JP2003047846A - Catalyst and method for reforming dimethyl ether - Google Patents
Catalyst and method for reforming dimethyl etherInfo
- Publication number
- JP2003047846A JP2003047846A JP2001238658A JP2001238658A JP2003047846A JP 2003047846 A JP2003047846 A JP 2003047846A JP 2001238658 A JP2001238658 A JP 2001238658A JP 2001238658 A JP2001238658 A JP 2001238658A JP 2003047846 A JP2003047846 A JP 2003047846A
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl ether
- catalyst
- reforming
- carrier
- solid acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002407 reforming Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011973 solid acid Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000006057 reforming reaction Methods 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 150000002739 metals Chemical class 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 12
- 239000000446 fuel Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ジメチルエーテル
から効率的に水素を製造するためのジメチルエーテル改
質触媒およびジメチルエーテル改質方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a dimethyl ether reforming catalyst and a dimethyl ether reforming method for efficiently producing hydrogen from dimethyl ether.
【０００２】[0002]
【従来の技術】燃料電池は、水素と酸素から水を得る電
池反応によって起電力を得ている。原料の水素は、原燃
料と水を改質触媒の存在下に反応させて得られる。この
ような燃料電池のうち、固体高分子型燃料電池（ＰＥＦ
Ｃ：Ｐｏｌｙｍｅｒ Ｅｌｅｃｔｒｏｌｙｔｅ Ｆｕｅ
ｌ Ｃｅｌｌ）が優れた性能を発揮できるものとして注
目されている。このような固体高分子型燃料電池では、
水素を燃料とし、アノード（燃料極）、カソード（空気
極）における電極反応によって起電力を得ている。2. Description of the Related Art Fuel cells obtain electromotive force by a cell reaction in which water is obtained from hydrogen and oxygen. Raw material hydrogen is obtained by reacting raw fuel and water in the presence of a reforming catalyst. Among such fuel cells, polymer electrolyte fuel cells (PEF)
C: Polymer Electrolyte Fue
l Cell) is attracting attention as a material capable of exhibiting excellent performance. In such a polymer electrolyte fuel cell,
Using hydrogen as fuel, electromotive force is obtained by electrode reaction at the anode (fuel electrode) and cathode (air electrode).
【０００３】上記原燃料としては、メタノール、エタノ
ールが用いられていたが、ジメチルエーテルも採用の選
択枝として採用されつつある。ジエチルエーテルと水
（水蒸気）から、以下の反応によって、水素と一酸化炭
素を生成する。
ＣＨ3ＯＣＨ3＋Ｈ2Ｏ→２ＣＯ＋４Ｈ2 ・・・・・（１）
このようなジメチルエーテルの改質は、従来、７００℃
以上の高温でＲｕまたはＮｉを触媒にして改質を行なっ
ていた。上記触媒では、副反応であるメタネーション反
応が併発し、水素の生成量が少ないため、７００℃以上
の高温にすることで、平衡的にメタンの副生を抑制して
いた。
ＣＨ3ＯＣＨ3＋Ｈ2Ｏ→（２ＣＯ＋４Ｈ2）→２ＣＨ4＋２Ｈ2Ｏ・・・（２
）
しかし、ジメチルエーテルを７００℃以上の高温にする
のには、大規模な装置を設ける必要があり、ＰＥＦＣ装
置の大きさをコンパクト化するにあたって改善が望まれ
ていた。Although methanol and ethanol have been used as the above-mentioned raw fuel, dimethyl ether is being adopted as an option. Hydrogen and carbon monoxide are produced from diethyl ether and water (steam) by the following reaction. CH 3 OCH 3 + H 2 O → 2CO + 4H 2 (1) Such reforming of dimethyl ether has conventionally been performed at 700 ° C.
At the above high temperature, reforming was carried out using Ru or Ni as a catalyst. In the above catalyst, a methanation reaction, which is a side reaction, occurs concurrently, and the amount of hydrogen produced is small. Therefore, by raising the temperature to 700 ° C. or higher, the by-production of methane was balancedly suppressed. CH 3 OCH 3 + H 2 O → (2CO + 4H 2 ) → 2CH 4 + 2H 2 O (2) However, in order to raise the temperature of dimethyl ether to 700 ° C. or higher, a large-scale device must be installed, and PEFC Improvements have been desired in reducing the size of the device.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記事情に対
してなされたもので、ジメチルエーテルの改質反応を７
００℃以下の低温でも行うことを可能とし、かつ高濃度
の水素を効率良く生成することができるジメチルエーテ
ル改質触媒およびジメチルエーテルの改質方法を提供す
ることを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it has been proposed that a dimethyl ether reforming reaction is performed.
An object of the present invention is to provide a dimethyl ether reforming catalyst and a method for reforming dimethyl ether, which can be carried out even at a low temperature of 00 ° C. or lower and which can efficiently generate high concentration hydrogen.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明に係るジメチルエーテル改質触媒は、固体酸
作用を有する担体に、少なくともＰｔを含む活性金属を
担持させたことを特徴とする。このように、固体酸作用
を有する担体が以下の逐次反応式（３）を促進し、ま
た、Ｐｔを含む活性金属が以下の逐次反応式（４）を促
進するとともに、メタネーション活性も低いため、約４
５０℃の低温でも、高濃度の水素を効率良く生成するこ
とができる。
ＣＨ3ＯＣＨ3＋Ｈ2Ｏ→２ＣＨ3ＯＨ ・・・・・（３）
ＣＨ3ＯＨ→ＣＯ＋２Ｈ2 ・・・・・（４）
ジメチルエーテル改質反応は、上記逐次反応式で進行す
ると推定できる。式（３）は平衡上転化率が高くない
が、式（３）と式（４）が逐次で進行することによって
効率的に高濃度の水素を生成することができる。To achieve the above object, the dimethyl ether reforming catalyst according to the present invention is characterized in that a carrier having a solid acid action is loaded with an active metal containing at least Pt. Thus, the carrier having a solid acid action promotes the following sequential reaction formula (3), the active metal containing Pt promotes the following sequential reaction formula (4), and the methanation activity is low. , About 4
High concentration hydrogen can be efficiently generated even at a low temperature of 50 ° C. CH 3 OCH 3 + H 2 O → 2CH 3 OH (3) CH 3 OH → CO + 2H 2 (4) It can be estimated that the dimethyl ether reforming reaction proceeds according to the above-mentioned sequential reaction formula. Equation (3) does not have a high conversion rate on equilibrium, but it is possible to efficiently generate high-concentration hydrogen by sequentially advancing equation (3) and equation (4).
【０００６】上記固体酸作用を有する担体としては、γ
アルミナ、θアルミナ、アナターゼ型チタニア、ジルコ
ニア、ゼオライトおよびメタロシリケートから成るグル
ープから選ばれた少なくとも１種か、またはＴｉ、Ｓ
ｉ、ＡｌおよびＺｒから成るグループから選ばれた少な
くとも２種以上の複合酸化物が好適である。そして、固
体酸作用を有する担体の固体酸量は、ピリジン吸着量で
０．１ｍｍｏｌ／ｇを超えることが好適である。上記Ｐ
ｔを含む活性金属としては、Ｐｔと、Ｆｅ、Ｍｎ、Ｚ
ｎ、Ｃｕ、Ｗ、Ｐ、Ｓ、Ｃｏ、ＣｒおよびＳｎから成る
グループから選ばれた少なくとも１種との組み合わせが
好適である。As the carrier having the above solid acid action, γ
At least one selected from the group consisting of alumina, θ-alumina, anatase type titania, zirconia, zeolite and metallosilicate, or Ti, S
At least two or more complex oxides selected from the group consisting of i, Al and Zr are suitable. The solid acid amount of the carrier having a solid acid action is preferably more than 0.1 mmol / g in terms of pyridine adsorption amount. Above P
As the active metal containing t, Pt, Fe, Mn, Z
A combination with at least one selected from the group consisting of n, Cu, W, P, S, Co, Cr and Sn is preferable.
【０００７】また、本発明は、別の側面において、上記
したジメチルエーテル改質触媒を用いたジメチルエーテ
ルの改質方法である。このようなジメチルエーテル改質
方法では、ジメチルエーテルに対し、水と酸素を加え、
部分酸化反応も生じさせるようにすることが好適であ
る。このように酸素を加えることによって、ジメチルエ
ーテル改質反応と上記部分酸化反応とを併発させ、オー
トサーマル反応を行うようにすることができる。The present invention, in another aspect, is a method for reforming dimethyl ether using the above-mentioned dimethyl ether reforming catalyst. In such a dimethyl ether reforming method, water and oxygen are added to dimethyl ether,
It is preferable to cause a partial oxidation reaction. By adding oxygen in this way, the dimethyl ether reforming reaction and the partial oxidation reaction can be caused to occur simultaneously, and the autothermal reaction can be carried out.
【０００８】[0008]
【発明の実施の形態】以下、本発明に係るジメチルエー
テル改質触媒とジメチルエーテル改質方法をその実施の
形態等についてさらに詳細に説明する。本発明に係るジ
メチルエーテル改質触媒は、固体酸作用を有する担体
に、少なくともＰｔを含む活性金属を担持させたことを
特徴とする。このような担体としては、γアルミナ（Ａ
ｌ2Ｏ3）、θアルミナ（Ａｌ2Ｏ3）、アナターゼ型チタ
ニア（ＴｉＯ2）、ジルコニア（ＺｒＯ2）、ゼオライ
ト、メタロシリケート等を用いることができる。また、
担体として、Ｔｉ、Ｓｉ、ＡｌおよびＺｒから成るグル
ープから選ばれた少なくとも２種以上の複合酸化物を用
いることもできる。これらの複合酸化物は主に共沈法等
によって調製される。複合酸化物の例として、シリカ・
アルミナ、シリカ・チタニア、チタニア・アルミナ、ア
ルミナ・ジルコニア等がある。これらの固体酸作用を有
する担体の固体酸量は、ピリジン吸着量で０．１ｍｍｏ
ｌ／ｇを超えるものが好適である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the dimethyl ether reforming catalyst and the dimethyl ether reforming method according to the present invention will be described in more detail with reference to embodiments thereof. The dimethyl ether reforming catalyst according to the present invention is characterized in that an active metal containing at least Pt is supported on a carrier having a solid acid action. As such a carrier, γ-alumina (A
l 2 O 3 ), θ-alumina (Al 2 O 3 ), anatase type titania (TiO 2 ), zirconia (ZrO 2 ), zeolite, metallosilicate and the like can be used. Also,
As the carrier, at least two kinds of complex oxides selected from the group consisting of Ti, Si, Al and Zr can be used. These complex oxides are mainly prepared by a coprecipitation method or the like. As an example of a complex oxide, silica
Alumina, silica / titania, titania / alumina, alumina / zirconia, etc. are available. The solid acid amount of these carriers having a solid acid action is 0.1 mmo in terms of pyridine adsorption amount.
Those exceeding 1 / g are preferable.
【０００９】上記担体に担持される金属としては、少な
くともＰｔを含む活性金属を用いる。Ｐｔはメタネーシ
ョン活性が低いため、７００℃以下の低温でも、高収量
の水素を生成することができる。さらに、Ｐｔは水蒸気
改質反応と部分酸化反応を促進するため、酸素を加える
ことにより、高収量の水素を生成することができる。Ｐ
ｔは含浸法またはイオン交換法によって担体に担持でき
る。Ｐｔの助触媒として、Ｆｅ、Ｍｎ、Ｚｎ、Ｃｕ、
Ｗ、Ｐ、Ｓ、Ｃｏ、ＣｒおよびＳｎから成るグループか
ら選ばれた少なくとも１種を用いることができる。Ｐｔ
を担体に担持した後、助触媒を主に含浸法等によって担
体に担持できる。As the metal supported on the carrier, an active metal containing at least Pt is used. Since Pt has a low methanation activity, a high yield of hydrogen can be generated even at a low temperature of 700 ° C. or lower. Further, since Pt promotes the steam reforming reaction and the partial oxidation reaction, a high yield of hydrogen can be generated by adding oxygen. P
t can be supported on the carrier by an impregnation method or an ion exchange method. As a Pt promoter, Fe, Mn, Zn, Cu,
At least one selected from the group consisting of W, P, S, Co, Cr and Sn can be used. Pt
After being loaded on the carrier, the cocatalyst can be loaded on the carrier mainly by an impregnation method or the like.
【００１０】さらに、本発明に係るジメチルエーテル改
質方法は、上記によって得られたジメチルエーテル改質
触媒を用いることを特徴とする。また、ジメチルエーテ
ルに対し、水（水蒸気）と酸素（空気）を加え、部分酸
化反応も生じさせるようにすることができる。部分酸化
反応をさらに適量に併発することによりオートサーマル
反応として実施することができる。これにより、約４５
０℃の低温でも、ジメチルエーテルの転化率を向上させ
ることができる。このとき、ジメチルエーテルに対し
て、空気と水蒸気は、空気／ジメチルエーテル（Ｃ１ベ
ース）＝０〜３（モル比）で、水蒸気／ジメチルエーテ
ル（Ｃ１ベース）＝０〜５（モル比）で混合することが
好ましいが、特にこれに限定されない。Furthermore, the dimethyl ether reforming method according to the present invention is characterized by using the dimethyl ether reforming catalyst obtained as described above. Further, water (steam) and oxygen (air) can be added to dimethyl ether to cause a partial oxidation reaction. The partial oxidation reaction can be carried out as an autothermal reaction by further concurrently generating an appropriate amount. With this, about 45
Even at a low temperature of 0 ° C., the conversion rate of dimethyl ether can be improved. At this time, with respect to dimethyl ether, air and water vapor may be mixed at air / dimethyl ether (C1 base) = 0 to 3 (molar ratio) and water vapor / dimethyl ether (C1 base) = 0 to 5 (molar ratio). Preferred, but not limited to this.
【００１１】[0011]
【実施例】実施例１（触媒の調製）
（触媒１の調製）担体として比表面積１５０ｍ2／ｇの
γ型アルミナ粉末（以下γ−Ａｌ2Ｏ3（γアルミナ）と
もいう）を蒸発皿に入れ、塩化白金酸水溶液をγ−Ａｌ
2Ｏ3に滴下し、１００℃のホットプレート上にて滴下し
た水分を蒸発させた。粉末を攪拌させながら均一に白金
が担持されるようにし、このような含浸法にて担体に対
して１重量％の白金（Ｐｔ）を担持した。上記γ−Ａｌ
2Ｏ3担持Ｐｔ触媒粉末を１２０℃で１２時間乾燥させた
後、５５０℃で５時間空気雰囲気下にて焼成を行った。
次に、本触媒粉末にアルミナゾルバインダー２％を添加
して、３ｍｍφの粒状触媒を成型した後、５００℃で５
時間焼成した。本粒状触媒を触媒１とした。Example 1 (Preparation of catalyst) (Preparation of catalyst 1) γ-type alumina powder (hereinafter also referred to as γ-Al 2 O 3 (γ-alumina)) having a specific surface area of 150 m 2 / g was used as a carrier in an evaporation dish. Put chloroplatinic acid aqueous solution into γ-Al
2 O 3 was dropped, and the dropped water was evaporated on a hot plate at 100 ° C. While stirring the powder, platinum was uniformly loaded, and 1% by weight of platinum (Pt) was loaded on the carrier by such an impregnation method. Γ-Al
The 2 O 3 -supported Pt catalyst powder was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an air atmosphere.
Next, 2% of alumina sol binder was added to the catalyst powder to form a 3 mmφ granular catalyst, and then the mixture was heated at 500 ° C. for 5 minutes.
Burned for hours. This granular catalyst was designated as catalyst 1.
【００１２】（触媒２〜６の調製）上記触媒１の調製法
において、γアルミナの代わりに，比表面積１２０ｍ2
／ｇのθアルミナ、比表面積８０ｍ2／ｇのアナターゼ
型チタニア、ジルコニア、Ｈ型のペンタシル型ゼオライ
ト（ＳｉＯ2／Ａｌ2Ｏ3モル比４０）、Ｈ型のメタロシ
リケート（ＳｉＯ2／Ａｌ2Ｏ3モル比３０、ＳｉＯ2／Ｆ
ｅ2Ｏ3モル比６００、ＳｉＯ2／Ｃｏ2Ｏ3モル比５０
０）を用いて、触媒１と同様な方法にて白金を担持し
て、粉末触媒２〜６を調製した。さらに、触媒１と同様
な方法により、３ｍｍφの粒状触媒を調製した後、５０
０℃で５時間焼成して、触媒２〜６を得た。(Preparation of Catalysts 2 to 6) In the above preparation method of Catalyst 1, a specific surface area of 120 m 2 was used in place of γ-alumina.
/ G of θ-alumina, specific surface area 80m 2 / g of anatase type titania, zirconia, H type pentasil type zeolite (SiO 2 / Al 2 O 3 molar ratio 40), H type metallosilicate (SiO 2 / Al 2 O). 3 molar ratio 30, SiO 2 / F
e 2 O 3 molar ratio 600, SiO 2 / Co 2 O 3 molar ratio 50
0) was used to carry platinum in the same manner as in catalyst 1 to prepare powder catalysts 2 to 6. Furthermore, after a granular catalyst having a diameter of 3 mm was prepared by the same method as the catalyst 1, 50
Calcination was performed at 0 ° C. for 5 hours to obtain catalysts 2 to 6.
【００１３】（触媒７〜１１の調製）上記触媒１の調製
法において、γアルミナの代わりとして、ＴｉＯ2・Ｓ
ｉＯ2複合酸化物（ＴｉＯ2：ＳｉＯ2＝８０：２０（重
量比）、比表面積１５０ｍ2／ｇ）、ＴｉＯ2・Ａｌ2Ｏ3
複合酸化物（ＴｉＯ2・Ａｌ2Ｏ3＝５０：５０（重量
比）、比表面積１６０ｍ2／ｇ）、Ａｌ2Ｏ3・ＺｒＯ2複
合酸化物（Ａｌ2Ｏ3：ＺｒＯ2＝９０:１０（重量比）、
比表面積２００ｍ2／ｇ）、ＴｉＯ2・ＺｒＯ2複合酸化
物（ＴｉＯ2：ＺｒＯ2＝５０:５０（重量比）、比表面
積１００ｍ2／ｇ）、ＳｉＯ2・Ａｌ2Ｏ3複合酸化物（Ｓ
ｉＯ2：Ａｌ2Ｏ3＝９０：１０（重量比）、比表面積１
５０ｍ2／ｇ）を調製した。調製方法は、各々の金属の
硝酸塩又は塩化物の水溶液に対してアンモニアを滴下
し、ｐＨ＝７付近にて共沈法により複合酸化物を得た。
この複合酸化物を乾燥した後、焼成を６００℃で５時間
行った。そして、触媒１と同様な方法にて白金を担持し
て、粉末触媒７〜１１を調製した。さらに、触媒１と同
様な方法により、３ｍｍφの粒状触媒を調製した後、５
００℃で５時間焼成して、触媒７〜１１を得た。(Preparation of catalysts 7 to 11) In the preparation method of the above catalyst 1, TiO 2 .S was used instead of γ-alumina.
iO 2 composite oxide (TiO 2 : SiO 2 = 80: 20 (weight ratio), specific surface area 150 m 2 / g), TiO 2 · Al 2 O 3
Composite oxide (TiO 2 · Al 2 O 3 = 50: 50 (weight ratio), specific surface area 160 m 2 / g), Al 2 O 3 · ZrO 2 composite oxide (Al 2 O 3 : ZrO 2 = 90: 10) (Weight ratio),
Specific surface area 200 m 2 / g), TiO 2 · ZrO 2 composite oxide (TiO 2 : ZrO 2 = 50: 50 (weight ratio), specific surface area 100 m 2 / g), SiO 2 · Al 2 O 3 composite oxide ( S
iO 2 : Al 2 O 3 = 90: 10 (weight ratio), specific surface area 1
50 m 2 / g) was prepared. As for the preparation method, ammonia was added dropwise to an aqueous solution of a nitrate or chloride of each metal, and a complex oxide was obtained by a coprecipitation method at around pH = 7.
After drying this composite oxide, firing was performed at 600 ° C. for 5 hours. Then, platinum was loaded in the same manner as the catalyst 1 to prepare powder catalysts 7 to 11. Further, a 3 mmφ granular catalyst was prepared in the same manner as in Catalyst 1, and then 5
Calcination was performed at 00 ° C. for 5 hours to obtain catalysts 7 to 11.
【００１４】（触媒１２〜２１の調製）上記触媒１の調
製法において、γ−Ａｌ2Ｏ3担持Ｐｔ触媒粉末に対し
て、助触媒としてＦｅ、Ｍｎ、Ｚｎ、Ｃｕ、Ｗ、Ｐ、
Ｓ、Ｃｏ、Ｃｒ、Ｓｎを担持するため、各金属のアンモ
ニウム塩又は硝酸塩の水溶液にγ−Ａｌ2Ｏ3担持Ｐｔ触
媒粉末を浸漬して、各々の金属で０．５％担持させ、乾
燥させた後、６００℃で５時間焼成を行った。さらに、
触媒１と同様な方法により３ｍｍφの粒状触媒を調製し
た後、５００℃で５時間焼成して、触媒１２〜２１を得
た。(Preparation of catalysts 12 to 21) In the preparation method of the above catalyst 1, Fe, Mn, Zn, Cu, W, P as a co-catalyst was added to the γ-Al 2 O 3 -supported Pt catalyst powder.
In order to support S, Co, Cr, and Sn, γ-Al 2 O 3 -supported Pt catalyst powder is immersed in an aqueous solution of ammonium salt or nitrate of each metal to support 0.5% of each metal, and dried. After that, firing was performed at 600 ° C. for 5 hours. further,
A 3 mmφ granular catalyst was prepared by a method similar to that of the catalyst 1, and then calcined at 500 ° C. for 5 hours to obtain catalysts 12 to 21.
【００１５】（触媒２２の調製）上記触媒１の調製法に
おいて、γアルミナに担持する白金の担持法として、含
浸法の代わりにイオン交換法を用いた。白金原料として
ジニトロジアミン白金水溶液（０．１Ｍ溶液）１００ｍ
ｌを用いて、これにγアルミナを１０ｇ添加し、４０℃
で３時間攪拌し、陽イオン交換を行った。そして濾過し
た後、イオン交換水で水洗し、触媒１と同様な方法にて
乾燥焼成し、３ｍｍφに調製した後、５００℃で５時間
焼成して、触媒２２を得た。なお、本触媒２２の白金担
持量は１．２重量％であった。(Preparation of catalyst 22) In the preparation method of catalyst 1 described above, an ion exchange method was used as a method for supporting platinum supported on γ-alumina instead of the impregnation method. 100m of dinitrodiamine platinum aqueous solution (0.1M solution) as platinum raw material
10 g of γ-alumina was added to this, and the temperature was 40 ° C.
After stirring for 3 hours, cation exchange was performed. Then, after filtering, it was washed with ion-exchanged water, dried and calcined in the same manner as the catalyst 1, adjusted to 3 mmφ, and calcined at 500 ° C. for 5 hours to obtain a catalyst 22. The amount of platinum supported on this catalyst 22 was 1.2% by weight.
【００１６】（触媒２３、２４の調製）上記触媒１の調
製法において、γアルミナに担持する白金として０．３
％、２％をそれぞれ担持した触媒を調製した。触媒１と
同様な方法にて乾燥焼成し、３ｍｍφに調製した後、５
００℃で５時間焼成して、触媒２３、２４を得た。(Preparation of catalysts 23 and 24) In the preparation method of the catalyst 1 described above, 0.3 as platinum supported on γ-alumina was used.
%, 2% were respectively supported to prepare a catalyst. After drying and firing in the same manner as in Catalyst 1 to prepare 3 mmφ, 5
The catalyst was calcined at 00 ° C. for 5 hours to obtain catalysts 23 and 24.
【００１７】（比較触媒１〜３の調製）上記触媒1の調
製法において、γアルミナに担持する触媒として、塩化
白金酸の代わりに、塩化ルテニウム、塩化ニッケル、塩
化ロジウムの各水溶液を各々含浸して粉末触媒化し、各
々金属でＲｕ：１％、Ｎｉ：１３％、Ｒｈ：１％を担持
させた。さらに、触媒１と同様な方法にて乾燥焼成し、
３ｍｍφに調製した後、５００℃で５時間焼成して、比
較触媒１〜３を得た。(Preparation of Comparative Catalysts 1 to 3) In the preparation method of Catalyst 1 above, as a catalyst supported on γ-alumina, each aqueous solution of ruthenium chloride, nickel chloride and rhodium chloride was impregnated in place of chloroplatinic acid. And powder-catalyzed to support Ru: 1%, Ni: 13%, and Rh: 1% by metal. Further, it is dried and calcined in the same manner as the catalyst 1,
After being adjusted to 3 mmφ, it was calcined at 500 ° C. for 5 hours to obtain comparative catalysts 1 to 3.
【００１８】（比較触媒４、５の調製）上記触媒１の調
製法において、γアルミナの代わりに、αアルミナ（比
表面積３ｍ2／ｇ）、非晶質ＳｉＯ2（比表面積３０ｍ2
／ｇ）を用いてＰｔを担持させた。さらに、触媒１と同
様な方法にて乾燥焼成し、３ｍｍφに調製した後、５０
０℃で５時間焼成して、比較触媒４、５を得た。(Preparation of Comparative Catalysts 4 and 5) In the preparation method of the above catalyst 1, α-alumina (specific surface area 3 m 2 / g), amorphous SiO 2 (specific surface area 30 m 2 ) were used in place of γ-alumina.
/ G) was used to support Pt. Further, after being dried and calcined in the same manner as the catalyst 1 to prepare 3 mmφ, 50
It was calcined at 0 ° C. for 5 hours to obtain comparative catalysts 4 and 5.
【００１９】実施例２（酸量測定方法）触媒担体の主要
な物性値である固体酸量の測定を触媒学会方法に準じ
て、以下の方法により行った。方法はパルス反応器を用
いた。ピリジン昇温脱離法により行った。昇温脱離法は
サンプル１２．５ｍｇ、キャリヤーガスＨｅ流量４５ｍ
ｌ／ｍｉｎの条件でサンプルの前処理をＨｅ気流中、４
５０℃で３０分間行った後、サンプルを１５０℃に保持
して、ピリジンを０．２μｌ、繰り返し５回パルス供給
した。次に、１５０の吸着温度から７５０℃まで昇温速
度３０℃／ｍｉｎで昇温し、脱離したピリジン量を水素
炎イオン検出器で測定して、固体酸量を求めた。上記触
媒１〜２４、比較触媒１〜４で用いた触媒の固体酸量を
以下の表１に示す。Example 2 (Method for measuring acid content) The solid acid content, which is the main physical property value of the catalyst carrier, was measured by the following method in accordance with the Society of Catalysis. The method used a pulse reactor. It was carried out by the pyridine temperature programmed desorption method. Thermal desorption method is 12.5 mg sample, carrier gas He flow rate is 45 m
The pretreatment of the sample was performed in a He air flow at a rate of 1 / min for 4
After 30 minutes at 50 ° C., the sample was kept at 150 ° C. and 0.2 μl of pyridine was repeatedly pulsed 5 times. Next, the temperature was raised from the adsorption temperature of 150 to 750 ° C. at a temperature rising rate of 30 ° C./min, and the amount of desorbed pyridine was measured by a hydrogen flame ion detector to determine the amount of solid acid. The solid acid amounts of the catalysts used in Catalysts 1 to 24 and Comparative Catalysts 1 to 4 are shown in Table 1 below.
【００２０】[0020]
【表１】 [Table 1]
【００２１】実施例３
（ジメチルエーテル水蒸気改質試験：反応条件１）上記
触媒1〜２４、比較触媒１〜５を用いて、以下の条件に
おいてジメチルエーテルの水蒸気改質試験を行った。原
料はジメチルエーテル（ＣＨ3ＯＣＨ3）と水蒸気と空気
を［水蒸気／ジメチルエーテル（Ｃ１ベース）］＝４．
０（モル比）の条件で混合させ、２０ｃｃ充填した触媒
層（３ｍｍφペレット充填：円筒形：径２６ｍｍφ、長
さ２５ｍｍ）を触媒層平均温度４５０℃、５５０℃、６
５０℃に保持し、上記原料をＧＨＳＶ５０００ｈ-1（流
量１００Ｌ／ｈ）で供給した。Example 3 (Dimethyl ether steam reforming test: reaction condition 1) Using the above catalysts 1 to 24 and comparative catalysts 1 to 5, a steam reforming test of dimethyl ether was conducted under the following conditions. The raw materials are dimethyl ether (CH 3 OCH 3 ), steam and air [steam / dimethyl ether (C1 base)] = 4.
The catalyst layer (3 mmφ pellet filling: cylindrical shape: diameter 26 mmφ, length 25 mm) was mixed under the condition of 0 (molar ratio) and filled with 20 cc, and the catalyst layer average temperature 450 ° C., 550 ° C., 6
The temperature was maintained at 50 ° C., and the above raw materials were supplied at GHSV 5000 h −1 (flow rate 100 L / h).
【００２２】反応管出口ガス組成の炭化水素はガスクロ
マトグラムで分析した。ジメチルエーテル転化率（η）
は＝［１−出口ジメチルエーテル／入口ジメチルエーテ
ル（Ｃ１ベース）］×１００にて求めた。また、生成物
の水素濃度、副生するＣＨ4濃度（いずれもドライベー
ス）もガスクロマトグラフ法にて求めた。上記触媒の活
性評価試験結果を表２に示す。Hydrocarbons having a gas composition at the outlet of the reaction tube were analyzed by a gas chromatogram. Dimethyl ether conversion (η)
= [1-outlet dimethyl ether / inlet dimethyl ether (C1 base)] × 100. Further, the hydrogen concentration of the product and the CH 4 concentration of by-product (both are dry bases) were also determined by gas chromatography. Table 2 shows the results of the activity evaluation test of the above catalyst.
【００２３】[0023]
【表２】 [Table 2]
【００２４】上記結果より、本発明に係る触媒１〜２４
はいずれの反応温度においてもジメチルエーテル転化率
９０％以上、水素濃度６０％以上、ＣＨ4副生率５％以
下となり、低温で高効率にて水素を製造できることを確
認した。しかし、比較触媒１〜５は何れも５５０℃以下
においてＣＨ4の副生が多く、水素濃度が低かった。よ
って、高濃度の水素を製造するためには、６５０℃付近
の高温が必要であることがわかる。なお、本発明の触媒
１〜２４において、十分な水素製造活性を有し、かつＣ
Ｈ 4が少ない理由として、メタネーション作用が低いＰ
ｔを活性金属に用いたことと、水とジメチルエーテルの
吸着力が強く、加水分解作用を有する０．１ｍｍｏｌ／
ｇ以上の固体酸量を持つ担体を用いたこととによると考
えられる。From the above results, the catalysts 1 to 24 according to the present invention
Is the conversion rate of dimethyl ether at any reaction temperature
90% or more, hydrogen concentration 60% or more, CHFourBy-product rate of 5% or less
Below, we confirmed that hydrogen can be produced with high efficiency at low temperature.
I confirmed. However, the comparative catalysts 1 to 5 are all 550 ° C. or lower.
At CHFourThe hydrogen concentration was low. Yo
Therefore, in order to produce high concentration hydrogen, around 650 ℃
It can be seen that the high temperature is required. The catalyst of the present invention
1 to 24 have sufficient hydrogen production activity, and C
H FourThe reason is that P is low in methanation action.
t was used as the active metal and that of water and dimethyl ether
0.1 mmol / with strong adsorptivity and hydrolysis
It is considered that it is because a carrier having a solid acid amount of g or more was used.
available.
【００２５】実施例４
上記触媒１を用いて、実施例３で行った水蒸気改質条件
において、空気／ジメチルエーテル（Ｃ１ベース）：
１．５、２．５（モル比）の空気を供給し、オートサー
マル条件において活性評価を行った。さらに、水蒸気／
ジメチルエーテル（Ｃ１ベース）モル比の影響について
も検討を行った。表３に触媒温度４５０℃、５５０℃の
試験条件と活性評価結果を示す（Ｒｕｎ番号３０〜３
４）。Example 4 Using the above catalyst 1, under the steam reforming conditions carried out in Example 3, air / dimethyl ether (C1 based):
Air was supplied at 1.5 and 2.5 (molar ratio), and the activity was evaluated under autothermal conditions. In addition, steam /
The influence of the dimethyl ether (C1 base) molar ratio was also examined. Table 3 shows the test conditions at catalyst temperatures of 450 ° C. and 550 ° C. and the activity evaluation results (Run numbers 30 to 3).
4).
【００２６】[0026]
【表３】 [Table 3]
【００２７】表３に示す試験結果より、本発明に係る触
媒１を用いて、空気を添加したオートサーマル条件や部
分酸化条件、および種々の空気、水蒸気分圧条件におい
ても４５０℃程度で十分なジメチルエーテル分解活性を
有し、さらにＣＨ4の副生も無いことを確認した。From the test results shown in Table 3, using the catalyst 1 according to the present invention, about 450 ° C. is sufficient even under autothermal conditions and partial oxidation conditions in which air is added, and various air and steam partial pressure conditions. It was confirmed that the compound had a dimethyl ether decomposition activity and that CH 4 was not a byproduct.
【００２８】[0028]
【発明の効果】上記したところから明らかなように、本
発明によれば、ジメチルエーテルの改質反応を７００℃
以下の低温でも行うことを可能とし、かつ高濃度の水素
を効率良く生成することができるジメチルエーテル改質
触媒およびジメチルエーテルの改質方法が提供される。As is apparent from the above, according to the present invention, the dimethyl ether reforming reaction is conducted at 700 ° C.
Provided are a dimethyl ether reforming catalyst and a method for reforming dimethyl ether, which can be carried out at the following low temperatures and can efficiently generate high concentration hydrogen.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 23/89 Ｂ０１Ｊ 27/185 Ｍ 27/02 29/44 Ｍ 27/185 29/88 Ｍ 29/44 32/00 29/88 37/30 32/00 Ｃ０１Ｂ 3/32 Ｚ 37/30 Ｂ０１Ｊ 23/64 １０４Ｍ Ｃ０１Ｂ 3/32 １０３Ｍ (72)発明者 米村 将直 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 渡辺 悟 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 Ｆターム(参考） 4G040 EA01 EA06 EA07 EC02 EC03 EC07 4G069 AA03 AA08 BA01A BA01B BA04A BA04B BA05A BA05B BA07A BB06A BB06B BC22A BC22B BC31A BC31B BC35A BC35B BC58A BC58B BC60A BC60B BC62A BC62B BC66A BC66B BC67A BC67B BC75A BC75B BD07A BD07B BD08A BD08B CC40 DA05 EA02Y EC22X EC22Y EC30 FA01 FA02 FB09 FB14 FB26 FB30 FB61 ZA10B ZA37B ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 23/89 B01J 27/185 M 27/02 29/44 M 27/185 29/88 M 29/44 32 / 00 29/88 37/30 32/00 C01B 3/32 Z 37/30 B01J 23/64 104M C01B 3/32 103M (72) Inventor Masanao Yonemura 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory (72) Inventor Satoru Watanabe 4-6-22 Kannon-shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture BA01B BA04A BA04B BA05A BA05B BA07A BB06A BB06B BC22A BC22B BC31A BC31B BC35A BC35B BC58A BC58B BC60A BC60B BC62A BC62B BC66A BC66B BC67A BC67B BC75A BC75B BD07A BD07B BD08A BD08B CC40 DA05 C30 FA01 FA02 FB09 FB14 FB26 FB30 FB61 ZA10B ZA37B
Claims (7)
Ｐｔを含む活性金属を担持させたことを特徴とするジメ
チルエーテル改質触媒。1. A dimethyl ether reforming catalyst characterized in that an active metal containing at least Pt is supported on a carrier having a solid acid action.
ナ、θアルミナ、アナターゼ型チタニア、ジルコニア、
ゼオライトおよびメタロシリケートから成るグループか
ら選ばれた少なくとも１種の担体であるか、またはＴ
ｉ、Ｓｉ、ＡｌおよびＺｒから成るグループから選ばれ
た少なくとも２種以上の複合酸化物であることを特徴と
する請求項１のジメチルエーテル改質触媒。2. The carrier having a solid acid action is γ-alumina, θ-alumina, anatase-type titania, zirconia,
At least one carrier selected from the group consisting of zeolites and metallosilicates, or T
The dimethyl ether reforming catalyst according to claim 1, which is a composite oxide of at least two kinds selected from the group consisting of i, Si, Al and Zr.
が、ピリジン吸着量で０．１ｍｍｏｌ／ｇを超えること
を特徴とする請求項１または２のジメチルエーテル改質
触媒。3. The dimethyl ether reforming catalyst according to claim 1, wherein the carrier having a solid acid action has a solid acid amount of more than 0.1 mmol / g in terms of pyridine adsorption amount.
ｅ、Ｍｎ、Ｚｎ、Ｃｕ、Ｗ、Ｐ、Ｓ、Ｃｏ、Ｃｒおよび
Ｓｎから成るグループから選ばれた少なくとも１種との
組み合わせであることを特徴とする請求項１〜３のいず
れかのジメチルエーテル改質触媒。4. The active metal containing Pt is Pt and F.
A combination with at least one member selected from the group consisting of e, Mn, Zn, Cu, W, P, S, Co, Cr and Sn. Quality catalyst.
テル改質触媒を用いてジメチルエーテルを改質すること
を特徴とするジメチルエーテル改質方法。5. A dimethyl ether reforming method, which comprises reforming dimethyl ether using the dimethyl ether reforming catalyst according to claim 1.
え、部分酸化反応も生じさせるようにしたことを特徴と
する請求項５のジメチルエーテル改質方法。6. The method for reforming dimethyl ether according to claim 5, wherein water and oxygen are added to dimethyl ether to cause a partial oxidation reaction.
おいて、ジメチルエーテル改質反応と上記部分酸化反応
とによって、オートサーマル反応を行うようにしたこと
を特徴とするジメチルエーテル改質方法。7. The dimethyl ether reforming method according to claim 6, wherein an autothermal reaction is performed by the dimethyl ether reforming reaction and the partial oxidation reaction.
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Cited By (4)
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|---|---|---|---|---|
| JP2005095738A (en) * | 2003-09-24 | 2005-04-14 | Mitsubishi Gas Chem Co Inc | Catalyst for steam reforming of dimethyl ether having solid acid-containing coating layer |
| JP2007001795A (en) * | 2005-06-22 | 2007-01-11 | Kansai Electric Power Co Inc:The | Dimethyl ether reforming system and its operation method |
| JP2007131519A (en) * | 2005-10-14 | 2007-05-31 | Osaka Gas Co Ltd | Method for producing hydrogen-containing gas |
| JP2014100684A (en) * | 2012-11-21 | 2014-06-05 | Nissan Motor Co Ltd | Hydrogen-generating catalyst and system using hydrogen-generating catalyst |
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| WO1999048804A1 (en) * | 1998-03-24 | 1999-09-30 | Johnson Matthey Public Limited Company | Catalytic generation of hydrogen |
| JPH11278803A (en) * | 1998-01-21 | 1999-10-12 | Haldor Topsoe As | Production of hydrogen rich gas |
| JP2000000466A (en) * | 1998-04-17 | 2000-01-07 | Nkk Corp | Catalyst for production of synthetic gas and production of synthetic gas |
| JP2001096159A (en) * | 1999-09-29 | 2001-04-10 | Daihatsu Motor Co Ltd | Dimethyl ether reforming catalyst and fuel cell device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06165936A (en) * | 1992-09-03 | 1994-06-14 | Chisso Corp | Platinum catalyst supported on alumina |
| JPH11278803A (en) * | 1998-01-21 | 1999-10-12 | Haldor Topsoe As | Production of hydrogen rich gas |
| WO1999048804A1 (en) * | 1998-03-24 | 1999-09-30 | Johnson Matthey Public Limited Company | Catalytic generation of hydrogen |
| JP2000000466A (en) * | 1998-04-17 | 2000-01-07 | Nkk Corp | Catalyst for production of synthetic gas and production of synthetic gas |
| JP2001096159A (en) * | 1999-09-29 | 2001-04-10 | Daihatsu Motor Co Ltd | Dimethyl ether reforming catalyst and fuel cell device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005095738A (en) * | 2003-09-24 | 2005-04-14 | Mitsubishi Gas Chem Co Inc | Catalyst for steam reforming of dimethyl ether having solid acid-containing coating layer |
| JP2007001795A (en) * | 2005-06-22 | 2007-01-11 | Kansai Electric Power Co Inc:The | Dimethyl ether reforming system and its operation method |
| JP2007131519A (en) * | 2005-10-14 | 2007-05-31 | Osaka Gas Co Ltd | Method for producing hydrogen-containing gas |
| JP2014100684A (en) * | 2012-11-21 | 2014-06-05 | Nissan Motor Co Ltd | Hydrogen-generating catalyst and system using hydrogen-generating catalyst |
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|---|---|
| JP4831800B2 (en) | 2011-12-07 |
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