydrocarbons and steam with a catalyst containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure and Ru supported on the support. A method for producing hydrogen.
改質反応により水素を製造するための原料となる炭化水素としては、これらに限定はされないが、例えば、メタン、エタン、プロパン、ブタン、ペンタン、天然ガス、ＬＰガスなどの常温で気体状態の炭化水素、ならびに、ナフサ、ガソリン、灯油、軽油などの常温で液体状態の石油系炭化水素を使用することができる。好ましくは、上記炭化水素は、ナフサ、ガソリン、灯油または軽油である。中でも、灯油は比較的安価であり、さらに輸送・貯蔵において取扱いやすい。従って、上記炭化水素は、特に好ましくは灯油である。灯油等の重質な炭化水素と芳香族炭化水素を含む原料は、改質反応性が低く、炭素析出による触媒劣化が問題となるが、本発明では、上記触媒が、重質炭化水素や芳香族炭化水素のモデル物質としてのドデカンやトルエンの水蒸気改質においても、炭素析出を抑制し、優れた活性と寿命を達成できることが見出された。 The hydrocarbon used as a raw material for producing hydrogen by the reforming reaction is not limited to these. For example, methane, ethane, propane, butane, pentane, natural gas, LP gas, etc. Hydrogen and petroleum-based hydrocarbons in a liquid state at room temperature such as naphtha, gasoline, kerosene, and light oil can be used. Preferably, the hydrocarbon is naphtha, gasoline, kerosene or light oil. Of these, kerosene is relatively inexpensive and easy to handle in transportation and storage. Therefore, the hydrocarbon is particularly preferably kerosene. Raw materials containing heavy hydrocarbons and aromatic hydrocarbons, such as kerosene, have low reforming reactivity, and there is a problem of catalyst degradation due to carbon deposition. However, in the present invention, the catalyst is used for heavy hydrocarbons and aromatics. In the steam reforming of dodecane and toluene as a model substance for aromatic hydrocarbons, it was found that carbon deposition can be suppressed and excellent activity and life can be achieved.
従って、本発明の１つの好ましい実施態様において、水素を製造するための炭化水素は、重質炭化水素および／または芳香族炭化水素を含む炭化水素である。ここで、重質炭化水素としては、例えば、炭素数９〜１８のアルカン類、例えばｎ−ノナン、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカン、ｎ−トリデカン、ｎ−テトラデカン、ｎ−ペンタデカン、ｎ−ヘキサデカン、ｎ−ヘプタデカン、ｎ−オクタデカン等が挙げられ、芳香族炭化水素としては、例えばアルキルベンゼン類、ナフテノベンゼン類、ジナフテノベンゼン類、ナフタレン類、例えば、キシレン、トルエン、エチルベンゼン、１，３，５−トリメチルベンゼン等が挙げられる。本発明の別の好ましい実施態様において、水素を製造するための炭化水素は、ナフサ、ガソリン、灯油または軽油、特に好ましくは灯油である。 Thus, in one preferred embodiment of the invention, the hydrocarbon for producing hydrogen is a hydrocarbon including heavy hydrocarbons and / or aromatic hydrocarbons. Here, as the heavy hydrocarbon, for example, alkanes having 9 to 18 carbon atoms such as n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane and the like can be mentioned. Examples of the aromatic hydrocarbon include alkylbenzenes, naphthenobenzenes, dinaphthenobenzenes, naphthalenes such as xylene, toluene, ethylbenzene, 1, 3,5-trimethylbenzene and the like can be mentioned. In another preferred embodiment of the invention, the hydrocarbon for producing hydrogen is naphtha, gasoline, kerosene or light oil, particularly preferably kerosene.
上記炭化水素は、水蒸気改質の前に、必要に応じて脱硫等の前処理を施すこともできる。 The hydrocarbon may be subjected to a pretreatment such as desulfurization, if necessary, before the steam reforming.
水蒸気改質処理において、反応温度は、５００〜１２００℃、好ましくは５５０〜１０００℃であることができ、その反応圧力は、１〜４０ｋｇ／ｃｍ２、例えば５〜３０ｋｇ／ｃｍ２であることができる。また、反応を固定床方式で行う場合のガス空間速度（ＧＨＳＶ）は、好ましくは５００〜６００００ｈｒ−１、より好ましくは１０００〜５００００ｈｒ−１である。 In the steam reforming treatment, the reaction temperature can be 500 to 1200 ° C., preferably 550 to 1000 ° C., and the reaction pressure can be 1 to 40 kg / cm 2 , for example 5 to 30 kg / cm 2. it can. The gas space velocity (GHSV) when the reaction is carried out in a fixed bed system is preferably 500 to 60000 hr −1 , more preferably 1000 to 50000 hr −1 .
炭化水素に対するスチーム使用割合については、スチーム／カーボン比（Ｓ／Ｃ）で表現され、上記炭化水素中の炭素１モル当り、水蒸気０．５〜５モル、好ましくは１〜３モル、更に好ましくは２〜２．７モルであることができる。 About the steam usage ratio with respect to hydrocarbon, it is expressed by a steam / carbon ratio (S / C), and 0.5 to 5 mol, preferably 1 to 3 mol, more preferably 1 to 3 mol of water vapor per mol of carbon in the hydrocarbon. It can be 2 to 2.7 mol.
以下、実施例及び比較例に基づき本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to these Examples.
Ａ．本発明によるＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒と既報の触媒との活性の比較
Ａ−１． 触媒調製方法
（実施例１）
本発明によるＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体にＲｕを担持した触媒）は以下の方法で調製した。具体的には、水酸化ストロンチウムとγ−アルミナを１２．２４：７（Ｓｒ／Ａｌ＝１２．２４：１４）で混合した原料粉末を、アルコール中で混合し、湿性窒素中で焼成し固相反応させ、その後室温まで約２５℃／分の速度で強制冷却した。ここで、焼成温度は６００℃とした。得られた生成物がＭａｙｅｎｉｔｅ構造を有することをＸ線回折法（使用Ｘ線 ＣｕＫα）により確認するとともに（図１）、生成物である１２ＳｒＯ・７Ａｌ２Ｏ３、３ＳｒＯ・Ａｌ２Ｏ３、ＳｒＣＯ３混晶中の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度を、Ｘ線回折法における１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）に帰属される２θ＝３２．３°の回折線強度、３ＳｒＯ・Ａｌ２Ｏ３に帰属される２θ＝３１．８°の回折線強度、ＳｒＣＯ３に帰属される２θ＝２５．１°の回折線強度等から求めた。以下にその詳細を示す。
A. Comparison of activity of Ru / 12SrO.7Al 2 O 3 catalyst according to the present invention and previously reported catalysts A-1. Catalyst preparation method (Example 1)
Ru / 12SrO.7Al 2 O 3 (a catalyst having Ru supported on a support containing a 12SrO.7Al 2 O 3 compound having a Mayenite structure) according to the present invention was prepared by the following method. Specifically, a raw material powder obtained by mixing strontium hydroxide and γ-alumina at 12.24: 7 (Sr / Al = 12.24: 14) is mixed in alcohol, fired in wet nitrogen, and solid phase. The reaction was followed by forced cooling to room temperature at a rate of about 25 ° C./min. Here, the firing temperature was 600 ° C. It is confirmed by X-ray diffraction method (used X-ray CuKα) that the obtained product has a Maynite structure (FIG. 1), and the products 12SrO · 7Al 2 O 3 , 3SrO · Al 2 O 3 , SrCO 12SrO · 7Al 2 O 3 (Mayenite phase) diffraction intensity of purity, 2θ = 32.3 ° attributed to 12SrO · 7Al 2 O 3 (Mayenite phase) in the X-ray diffraction method in the 3 mixed crystal, 3SrO · It was determined from the diffraction line intensity of 2θ = 31.8 ° attributed to Al 2 O 3 and the diffraction line intensity of 2θ = 25.1 ° attributed to SrCO 3 . The details are shown below.
この様にして求めた本担体の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度は９２重量％であった。 The 12SrO.7Al 2 O 3 (Mayenite phase) purity of the support thus obtained was 92% by weight.
この１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は、担体の全重量を基準として金属換算で、０．５重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例１の炭化水素の水蒸気改質触媒を得た。 A catalyst precursor was obtained by impregnating a 12SrO · 7Al 2 O 3 carrier having a purity of 92% by weight with 12SrO · 7Al 2 O 3 (Mayenite phase) with a mixed solution of RuCl 3 dissolved in ethanol. The amount of impregnated Ru was 0.5% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 1.
（比較例１）
非特許文献１で最も活性が高いとされるＮｉ／１２ＳｒＯ・７Ａｌ２Ｏ３を比較試料とした。本触媒は以下の方法で調製した。担体である１２ＳｒＯ・７Ａｌ２Ｏ３は実施例１と同様に合成した。１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度は９２重量％であった。この担体にＮｉ（ＮＯ３）２水溶液を含浸させることで触媒前駆体を得た。Ｎｉ含浸量は最大活性が得られる５重量％（担体の全重量を基準とする金属換算）とした。その前駆体を１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して比較例１の触媒を得た。
(Comparative Example 1)
Ni / 12SrO · 7Al 2 O 3, which has the highest activity in Non-Patent Document 1, was used as a comparative sample. This catalyst was prepared by the following method. The carrier 12SrO.7Al 2 O 3 was synthesized in the same manner as in Example 1. The purity of 12SrO.7Al 2 O 3 (Maynite phase) was 92% by weight. The catalyst precursor was obtained by impregnating the support with an aqueous Ni (NO 3 ) 2 solution. The amount of Ni impregnation was 5% by weight (metal conversion based on the total weight of the support) at which the maximum activity was obtained. The precursor was dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a catalyst of Comparative Example 1.
（比較例２）
ズードケミー社の工業用Ｒｕ／Ａｌ２Ｏ３触媒（商品名ＲＵＡ）も比較試料とした。Ｒｕ担持量は、担体の全重量を基準として金属換算で、２．０重量％であった。これを比較例２の炭化水素の水蒸気改質触媒とした。
(Comparative Example 2)
An industrial Ru / Al 2 O 3 catalyst (trade name RUA) manufactured by Sud Chemie was also used as a comparative sample. The amount of Ru supported was 2.0% by weight in terms of metal based on the total weight of the carrier. This was used as the hydrocarbon steam reforming catalyst of Comparative Example 2.
（比較例３）
実施例１におけるＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒の１２ＳｒＯ・７Ａｌ２Ｏ３担体の優位性を確認する為、Ｒｕ／１２ＣａＯ・７Ａｌ２Ｏ３触媒を比較試料とした。Ｒｕ／１２ＣａＯ・７Ａｌ２Ｏ３は以下の方法で調製した。担体である１２ＣａＯ・７Ａｌ２Ｏ３は特許文献４に従い合成した。この１２ＣａＯ・７Ａｌ２Ｏ３担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は担体の全重量を基準として金属換算で０．５重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して比較例３の炭化水素の水蒸気改質触媒を得た。
(Comparative Example 3)
In order to confirm the superiority of the 12SrO · 7Al 2 O 3 support of the Ru / 12SrO · 7Al 2 O 3 catalyst in Example 1, a Ru / 12CaO · 7Al 2 O 3 catalyst was used as a comparative sample. Ru / 12CaO.7Al 2 O 3 was prepared by the following method. 12CaO · 7Al 2 O 3 as a carrier was synthesized according to Patent Document 4. A catalyst precursor was obtained by impregnating the 12CaO · 7Al 2 O 3 carrier with a mixed solution in which RuCl 3 was dissolved in ethanol. The Ru impregnation amount was 0.5% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Comparative Example 3.
Ａ−２． 水蒸気改質活性と炭素析出量の測定方法
触媒の性能試験は、常圧の固定床流通反応試験装置で行った。性能試験に先立ち各触媒を純Ｈ２中で６００℃で１時間前処理した。炭化水素には炭素析出が起きやすいトルエンを用いた。反応は６００℃、水蒸気／炭素比＝２．０ ｍｏｌ／ｍｏｌ、触媒重量／トルエン比＝１３．５ ｇ ｈ ｍｏｌ−１の条件で行った。反応時間は１８０分とした。ガス分析はＦＩＤ型ガスクロマトグラフで行った。活性は次式で示されるトルエン転化率で見積もった。
A-2. Measuring method of steam reforming activity and carbon deposition amount The performance test of the catalyst was carried out by a fixed bed flow reaction test apparatus at normal pressure. Prior to the performance test, each catalyst was pretreated in pure H 2 at 600 ° C. for 1 hour. As the hydrocarbon, toluene was used which is likely to cause carbon deposition. The reaction was carried out under the conditions of 600 ° C., water vapor / carbon ratio = 2.0 mol / mol, catalyst weight / toluene ratio = 13.5 g h mol −1 . The reaction time was 180 minutes. The gas analysis was performed with an FID type gas chromatograph. The activity was estimated by the toluene conversion represented by the following formula.
トルエン転化率（％）＝
（（入口トルエン濃度）−（出口トルエン濃度））／ （入口トルエン濃度）× １００
Toluene conversion rate (%) =
((Inlet toluene concentration) − (Outlet toluene concentration)) / (Inlet toluene concentration) × 100
炭素析出量は、反応後の試料をＴＧ−ＤＴＡ装置に移し替え、空気中で昇温することで見積もった。 The amount of carbon deposition was estimated by transferring the sample after the reaction to a TG-DTA apparatus and raising the temperature in the air.
Ａ−３． 水蒸気改質活性と炭素析出量の測定結果
表１は、Ａ−１で述べた各触媒の活性と炭素析出量をまとめたものである。本発明による実施例１では、５０．９％のトルエン転化率が得られ、炭素析出は起こっていないことが確認された。
A-3. Measurement results of steam reforming activity and carbon deposition amount Table 1 summarizes the activity and carbon deposition amount of each catalyst described in A-1. In Example 1 according to the present invention, a toluene conversion of 50.9% was obtained, and it was confirmed that no carbon deposition occurred.
比較例１では、実施例１と同一の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の担体に５．０重量％のＮｉが担持されている。比較例１の触媒のトルエン転化率は４９．２％であり、実施例１の活性（５０．９％）とほぼ同じであったが、３０．３ ｍｇ−Ｃ／ｇ−ｃａｔ．の炭素が析出していた。これらの結果より、ＲｕはＮｉよりも水蒸気改質活性が高く、かつ、炭素を析出させないという耐コーキング性にも優れていることが明らかとなった。 In Comparative Example 1, 5.0% by weight of Ni is supported on the same 12SrO.7Al 2 O 3 (Mayenite phase) purity of 92% by weight as in Example 1. The toluene conversion of the catalyst of Comparative Example 1 was 49.2%, which was almost the same as the activity of Example 1 (50.9%), but 30.3 mg-C / g-cat. Of carbon was precipitated. From these results, it has been clarified that Ru has higher steam reforming activity than Ni and is excellent in coking resistance that carbon is not deposited.
比較例２の工業用Ｒｕ／Ａｌ２Ｏ３触媒は、炭素析出は起こらなかったものの、トルエン転化率２７．２％しか示さず低活性であった。比較例２のＲｕ担持量は２．０重量％であり、実施例１の本発明によるＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒のそれは０．５重量％である。Ｒｕ担持量の低い本発明によるＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒が、Ｒｕ担持量の高いＲｕ／Ａｌ２Ｏ３よりも高い活性を示すことは、Ａｌ２Ｏ３に対する１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）担体の優位性を明確に示している。 Although the industrial Ru / Al 2 O 3 catalyst of Comparative Example 2 did not cause carbon deposition, it exhibited only a toluene conversion of 27.2% and was low in activity. The Ru loading of Comparative Example 2 is 2.0% by weight, and that of the Ru / 12SrO.7Al 2 O 3 catalyst according to the present invention of Example 1 is 0.5% by weight. Ru / 12SrO · 7Al 2 O 3 catalyst according lower invention of Ru supported amount, to exhibit a higher activity than higher Ru / Al 2 O 3 of Ru supported amount, Al 2 O 3 12SrO · 7Al 2 O 3 with respect to (Mayenite phase) The superiority of the carrier is clearly shown.
比較例３のＲｕ／１２ＣａＯ・７Ａｌ２Ｏ３触媒は、炭素析出は認められなかったものの、９．１％のトルエン転化率しか示さなかった。本発明による実施例１のＲｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒は５０．９％の転化率を示しており、先の比較例２の結果も考え合わせると、Ｒｕと１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）の組み合わせが高活性でかつ炭素を析出させない特異な組み合わせであることが明らかである。
表１
The Ru / 12CaO.7Al 2 O 3 catalyst of Comparative Example 3 showed only 9.1% toluene conversion, although no carbon deposition was observed. The Ru / 12SrO.7Al 2 O 3 catalyst of Example 1 according to the present invention shows a conversion rate of 50.9%, and considering the result of Comparative Example 2 above, Ru and 12SrO.7Al 2 O 3 ( It is clear that the combination of the Mayenite phase) is a unique combination that is highly active and does not precipitate carbon.
Table 1
Ｂ．Ｒｕ／１２ＳｒＯ・７Ａｌ２Ｏ３触媒におけるＲｕ原料の影響とＲｕ含有量の最適化
Ｂ−１． 触媒調製方法
B. Effect of Ru raw material and optimization of Ru content in Ru / 12SrO.7Al 2 O 3 catalyst B-1. Catalyst preparation method
（実施例２）
実施例１と同様に１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体を合成した。この担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は、担体の全重量を基準として金属換算で、１．０重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例２の炭化水素の水蒸気改質触媒を得た。
(Example 2)
Was synthesized similarly 12SrO · 7Al 2 O 3 (Mayenite phase) Purity 92% by weight of 12SrO · 7Al 2 O 3 carrier as in Example 1. The catalyst precursor was obtained by impregnating this support with a mixed solution in which RuCl 3 was dissolved in ethanol. The Ru impregnation amount was 1.0% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 2.
（実施例３）
実施例１と同様に１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体を合成した。この担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は、担体の全重量を基準として金属換算で、２．０重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例３の炭化水素の水蒸気改質触媒を得た。
(Example 3)
Was synthesized similarly 12SrO · 7Al 2 O 3 (Mayenite phase) Purity 92% by weight of 12SrO · 7Al 2 O 3 carrier as in Example 1. The catalyst precursor was obtained by impregnating this support with a mixed solution in which RuCl 3 was dissolved in ethanol. The Ru impregnation amount was 2.0% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 3.
（実施例４）
実施例１と同様に１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体を合成した。この担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は、担体の全重量を基準として金属換算で、３．０重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例４の炭化水素の水蒸気改質触媒を得た。
Example 4
Was synthesized similarly 12SrO · 7Al 2 O 3 (Mayenite phase) Purity 92% by weight of 12SrO · 7Al 2 O 3 carrier as in Example 1. The catalyst precursor was obtained by impregnating this support with a mixed solution in which RuCl 3 was dissolved in ethanol. The amount of impregnated Ru was 3.0% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 4.
（実施例５）
実施例１と同様に１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度９２重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体を合成した。この担体に、Ｒｕ（ＰＰｈ３）３Ｃｌ２を混合し、めのう乳鉢で０．５時間すり潰し触媒前駆体を得た。Ｒｕ含浸量は、担体の全重量を基準として金属換算で、１．０重量％とした。この試料をＮ２中で６００℃で１時間焼成して実施例５の炭化水素の水蒸気改質触媒を得た。
(Example 5)
Was synthesized similarly 12SrO · 7Al 2 O 3 (Mayenite phase) Purity 92% by weight of 12SrO · 7Al 2 O 3 carrier as in Example 1. Ru (PPh 3 ) 3 Cl 2 was mixed with this support and ground in an agate mortar for 0.5 hours to obtain a catalyst precursor. The Ru impregnation amount was 1.0% by weight in terms of metal based on the total weight of the support. This sample was calcined in N 2 at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 5.
Ｂ−２． 水蒸気改質活性の測定方法
触媒の性能試験は、常圧の固定床流通反応試験装置で行った。性能試験に先立ち表２記載の実施例１から４の触媒を純Ｈ２中で６００℃で１時間前処理した。実施例５の触媒では純Ｎ２中で６００℃で１時間前処理した。炭化水素にはトルエン（Ｃ７Ｈ８）を用いた。反応は６００℃、水蒸気／炭素比＝２．０ ｍｏｌ／ｍｏｌ、充填触媒量と単位時間当たりのトルエン供給量（モル）の比が、触媒重量／トルエン比＝７．０または１４．０ ｇ ｈ ｍｏｌ−１、Ｎ２／（Ｃ７Ｈ８＋Ｈ２Ｏ）＝０．２５ ｍｏｌ／ｍｏｌの条件で行った。反応時間は３０分とした。ガス分析はＦＩＤ型ガスクロマトグラフで行った。活性は次式で示されるトルエン転化率で見積もった。
B-2. Method for measuring steam reforming activity The performance test of the catalyst was carried out with a fixed bed flow reaction test apparatus at normal pressure. Prior to the performance test, the catalysts of Examples 1 to 4 listed in Table 2 were pretreated at 600 ° C. for 1 hour in pure H 2 . The catalyst of Example 5 was pretreated at 600 ° C. for 1 hour in pure N 2 . Toluene (C 7 H 8 ) was used as the hydrocarbon. Reaction is 600 ° C., water vapor / carbon ratio = 2.0 mol / mol, ratio of packed catalyst amount and toluene supply amount (mol) per unit time is catalyst weight / toluene ratio = 7.0 or 14.0 g h It was performed under the conditions of mol −1 , N 2 / (C 7 H 8 + H 2 O) = 0.25 mol / mol. The reaction time was 30 minutes. The gas analysis was performed with an FID type gas chromatograph. The activity was estimated by the toluene conversion represented by the following formula.
トルエン転化率（％）＝
（（入口トルエン濃度）−（出口トルエン濃度））／ （入口トルエン濃度）× １００
Toluene conversion rate (%) =
((Inlet toluene concentration) − (Outlet toluene concentration)) / (Inlet toluene concentration) × 100
Ｂ−３． 水蒸気改質活性の測定結果
上記の実施例１から５の活性試験結果を表２にまとめた。初めに、Ｒｕ原料を変化させた場合の影響を実施例２と５の比較から検討した。両試料Ｒｕ担持量は共に１．０重量％である。ＲｕＣｌ３原料を用いた実施例２のトルエン転化率は３６．１％、Ｒｕ（ＰＰｈ３）３Ｃｌ２原料を用いた実施例５のそれは触媒重量／トルエン比＝７．０ｇ ｈ ｍｏｌ−１、すなわち触媒量が半分にもかかわらず、３４．２重量％であった。このことから、種々のＲｕ塩類や錯体のなかでも、特にＲｕ（ＰＰｈ３）３Ｃｌ２が本触媒の原料として好適であることが分かった。
B-3. Measurement Results of Steam Reforming Activity Table 2 summarizes the activity test results of Examples 1 to 5 above. First, the effect of changing the Ru material was examined from a comparison between Examples 2 and 5. Both sample Ru loadings are 1.0% by weight. The toluene conversion of Example 2 using RuCl 3 feedstock was 36.1%, that of Example 5 using Ru (PPh 3 ) 3 Cl 2 feedstock was catalyst weight / toluene ratio = 7.0 g h mol −1 , That is, although the catalyst amount was half, it was 34.2% by weight. From this, it was found that Ru (PPh 3 ) 3 Cl 2 is particularly suitable as a raw material for the catalyst among various Ru salts and complexes.
次に、Ｒｕ担持量の最適化検討を行った。表２の実施例１から４の結果より、Ｒｕ担持量には最適値が存在し、最大活性は２．０重量％で得られることが明らかである。この結果より、本発明によるＲｕ担持量の最適値は０．５重量％〜３重量％とした。
表２
Next, optimization study of the Ru loading amount was performed. From the results of Examples 1 to 4 in Table 2, it is clear that there is an optimum value for the Ru loading, and the maximum activity is obtained at 2.0% by weight. From this result, the optimum value of the Ru loading amount according to the present invention was set to 0.5 wt% to 3 wt%.
Table 2
Ｃ．水蒸気改質活性に与える１２ＳｒＯ・７Ａｌ２Ｏ３純度の影響
Ｃ−１． 触媒調製方法
１２ＳｒＯ・７Ａｌ２Ｏ３担体中の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度は１２ＳｒＯ・７Ａｌ２Ｏ３担体合成時の焼成温度を変化させることで制御した。詳細を以下に記す。
C. Effect of 12SrO · 7Al 2 O 3 purity on steam reforming activity C-1. 12SrO · 7Al 2 O 3 (Mayenite phase) Purity of the catalyst preparation method 12SrO · 7Al 2 O 3 carrier was controlled by changing the sintering temperature during 12SrO · 7Al 2 O 3 carrier synthesis. Details are described below.
（実施例６）
担体である１２ＳｒＯ・７Ａｌ２Ｏ３は実施例１と同様に合成した。先の実施例１から５の焼成温度は６００℃であったが、実施例６ではこれを７００℃とした。この様にして合成した担体の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度は８３重量％であった。
(Example 6)
The carrier 12SrO.7Al 2 O 3 was synthesized in the same manner as in Example 1. The firing temperature of the previous Examples 1 to 5 was 600 ° C., but in Example 6, this was 700 ° C. The carrier synthesized in this manner had a purity of 12SrO · 7Al 2 O 3 (Mayenite phase) of 83% by weight.
この１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度８３重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は担体の全重量を基準として金属換算で０．５重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例６の炭化水素の水蒸気改質触媒を得た。 A catalyst precursor was obtained by impregnating a 12SrO · 7Al 2 O 3 carrier having a purity of 83 wt% with 12SrO · 7Al 2 O 3 (Mayenite phase) with a mixed solution of RuCl 3 dissolved in ethanol. The Ru impregnation amount was 0.5% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 6.
（実施例７）
担体である１２ＳｒＯ・７Ａｌ２Ｏ３は実施例１と同様に合成した。実施例７では焼成温度を８００℃とした。この様にして合成した担体の１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度は７３重量％であった。
(Example 7)
The carrier 12SrO.7Al 2 O 3 was synthesized in the same manner as in Example 1. In Example 7, the firing temperature was 800 ° C. The carrier synthesized in this manner had a purity of 12SrO · 7Al 2 O 3 (Mayenite phase) of 73% by weight.
この１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度７３重量％の１２ＳｒＯ・７Ａｌ２Ｏ３担体に、エタノールにＲｕＣｌ３を溶解させた混合溶液を含浸することで触媒前駆体を得た。Ｒｕ含浸量は担体の全重量を基準として金属換算で０．５重量％とした。その前駆体を蒸発乾固後、１００℃で１６時間乾燥を行い、その後、空気中で６００℃で１時間焼成して実施例７の炭化水素の水蒸気改質触媒を得た。 This 12SrO · 7Al 2 O 3 (Mayenite phase) 12SrO · 7Al 2 O 3 carrier with a purity of 73% by weight was impregnated with a mixed solution of RuCl 3 dissolved in ethanol to obtain a catalyst precursor. The Ru impregnation amount was 0.5% by weight in terms of metal based on the total weight of the support. The precursor was evaporated to dryness, dried at 100 ° C. for 16 hours, and then calcined in air at 600 ° C. for 1 hour to obtain a hydrocarbon steam reforming catalyst of Example 7.
Ｃ−２． 水蒸気改質活性の測定方法
触媒の性能試験は、常圧の固定床流通反応試験装置で行った。性能試験に先立ち触媒を純Ｈ２中で６００℃で１時間前処理した。炭化水素にはドデカン（Ｃ１２Ｈ２６）を用いた。反応は６００℃、水蒸気／炭素比＝３．０ ｍｏｌ／ｍｏｌ、スチームとドデカン合計ＳＶ＝４００００ ｈ−１、Ｎ２／（Ｃ１２Ｈ２６＋Ｈ２Ｏ）比＝０．１２５ ｍｏｌ／ｍｏｌの条件で行った。反応時間は１８０分とした。ガス分析はＦＩＤ型ガスクロマトグラフで行った。活性は次式で示されるドデカン転化率で見積もった。
C-2. Method for measuring steam reforming activity The performance test of the catalyst was carried out with a fixed bed flow reaction test apparatus at normal pressure. Prior to the performance test, the catalyst was pretreated in pure H 2 at 600 ° C. for 1 hour. Dodecane (C 12 H 26 ) was used as the hydrocarbon. Reaction is 600 ° C., water vapor / carbon ratio = 3.0 mol / mol, steam and dodecane total SV = 40000 h −1 , N 2 / (C 12 H 26 + H 2 O) ratio = 0.125 mol / mol I went there. The reaction time was 180 minutes. The gas analysis was performed with an FID type gas chromatograph. The activity was estimated by the dodecane conversion shown by the following formula.
ドデカン転化率（％）＝
（（入口ドデカン濃度）−（出口ドデカン濃度））／ （入口ドデカン濃度）× １００
Dodecane conversion (%) =
((Inlet dodecane concentration) − (Outlet dodecane concentration)) / (Inlet dodecane concentration) × 100
Ｃ−３． 水蒸気改質活性の測定結果
実施例１、６、７と比較例２の触媒の活性試験結果を表３にまとめた。１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度が増加するに従いドデカン転化率が急激に増加することが分かった。この結果は、高い炭化水素の水蒸気改質活性を得るためには、高い１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度が必須であることを示している。
C-3. Measurement Results of Steam Reforming Activity Table 3 summarizes the activity test results of the catalysts of Examples 1, 6, and 7 and Comparative Example 2. It was found that the dodecane conversion increased rapidly as the purity of 12SrO.7Al 2 O 3 (Maynite phase) increased. This result shows that high 12SrO.7Al 2 O 3 (Mayenite phase) purity is essential to obtain high hydrocarbon steam reforming activity.
比較例２の工業触媒のドデカン転化率は３２．３％であり、Ｒｕ担持量の大きな相違があるにも拘わらず、実施例１、６および７の触媒はこれと同等かそれ以上の性能を有していた。この結果より、本発明における２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度の好適値は７０％以上、特に好ましくは８０重量％以上、例えば９０％以上であるとした。
表３
The industrial catalyst of Comparative Example 2 has a dodecane conversion rate of 32.3%, and the catalysts of Examples 1, 6 and 7 have the same or better performance despite the large difference in the Ru loading. Had. From this result, the preferred value of 2SrO.7Al 2 O 3 (Mayenite phase) purity in the present invention is 70% or more, particularly preferably 80% by weight or more, for example 90% or more.
Table 3
以上で述べたＡ、Ｂ、Ｃの実験結果から、Ｒｕと１２ＳｒＯ・７Ａｌ２Ｏ３（Ｍａｙｅｎｉｔｅ相）純度が７０重量％以上、特に８０重量％以上の高純度１２ＳｒＯ・７Ａｌ２Ｏ３担体との組み合わせが炭化水素の水蒸気改質反応において特に高活性であり、かつ、炭素を析出させない特異な組み合わせであることを発見した。加えて、Ｒｕ担持時のＲｕ原料として種々のＲｕ塩やＲｕ錯体が好適であること、Ｒｕ担持量を０．５ｗｔ％〜３．０重量％とすることで触媒性能と経済性の双方を特に良好に満足することを発見した。これらの発見に基づき本発明がなされた。 From the experimental results of A, B, and C described above, Ru and 12SrO · 7Al 2 O 3 (Mayenite phase) purity of 70% by weight or more, particularly 80% by weight or more of high purity 12SrO · 7Al 2 O 3 support It has been discovered that the combination is a particularly high combination in hydrocarbon steam reforming reactions and is a unique combination that does not deposit carbon. In addition, various Ru salts and Ru complexes are suitable as Ru raw materials at the time of Ru loading, and the catalyst performance and economy are particularly improved by setting the Ru loading to 0.5 wt% to 3.0 wt%. I found it satisfactory. The present invention has been made based on these findings.
Claims (7)
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| PCT/JP2016/001169 WO2016143313A1 (en) | 2015-03-09 | 2016-03-03 | STEAM REFORMING CATALYST FOR HYDROCARBONS, WHICH IS OBTAINED BY HAVING 12SrO·7Al2O3 COMPOUND HAVING MAYENITE STRUCTURE SUPPORT Ru |
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