JP2008080246A - Method for pretreating hydrogen production catalyst and method for producing hydrogen for fuel cell - Google Patents
Method for pretreating hydrogen production catalyst and method for producing hydrogen for fuel cell Download PDFInfo
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- JP2008080246A JP2008080246A JP2006263263A JP2006263263A JP2008080246A JP 2008080246 A JP2008080246 A JP 2008080246A JP 2006263263 A JP2006263263 A JP 2006263263A JP 2006263263 A JP2006263263 A JP 2006263263A JP 2008080246 A JP2008080246 A JP 2008080246A
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- catalyst
- hydrogen
- oxidation
- reforming
- reduction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 15
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
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- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 41
- 238000002407 reforming Methods 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 32
- 238000002203 pretreatment Methods 0.000 claims abstract description 17
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- 230000003647 oxidation Effects 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 20
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は、水素製造触媒の前処理方法および燃料電池用水素の製造方法に関する。さらに詳しくは、本発明は、炭化水素を改質して水素含有ガスを製造する触媒の活性を向上させるために、同触媒に活性化前処理として、還元−酸化の繰り返し処理を施す方法、および炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に前記活性化前処理を施し、効率よく燃料電池用水素を製造する方法に関するものである。 The present invention relates to a pretreatment method for a hydrogen production catalyst and a method for producing hydrogen for a fuel cell. More specifically, the present invention relates to a method for subjecting the catalyst to a reduction-oxidation repeated treatment as a pretreatment for activation in order to improve the activity of the catalyst for reforming hydrocarbons to produce a hydrogen-containing gas, and The present invention relates to a method for efficiently producing hydrogen for fuel cells by reforming hydrocarbons to produce a hydrogen-containing gas by subjecting the catalyst to be used to the pretreatment for activation.
近年、環境問題から新エネルギー技術が脚光を浴びており、この新エネルギー技術の一つとして燃料電池が注目を集めている。この燃料電池は、水素と酸素を電気化学的に反応させることにより、化学エネルギーを電気エネルギーに変換させるものであって、エネルギーの利用効率が高いという特徴を有しており、民生用、産業用または自動車用等として、実用化研究が積極的になされている。
この燃料電池には、使用する電解質の種類に応じて、リン酸型、溶融炭酸塩型、固体酸化物型および固体高分子型等のタイプが知られている。一方、水素源としては、メタノールおよびメタンを主体とする液化天然ガス、この天然ガスを主成分とする都市ガス、天然ガスを原料とする合成液体燃料、さらには、石油系のＬＰＧ、ナフサおよび灯油等の石油系炭化水素の使用の研究がなされている。
これらの石油系炭化水素を用いて水素を製造する場合、一般に、同炭化水素に対して、触媒の存在下に水蒸気改質処理、自己熱改質処理、部分酸化改質処理などがなされている。
In recent years, new energy technology has attracted attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies. This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. In addition, research into practical use has been actively conducted for automobiles and the like.
For this fuel cell, types such as a phosphoric acid type, a molten carbonate type, a solid oxide type and a solid polymer type are known depending on the type of electrolyte used. On the other hand, as a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, synthetic liquid fuel using natural gas as a raw material, petroleum LPG, naphtha and kerosene Studies on the use of petroleum hydrocarbons such as
When hydrogen is produced using these petroleum hydrocarbons, steam reforming treatment, autothermal reforming treatment, partial oxidation reforming treatment, etc. are generally performed on the hydrocarbon in the presence of a catalyst. .
このような炭化水素の改質触媒として、従来ルテニウム系触媒やニッケル系触媒が知られており、そして、ハイドロタルサイト（多孔性複合水酸化物の水和物）を経由して調製された触媒は、活性が高いことも知られている。
ハイドロタルサイト経由で調製された炭化水素改質触媒としては、例えば（１）ハイドロタルサイトを前駆体として、その構成元素（Ｍｇ、Ａｌ）の一部を活性金属である貴金属（ＲｈまたはＲｕ）または遷移金属元素で置換、焼成し、活性金属種を内部から表面に染み出させて高分散化した金属微粒子担持炭化水素改質用触媒（例えば、特許文献１参照）、（２）マグネシウムとアルミニウムとニッケルを含む、ハイドロタルサイト経由で調製した改質触媒（例えば、特許文献２および３参照）、（３）ハイドロタルサイトの層間にＲｕをイオン交換により導入し、それを焼成したのち、還元により活性化してなる改質触媒（例えば、特許文献４参照）、（４）マグネシウムとアルミニウムとニッケル、鉄を含む、ハイドロタルサイト経由で調製したアンモニアの副生を抑えた自己熱改質触媒(例えば、特許文献５参照)、（５）ハイドロタルサイト状層状化合物を焼成することにより調製された、Ｒｕ、Ｐｔ、Ｐｄ、ＲｈおよびＩｒの中から選ばれる少なくとも1種の金属を含むメタン含有ガス改質触媒（例えば、特許文献６参照）、（６）ハイドロタルサイト経由で調製したマグネシウム、アルミニウム、ニッケルおよびルテニウムを構成元素とする炭化水素分解用触媒（例えば、特許文献７参照）、および
（７）ハイドロタルサイト経由で調製したマグネシウム、アルミニウム、ニッケルを構成元素とし、かつアルカリ金属（Ｎａを除く）、アルカリ土類金属（Ｍｇを除く）、Ｚｎ、Ｃｏ、Ｃｅ、Ｃｒ、ＦｅおよびＬａの中から選ばれる少なくとも1種の元素を含有する触媒（例えば、特許文献８参照）が開示されている。
Ruthenium-based catalysts and nickel-based catalysts have been known as such hydrocarbon reforming catalysts, and catalysts prepared via hydrotalcite (porous composite hydroxide hydrate) Is also known to have high activity.
As the hydrocarbon reforming catalyst prepared via hydrotalcite, for example, (1) noble metal (Rh or Ru) in which hydrotalcite is a precursor and a part of its constituent elements (Mg, Al) is an active metal Alternatively, a metal fine particle-supported hydrocarbon reforming catalyst (see, for example, Patent Document 1), which is substituted with a transition metal element and baked to exude an active metal species from the inside to the surface to be highly dispersed, (2) magnesium and aluminum Reforming catalyst prepared via hydrotalcite containing nickel and nickel (see, for example, Patent Documents 2 and 3), (3) Ru is introduced between the layers of hydrotalcite by ion exchange, calcined, and then reduced (4) via hydrotalcite containing magnesium, aluminum, nickel and iron Autothermal reforming catalyst with reduced by-product of ammonia prepared (for example, see Patent Document 5), (5) Ru, Pt, Pd, Rh and Ir prepared by calcining a hydrotalcite layered compound A methane-containing gas reforming catalyst containing at least one metal selected from the above (for example, see Patent Document 6), (6) Carbonization containing magnesium, aluminum, nickel and ruthenium prepared via hydrotalcite as constituent elements Catalysts for hydrogenolysis (see, for example, Patent Document 7), and (7) Magnesium, aluminum and nickel prepared via hydrotalcite as constituent elements, and alkali metals (except for Na), alkaline earth metals (Mg Catalyst) containing at least one element selected from Zn, Co, Ce, Cr, Fe and La (excluding) If, see Patent Document 8) have been disclosed.
しかしながら、前記（１）の改質触媒においては、前駆体であるハイドロタルサイトの構成元素を貴金属元素で置換する記載はあるが、還元−酸化の繰り返しについての記載はない。（２）の改質触媒においては、貴金属元素の含有については記載がない。（３）の改質触媒においては、焼成温度および還元温度について、それぞれ３００〜１３００℃、好ましくは５００〜１１００℃および４００〜１３００℃、好ましくは５００〜１０００℃と記載されているが、還元−酸化の繰り返しについての記載はない。（４）の自己熱改質触媒においては、金、銀、白金、パラジウム、ロジウム、イリジウム、レニウム、銅、マンガン、クロム、バナジウム、チタンの担持、４００〜１５００℃での焼成および６５０〜１１００℃での還元についての記載はあるが、還元−酸化の繰り返しについての記載はない。
前記（５）の改質触媒においては、焼成処理を，４００〜１２００℃で５〜１０時間、好ましくは５００〜１０００℃で５〜１０時間行うことが記載されているが、還元についての記載がない。また、Ｒｕ、Ｐｔ、Ｐｄ、ＲｈおよびＩｒは、炭素析出が生じにくい金属であることが記載されているが、還元−酸化の繰り返しについての記載はない。（６）の炭化水素分解用触媒においては、焼成温度（４００〜１６００℃）、および還元温度（７００〜１１００℃）が記載されてあり、また、微粒子ＮｉとＲｕの存在により、低温高活性で耐コーキング性にも優れると記載されているが、還元−酸化の繰り返しについての記載はない。（７）の触媒においては、Ｒｕを含有した触媒についての記載および耐酸化性、低温活性、耐コーキング性に優れるとの記載があり、また、焼成温度（４００〜１６００℃）および還元温度（７００〜１１００℃）についての記載があるが、還元−酸化の繰り返しについての記載はない。
さらに、このような従来の炭化水素改質触媒は、その活性については、必ずしも十分に満足し得るとは言えなかった。
However, in the reforming catalyst (1), there is a description that the constituent element of the hydrotalcite that is a precursor is replaced with a noble metal element, but there is no description about the repetition of reduction-oxidation. In the reforming catalyst (2), there is no description about the content of noble metal elements. In the reforming catalyst of (3), the firing temperature and the reduction temperature are 300 to 1300 ° C., preferably 500 to 1100 ° C. and 400 to 1300 ° C., preferably 500 to 1000 ° C., respectively. There is no description of repeated oxidation. In the autothermal reforming catalyst of (4), gold, silver, platinum, palladium, rhodium, iridium, rhenium, copper, manganese, chromium, vanadium, titanium are supported, calcined at 400 to 1500 ° C, and 650 to 1100 ° C. However, there is no description about the repetition of reduction-oxidation.
In the reforming catalyst (5), it is described that the calcination treatment is performed at 400 to 1200 ° C. for 5 to 10 hours, preferably at 500 to 1000 ° C. for 5 to 10 hours. Absent. In addition, Ru, Pt, Pd, Rh, and Ir are described as being metals that are unlikely to cause carbon deposition, but there is no description of repeated reduction-oxidation. In the hydrocarbon decomposition catalyst of (6), the calcination temperature (400 to 1600 ° C.) and the reduction temperature (700 to 1100 ° C.) are described. Although it is described that the coking resistance is also excellent, there is no description about repeated reduction-oxidation. In the catalyst of (7), there is a description of a catalyst containing Ru and a description that it is excellent in oxidation resistance, low-temperature activity, and coking resistance, and a firing temperature (400 to 1600 ° C.) and a reduction temperature (700 ˜1100 ° C.), but there is no description of repeated reduction-oxidation.
Furthermore, such conventional hydrocarbon reforming catalysts have not always been sufficiently satisfactory in terms of their activity.
本発明は、このような状況下で、炭化水素を改質して水素含有ガスを製造する触媒の活性を向上させる方法、および炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に、前記の活性を向上させる方法を施し、効率よく燃料電池用水素を製造する方法を提供することを目的とするものである。 Under such circumstances, the present invention uses a method for improving the activity of a catalyst for reforming hydrocarbons to produce a hydrogen-containing gas, and a method for reforming hydrocarbons to produce a hydrogen-containing gas. An object of the present invention is to provide a method for efficiently producing hydrogen for a fuel cell by applying a method for improving the activity to the catalyst.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の金属元素を含む炭化水素改質触媒、特にハイドロタルサイト状層状化合物を経由して得られる触媒に、活性化前処理として、還元−酸化の繰り返し処理を施すことにより、また、炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に、前記の活性化前処理を施すことにより、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive research to achieve the above object, the present inventors have activated hydrocarbon reforming catalysts containing specific metal elements, particularly catalysts obtained via hydrotalcite-like layered compounds. The purpose of the pretreatment is by subjecting the catalyst to be used to the aforementioned activation pretreatment to repeated reduction-oxidation treatment and reforming hydrocarbons to produce a hydrogen-containing gas. Found that it can be achieved. The present invention has been completed based on such findings.
すなわち、本発明は
（１）Ｎｉ、ＭｇおよびＡｌを含むと共にＰｔ、Ｐｄ、Ｉｒ、ＲｈおよびＲｕの中から選ばれる少なくとも一種の貴金属元素を含む、炭化水素を改質して水素含有ガスを製造する触媒に活性化前処理として、還元−酸化の繰り返し処理を施すことを特徴とする水素製造触媒の前処理方法、
（２）前記還元−酸化の繰り返し処理において、還元処理が、水素含有ガス雰囲気下、６００〜１１００℃の範囲の温度で行われる上記（１）に記載の水素製造触媒の前処理方法、
（３）前記還元−酸化の繰り返し処理において、酸化処理が、酸素含有ガス雰囲気下、４００〜１２００℃の範囲の温度で行われる上記（１）または（２）に記載の水素製造触媒の前処理方法、
（４）前記触媒がハイドロタルサイト状層状化合物を経由して得られたものである上記（１）〜（３）のいずれかに記載の水素製造触媒の前処理方法、
（５）前記触媒がハイドロタルサイト状層状化合物の焼成後に貴金属成分を担持させることにより得られたものである上記（４）に記載の水素製造触媒の前処理方法、
（６）前記貴金属元素が、Ｒｈおよび/またはＲｕである上記（１）〜（５）のいずれかに記載の水素製造触媒の前処理方法、
（７）焼成した前記触媒を還元処理後、「酸化−還元」の繰り返し処理を１〜２０回施す上記（１）〜（６）のいずれかに記載の水素製造触媒の前処理方法、
（８）前記炭化水素の改質が、水蒸気改質、自己熱改質または部分酸化改質である上記（１）〜（７）のいずれかに記載の水素製造触媒の前処理方法および
（９）炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に、上記（１）〜（８）のいずれかに記載の前処理方法を施すことを特徴とする燃料電池用水素の製造方法を提供するものである。
That is, the present invention (1) produces a hydrogen-containing gas by reforming a hydrocarbon containing Ni, Mg and Al and at least one noble metal element selected from Pt, Pd, Ir, Rh and Ru. A pretreatment method of a hydrogen production catalyst, characterized by subjecting the catalyst to be subjected to a reduction-oxidation repeated treatment as an activation pretreatment,
(2) The pretreatment method for a hydrogen production catalyst according to (1) above, wherein the reduction treatment is performed at a temperature in the range of 600 to 1100 ° C. in a hydrogen-containing gas atmosphere in the reduction-oxidation repeated treatment,
(3) The pretreatment of the hydrogen production catalyst according to the above (1) or (2), wherein in the repetitive treatment of reduction-oxidation, the oxidation treatment is performed at a temperature in the range of 400 to 1200 ° C. in an oxygen-containing gas atmosphere. Method,
(4) The pretreatment method for a hydrogen production catalyst according to any one of (1) to (3), wherein the catalyst is obtained via a hydrotalcite-like layered compound,
(5) The pretreatment method for a hydrogen production catalyst according to (4) above, wherein the catalyst is obtained by supporting a noble metal component after calcination of the hydrotalcite layered compound,
(6) The pretreatment method for a hydrogen production catalyst according to any one of (1) to (5), wherein the noble metal element is Rh and / or Ru,
(7) The pretreatment method for a hydrogen production catalyst according to any one of (1) to (6) above, wherein the calcined catalyst is subjected to reductive treatment, followed by repeated oxidation-reduction treatment 1 to 20 times.
(8) The method for pretreating a hydrogen production catalyst according to any one of (1) to (7) above, wherein the reforming of the hydrocarbon is steam reforming, autothermal reforming or partial oxidation reforming, and (9 When a hydrogen-containing gas is produced by reforming hydrocarbons, the pretreatment method according to any one of (1) to (8) above is applied to the catalyst used. A manufacturing method is provided.
本発明によれば、特定の金属元素を含む炭化水素改質触媒、特にハイドロタルサイト状層状化合物を経由して得られる触媒に、活性化前処理として、還元−酸化の繰り返し処理を施すことにより、同触媒の活性向上を図ることができる。また、炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に、前記の活性化前処理を施すことにより、効率よく燃料電池用水素を製造することができる。 According to the present invention, a hydrocarbon reforming catalyst containing a specific metal element, particularly a catalyst obtained via a hydrotalcite-like layered compound, is subjected to a reduction-oxidation repeated treatment as a pretreatment for activation. The activity of the catalyst can be improved. Further, when producing a hydrogen-containing gas by reforming a hydrocarbon, hydrogen for a fuel cell can be efficiently produced by subjecting the catalyst to be used to the above-mentioned pretreatment for activation.
本発明の水素製造触媒の前処理方法は、Ｎｉ、ＭｇおよびＡｌを含むと共に、Ｐｔ、Ｐｄ、Ｉｒ、ＲｈおよびＲｕの中から選ばれる少なくとも１種の貴金属元素を含む、炭化水素を改質して水素含有ガスを製造する触媒（以下、炭化水素改質触媒と称することがある）に、活性化前処理として、還元−酸化の繰り返し処理を施すことを特徴とする。
本発明の前処理方法が適用される炭化水素改質触媒は、Ｎｉ元素とＭｇ元素とＡｌ元素を含む担体に、貴金属成分が担持された触媒であり、同貴金属成分としては、Ｐｔ、Ｐｄ、Ｉｒ、ＲｈおよびＲｕの中から選ばれる少なくとも１種の元素を含有するものが用いられる。また、前記担体中のＮｉは活性成分としての役割も有している。
この炭化水素改質触媒は、特にハイドロタルサイト状層状化合物を経由して得られたものであることが、触媒活性の面から好ましい。
The pretreatment method for a hydrogen production catalyst of the present invention reforms a hydrocarbon containing Ni, Mg and Al and at least one noble metal element selected from Pt, Pd, Ir, Rh and Ru. Thus, a catalyst for producing a hydrogen-containing gas (hereinafter sometimes referred to as a hydrocarbon reforming catalyst) is subjected to a reduction-oxidation repeated treatment as a pretreatment for activation.
The hydrocarbon reforming catalyst to which the pretreatment method of the present invention is applied is a catalyst in which a noble metal component is supported on a support containing Ni element, Mg element and Al element, and as the noble metal component, Pt, Pd, A material containing at least one element selected from Ir, Rh and Ru is used. Ni in the carrier also has a role as an active ingredient.
This hydrocarbon reforming catalyst is particularly preferably obtained via a hydrotalcite-like layered compound from the viewpoint of catalytic activity.
ハイドロタルサイトは、元来下記式（１）表される粘土鉱物である。
Ｍｇ6Ａｌ2(ＯＨ)16ＣＯ3・４Ｈ2Ｏ・・・・・（１）
近年になり、２価の金属陽イオン[Ｍ(II)2+] 、３価の金属陽イオン［M(III)3+］およびｎ価の層間陰イオン（Ａn-）を含む下記式（２）で表される物質が、ハイドロタルサイト状物質、ハイドロタルサイト様化合物、ハイドロタルサイト構造体、あるいは単にハイドロタルサイトと呼称されるようになった。
［（Ｍ(II)2+）1-X（Ｍ（III）3+）x（ＯＨ-）2］X+（Ａn- x/n）・ｍH2O
・・・・・式（２）
式（１)で表されるハイドロタルサイトは、「ＯＨ-（０．７５Ｍｇ2+、０．２５ＡＩ3+）ＯＨ-」がブルサイト層として面状の骨格をなし、その層間に負の電荷をもつ０．１２５ＣＯ3 2-と０．５Ｈ2Ｏとが挟まれた構造を有している。ブルサイト層内のＭｇ2+とＡｌ3+との比率は広い範囲で変えることができ、それにより、ブルサイト層内の正電荷の密度を制御することが可能である。
Hydrotalcite is originally a clay mineral represented by the following formula (1).
Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O (1)
Recently, a divalent metal cation [M (II) 2+ ], a trivalent metal cation [M (III) 3+ ] and an n-valent interlayer anion (A n− ) The substance represented by 2) has come to be called hydrotalcite-like substance, hydrotalcite-like compound, hydrotalcite structure, or simply hydrotalcite.
[(M (II) 2+ ) 1-X (M (III) 3+ ) x (OH − ) 2 ] X + (A n− x / n ) · mH 2 O
・ ・ ・ ・ ・ Formula (2)
In the hydrotalcite represented by the formula (1), “OH − (0.75Mg 2+ , 0.25AI 3+ ) OH − ” forms a planar skeleton as a brucite layer, and negative charges are formed between the layers. It has a structure in which 0.125 CO 3 2- having 0.5 and 0.5H 2 O are sandwiched. The ratio of Mg 2+ to Al 3+ in the brucite layer can be varied within a wide range, thereby making it possible to control the density of positive charges in the brucite layer.
上記触媒における貴金属成分の含有量は、酸化に対する耐性、触媒活性および経済性のバランスなどの観点から、金属元素として好ましくは０．０５〜３質量％、より好ましくは０．１〜２．０質量％、さらに好ましくは０．２〜１．０質量％である。なお、貴金属元素としては、触媒活性の観点から、特にＲｈおよび/またはＲｕであることが好ましい。
Ｎｉ成分の含有量は、触媒活性および経済性のバランスなどの観点から、金属元素として、好ましくは５〜２５質量％、より好ましくは８〜２０質量％、さらに好ましくは１０〜２０質量％である。
また、Ｍｇ元素およびＡｌ元素の含有量については、Ｍｇ元素とＡｌ元素との合計モル数を１とした場合、Ｍｇ元素は０．５〜０．８５であることが好ましく、０．６〜０．８であることがより好ましい。Ｍｇ元素のモル数が０．５以上であれば多孔質担体としての特性が発揮され、また０．８５以下であれば十分な強度が得られる。
The content of the noble metal component in the catalyst is preferably 0.05 to 3% by mass, more preferably 0.1 to 2.0% by mass as a metal element from the viewpoint of resistance to oxidation, a balance between catalytic activity and economy. %, More preferably 0.2 to 1.0% by mass. The noble metal element is particularly preferably Rh and / or Ru from the viewpoint of catalytic activity.
The content of the Ni component is preferably 5 to 25% by mass, more preferably 8 to 20% by mass, and still more preferably 10 to 20% by mass as a metal element from the viewpoint of a balance between catalytic activity and economy. .
As for the contents of Mg element and Al element, when the total number of moles of Mg element and Al element is 1, the Mg element is preferably 0.5 to 0.85, and 0.6 to 0 .8 is more preferable. When the number of moles of Mg element is 0.5 or more, the characteristics as a porous carrier are exhibited, and when it is 0.85 or less, sufficient strength is obtained.
上記触媒を構成する各元素源としては、以下に示す化合物を挙げることができる。
貴金属元素（Ｒｕ）源であるルテニウム化合物としては、例えばＲｕＣｌ3・ｎＨ2Ｏ、Ｒｕ（ＮＯ3）3、Ｒｕ2（ＯＨ）2Ｃｌ4・７ＮＨ3・３Ｈ2Ｏ、Ｋ2（ＲｕＣｌ5（Ｈ2Ｏ））、（ＮＨ4）2（ＲｕＣｌ5（Ｈ2Ｏ））、Ｋ（ＲｕＣｌ5（ＮＯ））、ＲｕＢｒ3・ｎＨ2Ｏ、Ｎａ2ＲｕＯ4、Ｒｕ（ＮＯ）（ＮＯ3）3、（Ｒｕ3Ｏ（ＯＡｃ）6（Ｈ2Ｏ）3）ＯＡｃ・ｎＨ2Ｏ、Ｋ4（Ｒｕ（ＣＮ）6）・ｎＨ2Ｏ、Ｋ2（Ｒｕ（ＮＯ2）4（ＯＨ）（ＮＯ））、（Ｒｕ（ＮＨ3）6）Ｃｌ3、（Ｒｕ（ＮＨ3）6）Ｂｒ3、（Ｒｕ（ＮＨ3）6）Ｃｌ2、（Ｒｕ（ＮＨ3）6）Ｂｒ2、（Ｒｕ3Ｏ2（ＮＨ3）14）Ｃｌ6・Ｈ2Ｏ、（Ｒｕ（ＮＯ）（ＮＨ3）5）Ｃｌ3、（Ｒｕ（ＯＨ）（ＮＯ）（ＮＨ3）4）（ＮＯ3）2、ＲｕＣｌ2（ＰＰｈ3）3、ＲｕＣｌ2（ＰＰｈ3）4、ＲｕＣｌＨ（ＰＰｈ3）3・Ｃ7Ｈ8、ＲｕＨ2（ＰＰｈ3）4、ＲｕＣｌＨ（ＣＯ）（ＰＰｈ3）3、ＲｕＨ2（ＣＯ）（ＰＰｈ3）3、（ＲｕＣｌ2（ｃｏｄ））n、Ｒｕ（ＣＯ）12、Ｒｕ（ａｃａｃ）3、（Ｒｕ（ＨＣＯＯ）（ＣＯ）2）n、Ｒｕ2Ｉ4（ｐ−ｃｙｍｅｎｅ）2、［Ｒｕ（ＮＯ）（edta）］-等のルテニウム塩を挙げることができる［（edta）はエチレンジアミン四酢酸］。
これらの成分を1種単独でも、２種以上を併用してもよい。
好ましくは、取扱い上の観点からＲｕＣｌ3・ｎＨ2Ｏ、Ｒｕ（ＮＯ3）3、Ｒｕ2（ＯＨ）2Ｃｌ4・７ＮＨ3・３Ｈ2Ｏが用いられる。
Examples of each element source constituting the catalyst include the following compounds.
Examples of the ruthenium compound as a noble metal element (Ru) source include RuCl 3 .nH 2 O, Ru (NO 3 ) 3 , Ru 2 (OH) 2 Cl 4 .7NH 3 .3H 2 O, K 2 (RuCl 5 ( H 2 O)), (NH 4 ) 2 (RuCl 5 (H 2 O)), K (RuCl 5 (NO)), RuBr 3 .nH 2 O, Na 2 RuO 4 , Ru (NO) (NO 3 ) 3 , (Ru 3 O (OAc) 6 (H 2 O) 3 ) OAc · nH 2 O, K 4 (Ru (CN) 6 ) · nH 2 O, K 2 (Ru (NO 2 ) 4 (OH) ( NO)), (Ru (NH 3 ) 6 ) Cl 3 , (Ru (NH 3 ) 6 ) Br 3 , (Ru (NH 3 ) 6 ) Cl 2 , (Ru (NH 3 ) 6 ) Br 2 , (Ru 3 O 2 (NH 3) 14 ) Cl 6 · H 2 O, (Ru (NO) (NH 3) 5) Cl 3, (Ru (OH) (NO) (NH 3) 4) (NO 3) 2 RuCl 2 (PPh 3) 3, RuCl 2 (PPh 3) 4, RuClH (PPh 3) 3 · C 7 H 8, RuH 2 (PPh 3) 4, RuClH (CO) (PPh 3) 3, RuH 2 (CO ) (PPh 3 ) 3 , (RuCl 2 (cod)) n , Ru (CO) 12 , Ru (acac) 3 , (Ru (HCOO) (CO) 2 ) n , Ru 2 I 4 (p-cymene) 2 And ruthenium salts such as [Ru (NO) (edta)] 2 - [(edta) is ethylenediaminetetraacetic acid].
These components may be used alone or in combination of two or more.
From the viewpoint of handling, RuCl 3 .nH 2 O, Ru (NO 3 ) 3 , Ru 2 (OH) 2 Cl 4 .7NH 3 .3H 2 O are preferably used.
貴金属元素（Ｒｈ）源であるロジウム化合物としては、例えば、Ｎａ3ＲｈＣｌ6、（ＮＨ4）2ＲｈＣｌ6、Ｒｈ（ＮＨ3）5Ｃｌ3、Ｒｈ（ＮＯ3）3、ＲｈＣｌ3等を挙げることができる。
貴金属元素（Ｐｔ）源である白金化合物としては、例えば、ＰｔＣｌ4、Ｈ2ＰｔＣｌ6、Ｐｔ（ＮＨ3）4Ｃｌ2、（ＭＨ4）2ＰｔＣｌ2、Ｈ2ＰｔＢｒ6、ＮＨ4［Ｐｔ（Ｃ2Ｈ4）Ｃｌ3］、Ｐｔ（ＮＨ3）4（ＯＨ）2、Ｐｔ（ＮＨ3）2（ＮＯ2）2等を挙げることができる。
貴金属元素（Ｐｄ）源であるパラジウム化合物としては、例えば、（ＮＨ4）2ＰｄＣｌ6、（ＮＨ4）2ＰｄＣｌ4、Ｐｄ（ＮＨ3）4Ｃｌ2、ＰｄＣｌ2、Ｐｄ（ＮＯ3）2等を挙げることができる。
貴金属元素（Ｉｒ）源であるイリジウム化合物としては、例えば、（ＮＨ4）2ＩｒＣｌ6、ＩｒＣｌ3、Ｈ2ＩｒＣｌ6等を挙げることができる。
Examples of rhodium compounds that are noble metal element (Rh) sources include Na 3 RhCl 6 , (NH 4 ) 2 RhCl 6 , Rh (NH 3 ) 5 Cl 3 , Rh (NO 3 ) 3 , RhCl 3 and the like. Can do.
Examples of the platinum compound as a noble metal element (Pt) source include PtCl 4 , H 2 PtCl 6 , Pt (NH 3 ) 4 Cl 2 , (MH 4 ) 2 PtCl 2 , H 2 PtBr 6 , NH 4 [Pt ( C 2 H 4 ) Cl 3 ], Pt (NH 3 ) 4 (OH) 2 , Pt (NH 3 ) 2 (NO 2 ) 2 and the like.
Examples of the palladium compound that is a noble metal element (Pd) source include (NH 4 ) 2 PdCl 6 , (NH 4 ) 2 PdCl 4 , Pd (NH 3 ) 4 Cl 2 , PdCl 2 , Pd (NO 3 ) 2 and the like. Can be mentioned.
Examples of the iridium compound that is a noble metal element (Ir) source include (NH 4 ) 2 IrCl 6 , IrCl 3 , H 2 IrCl 6, and the like.
Ｎｉ元素源であるニッケル化合物としては、例えばＮｉ（ＮＯ3）2・6Ｈ2Ｏ、ＮｉＯ、ＮｉＯＨ）2、ＮｉＳＯ4・6Ｈ2Ｏ、ＮｉＣＯ3、ＮｉＣＯ3・2Ｎｉ（ＯＨ）2・ｎＨ2Ｏ、ＮｉＣｌ2・6Ｈ2Ｏ、（ＨＣＯＯ）2Ｎｉ・２Ｈ2Ｏ、（ＣＨ3ＣＯＯ）2Ｎｉ・4Ｈ2Ｏなどを挙げることができる。
Ｍｇ元素源であるマグネシウム化合物としては、例えばＭｇ（ＮＯ3）2・6Ｈ2Ｏ、ＭｇＯ、Ｍｇ（ＯＨ）2、ＭｇＣ2Ｈ4・2Ｈ2Ｏ、ＭｇＳＯ4・7Ｈ2Ｏ、ＭｇＳＯ4・6Ｈ2Ｏ、ＭｇＣｌ2・6Ｈ2Ｏ、Ｍｇ3（Ｃ6Ｈ5Ｏ7）2・ｎＨ2Ｏ、３ＭｇＣＯ3・Ｍｇ（ＯＨ）2、Ｍｇ（Ｃ6Ｈ5ＣＯＯ）2・４Ｈ2Ｏなど挙げることができる。
Ａｌ元素源であるアルミニウム化合物としては、例えばＡｌ（ＮＯ3）3・9Ｈ2Ｏ、Ａｌ2Ｏ3、Ａｌ（ＯＨ）3、ＡｌＣｌ3・6Ｈ2Ｏ、ＡｌＯ（ＣＯＯＣＨ3）・ｎＨ2Ｏ、Ａｌ2（Ｃ2Ｏ4）3・ｎＨ2Ｏなどを挙げることができる。
Examples of nickel compounds that are Ni element sources include Ni (NO 3 ) 2 .6H 2 O, NiO, NiOH) 2 , NiSO 4 .6H 2 O, NiCO 3 , NiCO 3 .2Ni (OH) 2 .nH 2 O. NiCl 2 .6H 2 O, (HCOO) 2 Ni.2H 2 O, (CH 3 COO) 2 Ni.4H 2 O, and the like.
Examples of the magnesium compound as the Mg element source include Mg (NO 3 ) 2 .6H 2 O, MgO, Mg (OH) 2 , MgC 2 H 4 .2H 2 O, MgSO 4 .7H 2 O, MgSO 4 .6H. include 2 O, MgCl 2 · 6H 2 O, Mg 3 (C 6 H 5 O 7) 2 · nH 2 O, 3MgCO 3 · Mg (OH) 2, Mg (C 6 H 5 COO) such as 2 · 4H 2 O be able to.
Examples of the aluminum compound as the Al element source include Al (NO 3 ) 3 .9H 2 O, Al 2 O 3 , Al (OH) 3 , AlCl 3 .6H 2 O, AlO (COOCH 3 ) · nH 2 O, Examples include Al 2 (C 2 O 4 ) 3 .nH 2 O.
上記触媒はハイドロタルサイト状層状化合物の焼成後に、貴金属成分を担持させることにより得られたものであることが好ましい。
このような触媒は、例えば以下に示す方法により、調製することができる。
硝酸ニッケルなどのＮｉ源、硝酸マグネシウムなどのＭｇ源、硝酸アルミニウムなどのＡｌ源を水に溶かした水溶液と、水酸化ナトリウム水溶液を、炭酸ナトリウム水溶液中に同時にゆっくり滴下し、滴下中常にｐＨが一定となるように調整する。ｐＨは９〜１３程度がよい。次いで、生成した沈殿物を４０〜１００℃程度で３０分ないし８０時間程度、好ましくは１〜２４時間程度熟成したのち、ろ過し、さらに８０〜１５０℃程度で乾燥処理する。
次に、このようにして得られたハイドロタルサイト状層状化合物を、４００〜１５００℃程度の温度で焼成処理することにより、ＮｉＭｇＡｌの複合酸化物を得ることができる。次いで、この複合酸化物に、Ｒｕ源であるＲｕ（ＮＯ3）3のような貴金属化合物を含む水溶液を含浸させ、所定量の貴金属元素を担持させる。この際、貴金属元素がアニオン錯体の中に存在する場合には、イオン交換により貴金属元素を担持することも可能である。イオン交換を行う場合、ＮｉＭｇＡｌの複合酸化物を水溶液中に入れると、メモリー効果により、ハイドロタルサイト構造に戻り、層間にアニオンサイトができるためである。貴金属元素を担持後、さらに４００〜１５００℃程度の温度で焼成処理する。
また、貴金属元素は、最初の沈殿生成反応中に、例えばニッケル源、マグネシウム源およびアルミニウム源と共に、貴金属源となる貴金属化合物を水溶液として導入することも可能である。
上記のように、ハイドロタルサイト状層状化合物を経由して調製された触媒の比表面積は通常５〜２５０ｍ2/ｇ、好ましくは７〜２００ｍ2/ｇである。比表面積が５ｍ2/ｇ未満の場合には、個々の粒子の板面径及び厚みが共に大きいため、触媒は、成形が困難である。２５０ｍ2/ｇを越える場合には、個々の粒子があまりに微細であるため、水洗工程、濾別工程上の問題がある。
The catalyst is preferably obtained by supporting a noble metal component after the calcining of the hydrotalcite layered compound.
Such a catalyst can be prepared, for example, by the method shown below.
An aqueous solution in which an Ni source such as nickel nitrate, an Mg source such as magnesium nitrate, and an Al source such as aluminum nitrate are dissolved in water and an aqueous sodium hydroxide solution are slowly dropped into the aqueous sodium carbonate solution simultaneously, and the pH is always constant during the dropwise addition. Adjust so that The pH is preferably about 9-13. Next, the formed precipitate is aged at about 40 to 100 ° C. for about 30 minutes to 80 hours, preferably about 1 to 24 hours, filtered, and further dried at about 80 to 150 ° C.
Next, a NiMgAl composite oxide can be obtained by firing the hydrotalcite-like layered compound thus obtained at a temperature of about 400 to 1500 ° C. Next, the composite oxide is impregnated with an aqueous solution containing a noble metal compound such as Ru (NO 3 ) 3 which is a Ru source, and a predetermined amount of noble metal element is supported. At this time, when the noble metal element is present in the anion complex, the noble metal element can be supported by ion exchange. This is because, when ion exchange is performed, if a composite oxide of NiMgAl is placed in an aqueous solution, it returns to the hydrotalcite structure due to the memory effect, and anion sites are formed between the layers. After supporting the noble metal element, it is further fired at a temperature of about 400 to 1500 ° C.
In addition, for the noble metal element, it is possible to introduce a noble metal compound serving as a noble metal source as an aqueous solution together with, for example, a nickel source, a magnesium source and an aluminum source during the initial precipitation reaction.
As described above, the specific surface area of the catalyst prepared via the hydrotalcite-like layered compound is usually 5 to 250 m 2 / g, preferably 7 to 200 m 2 / g. When the specific surface area is less than 5 m 2 / g, the catalyst is difficult to mold because both the plate surface diameter and thickness of each particle are large. If it exceeds 250 m 2 / g, the individual particles are too fine, and there is a problem in the water washing process and the filtration process.
本発明の特徴は、このようにして調製した炭化水素改質触媒（焼成後）に、還元−酸化を繰り返す前処理を施すことにより、活性を向上させることにある。
還元−酸化の繰り返し処理において、還元処理は、通常、水素含有ガス雰囲気下、６００〜１１００℃程度、好ましくは７００〜１０００℃の範囲の温度で行われる。この温度が６００℃以上であれば、Ｎｉ成分の還元が十分に行われ、活性の高い触媒を得ることができ、また１１００℃以下であれば、Ｎｉ成分や、Ｒｕ成分などの貴金属成分のシンタリングによる活性低下を抑制することができる。
還元処理時間は、処理温度にもよるが、Ｎｉ成分の十分な還元および経済性のバランスなどの観点から、３０分ないし１０時間程度が好ましく、１〜５時間がより好ましい。
The feature of the present invention is to improve the activity by subjecting the hydrocarbon reforming catalyst thus prepared (after calcination) to pretreatment that repeats reduction-oxidation.
In the reduction-oxidation repeated treatment, the reduction treatment is usually performed at a temperature in the range of about 600 to 1100 ° C., preferably 700 to 1000 ° C. in a hydrogen-containing gas atmosphere. If the temperature is 600 ° C. or higher, the Ni component is sufficiently reduced, and a highly active catalyst can be obtained. If the temperature is 1100 ° C. or lower, the sintering of noble metal components such as the Ni component and the Ru component is possible. The decrease in activity due to the ring can be suppressed.
Although the reduction treatment time depends on the treatment temperature, it is preferably about 30 minutes to 10 hours, more preferably 1 to 5 hours, from the viewpoint of sufficient reduction of the Ni component and economic balance.
一方、還元−酸化の繰り返し処理において、酸化処理は、通常、酸素含有ガス雰囲気下、４００〜１２００℃程度、好ましくは５００〜１０００℃の範囲の温度で行われる。前記酸素含有ガスとしては、通常空気が用いられるが、空気を、窒素やアルゴンなどの不活性ガスで希釈したガス、あるいは水蒸気などを用いることもできる。
酸化処理温度が４００℃以上であれば、Ｎｉ元素や、Ｒｕなどの貴金属元素の酸化が十分に進行し、本発明の効果が良好に発揮され、また１２００℃以下であればＲｕなどの貴金属成分の揮発や表面積の低下が生じにくい。
酸化処理時間は、処理温度にもよるが、Ｎｉ元素や、Ｒｕなどの貴金属元素の十分な酸化および経済性のバランスなどの観点から、３０分ないし１０時間程度が好ましく、１〜５時間がより好ましい。
On the other hand, in the reduction-oxidation repeated treatment, the oxidation treatment is usually performed at a temperature in the range of about 400 to 1200 ° C., preferably 500 to 1000 ° C. in an oxygen-containing gas atmosphere. As the oxygen-containing gas, air is usually used, but a gas obtained by diluting air with an inert gas such as nitrogen or argon, or water vapor can also be used.
When the oxidation treatment temperature is 400 ° C. or higher, the oxidation of Ni elements and noble metal elements such as Ru proceeds sufficiently, and the effects of the present invention are exhibited satisfactorily, and when it is 1200 ° C. or lower, noble metal components such as Ru. Volatilization and surface area reduction are unlikely to occur.
Although depending on the treatment temperature, the oxidation treatment time is preferably about 30 minutes to 10 hours, more preferably 1 to 5 hours, from the viewpoint of sufficient oxidation of Ni element and noble metal elements such as Ru and balance of economy. preferable.
通常、焼成された触媒を還元処理後に反応を行うが、本発明では反応に入る前にさらに酸素含有ガスや水蒸気などで触媒を酸化する。特に酸素含有ガスが好ましく、通常は空気が用いられる。その後還元を行って反応に入ってもよいし、還元を行わずに反応に入ることも可能である。
なお、触媒調製時に触媒は焼成される。この焼成は、Ｎｉ、Ｍｇ、Ａｌの各元素を含むハイドロタルサイトを焼成し、さらに貴金属成分を担持後に焼成する場合もあるし、Ｎｉ、Ｍｇ、Ａｌと同時に、貴金属元素をハイドロタルサイト構造に導入する場合は、１回の焼成で済む場合もある。これらは、いずれも触媒調製時の焼成である。これらも酸化の１種であるが、この焼成（酸化）はここでいう繰り返し酸化の数には数えない。
本発明においては、焼成した触媒を還元処理し、その後、「酸化−還元」を１回繰り返すことを１回繰り返し、「酸化−還元−酸化−還元」とした場合を２回繰り返しとする。
ただし、前述のように、焼成した触媒を還元処理し、その後「酸化」した後反応に入る、０．５回繰り返しや、「酸化−還元−酸化」後に反応にはいる１．５回繰り返しも、本発明の範囲に含まれる。
本発明においては、触媒活性の向上の観点から、焼成した触媒を還元処理後、「酸化−還元」の繰り返し処理を１〜２０回施すことが好ましく、１〜１０回施すことがより好ましく、１〜３回施すことがさらに好ましい。
このように、炭化水素改質触媒に、活性化前処理として、還元−酸化の繰り返し処理を施すことにより、同炭化水素改質触媒の活性や耐久性が向上する理由としては、次のことが考えられる。
活性金属元素であるＮｉとＲｕやＲｈなどの貴金属元素との相互作用により、活性金属元素が高分散化する還元−酸化の繰り返し処理により、相互作用がより強くなって、高活性化および高耐久化をもたらすことが考えられる。しかし、ある一定以上の回数を繰り返すと、活性金属元素の凝集が生じるようになり、活性が低下するものと思われる。
Usually, the calcined catalyst is reacted after the reduction treatment. In the present invention, however, the catalyst is further oxidized with an oxygen-containing gas or water vapor before entering the reaction. An oxygen-containing gas is particularly preferable, and air is usually used. Thereafter, reduction may be performed to enter the reaction, or the reaction may be performed without performing reduction.
The catalyst is calcined at the time of catalyst preparation. In this firing, the hydrotalcite containing each element of Ni, Mg, and Al is fired, and further, the noble metal component may be fired after being supported. In the case of introduction, there is a case where only one firing is sufficient. These are all calcinations during catalyst preparation. These are also one kind of oxidation, but this firing (oxidation) is not counted in the number of repeated oxidations referred to here.
In the present invention, the calcined catalyst is subjected to a reduction treatment, and thereafter, “oxidation-reduction” is repeated once, and “oxidation-reduction-oxidation-reduction” is repeated twice.
However, as described above, the calcined catalyst is reduced, and after being "oxidized", the reaction is repeated 0.5 times, or the reaction is repeated 1.5 times after "oxidation-reduction-oxidation". And within the scope of the present invention.
In the present invention, from the viewpoint of improving the catalytic activity, the calcined catalyst is preferably subjected to the "oxidation-reduction" repeated treatment 1 to 20 times after reduction treatment, more preferably 1 to 10 times, and more preferably 1 to 1. More preferably, it is applied 3 times.
As described above, the reason why the activity and durability of the hydrocarbon reforming catalyst is improved by subjecting the hydrocarbon reforming catalyst to repeated reduction-oxidation treatment as pretreatment for activation is as follows. Conceivable.
Due to the interaction between the active metal element Ni and noble metal elements such as Ru and Rh, the active metal element becomes highly dispersed by the repeated reduction-oxidation process, resulting in higher interaction and higher durability. It is possible to bring about However, if it is repeated a certain number of times or more, aggregation of active metal elements occurs, and the activity is considered to decrease.
前記のようにして、活性化前処理として、還元−酸化の繰り返し処理が施された炭化水素改質触媒を用いて行う炭化水素の改質としては、水蒸気改質、自己熱改質および部分酸化改質を好ましく挙げることができる。
この改質反応に用いられる原料炭化水素としては、例えば、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等の炭素数が１〜１６程度の直鎖状または分岐状の飽和脂肪族炭化水素、シクロヘキサン、メチルシクロヘキサン、シクロオクタン等の脂環式飽和炭化水素、単環および多環芳香族炭化水素、都市ガス、ＬＰＧ、ナフサ、灯油等の各種の炭化水素を挙げることができる。
また、一般に、これらの原料炭化水素中に硫黄分が存在する場合には、脱硫工程を通して、通常、硫黄分が０．１質量ｐｐｍ以下になるまで脱硫を行うことが好ましい。原料炭化水素中の硫黄分が０．１質量ｐｐｍ程度より多くなると、炭化水素改質触媒が失活する原因になることがある。脱硫方法は特に限定されないが、水添脱硫、吸着脱硫等を適宜採用することができる。
As described above, steam reforming, autothermal reforming, and partial oxidation include hydrocarbon reforming using a hydrocarbon reforming catalyst that has been subjected to repeated reduction-oxidation treatment as pretreatment for activation. Modification can be preferably mentioned.
Examples of the raw material hydrocarbon used in the reforming reaction include straight chain or branched chains having about 1 to 16 carbon atoms such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, etc. Saturated aliphatic hydrocarbons, cycloaliphatic saturated hydrocarbons such as cyclohexane, methylcyclohexane and cyclooctane, monocyclic and polycyclic aromatic hydrocarbons, city gas, LPG, naphtha, kerosene and other hydrocarbons Can do.
In general, when sulfur content is present in these raw material hydrocarbons, it is usually preferable to perform desulfurization through the desulfurization step until the sulfur content becomes 0.1 mass ppm or less. If the sulfur content in the raw material hydrocarbon exceeds about 0.1 ppm by mass, the hydrocarbon reforming catalyst may be deactivated. The desulfurization method is not particularly limited, but hydrodesulfurization, adsorptive desulfurization and the like can be appropriately employed.
次に、炭化水素の各改質反応について説明する。
［水蒸気改質反応］
反応条件としては、通常、スチーム/カーボン比（モル比）が１．５〜１０、好ましくは１．５〜５、より好ましくは２〜４となるように炭化水素量と水蒸気量を決定すればよい。このようにスチーム/カーボン比（モル比）を調整することにより、水素含有量の多い生成ガスを効率よく得ることができる。
反応温度は、通常、２００〜９００℃、好ましくは２５０〜９００℃、さらに好ましくは３００〜８００℃である。反応圧力は、通常０〜３ＭＰａ・Ｇ、好ましくは０〜１ＭＰａ・Ｇである。
灯油またはそれ以上の沸点を有する炭化水素を原料とする場合、炭化水素改質触媒層の入口温度を６３０℃以下、好ましくは６００℃以下に保って水蒸気改質を行うのがよい。入口温度が６３０℃を超えると、炭化水素の熱分解が促進され、生成したラジカルを経由して触媒または反応管壁に炭素が析出して、運転が困難になる場合がある。
触媒層出口温度は特に制限はないが、６５０〜８００℃の範囲が好ましい。出口温度が６５０℃以上であれば、水素の生成量が充分であり、また８００℃以下であれば、反応装置は耐熱材料を用いなくてもよく、経済的に好ましい。
なお、水蒸気改質反応に使用する水蒸気としては特に制限はない。
Next, each reforming reaction of hydrocarbon will be described.
[Steam reforming reaction]
As the reaction conditions, the amount of hydrocarbon and the amount of water vapor are usually determined so that the steam / carbon ratio (molar ratio) is 1.5 to 10, preferably 1.5 to 5, more preferably 2 to 4. Good. Thus, by adjusting the steam / carbon ratio (molar ratio), a product gas having a high hydrogen content can be obtained efficiently.
The reaction temperature is usually 200 to 900 ° C, preferably 250 to 900 ° C, more preferably 300 to 800 ° C. The reaction pressure is usually 0 to 3 MPa · G, preferably 0 to 1 MPa · G.
When kerosene or a hydrocarbon having a boiling point higher than that is used as a raw material, the steam reforming may be performed while maintaining the inlet temperature of the hydrocarbon reforming catalyst layer at 630 ° C. or lower, preferably 600 ° C. or lower. When the inlet temperature exceeds 630 ° C., thermal decomposition of hydrocarbons is promoted, and carbon may precipitate on the catalyst or reaction tube wall via the generated radicals, which may make operation difficult.
The catalyst layer outlet temperature is not particularly limited, but is preferably in the range of 650 to 800 ° C. If the outlet temperature is 650 ° C. or higher, the amount of hydrogen produced is sufficient, and if it is 800 ° C. or lower, the reaction apparatus does not need to use a heat-resistant material, which is economically preferable.
The steam used for the steam reforming reaction is not particularly limited.
［自己熱改質反応］
自己熱改質反応は炭化水素の酸化反応と炭化水素と水蒸気の反応が同一リアクター内または連続したリアクター内で起こり、通常、反応温度は２００〜１，３００℃、好ましくは４００〜１，２００℃、より好ましくは５００〜９００℃である。
スチーム/カーボン比（モル比）は、通常、０．１〜１０、好ましくは０．４〜４である。酸素/カーボン比（モル比）は、通常、０．１〜１、好ましくは０．２〜０．８である。
反応圧力は、通常、０〜１０ＭＰａ・Ｇ、好ましくは０〜５ＭＰａ・Ｇ、より好ましくは０〜３ＭＰａ・Ｇである。
炭化水素としては、水蒸気改質反応と同様なものが使用される。
［部分酸化改質反応］
部分酸化改質反応は炭化水素の部分酸化反応が起こり、通常、反応温度は３５０〜１，２００℃、好ましくは４５０〜９００℃である。酸素/カーボン比（モル比）は、通常、０．４〜０．８、好ましくは０．４５〜０．６５である。
反応圧力は、通常、０〜３０ＭＰａ・Ｇ、好ましくは０〜５ＭＰａ・Ｇ、より好ましくは０〜３ＭＰａ・Ｇである。
炭化水素としては、水蒸気改質反応と同様なものが使用される。
[Self-thermal reforming reaction]
The autothermal reforming reaction takes place in the same reactor or in a continuous reactor in which the hydrocarbon oxidation reaction and the hydrocarbon-steam reaction occur. Usually, the reaction temperature is 200 to 1,300 ° C, preferably 400 to 1,200 ° C. More preferably, it is 500-900 degreeC.
The steam / carbon ratio (molar ratio) is usually 0.1 to 10, preferably 0.4 to 4. The oxygen / carbon ratio (molar ratio) is usually 0.1 to 1, preferably 0.2 to 0.8.
The reaction pressure is usually 0 to 10 MPa · G, preferably 0 to 5 MPa · G, more preferably 0 to 3 MPa · G.
As the hydrocarbon, those similar to the steam reforming reaction are used.
[Partial oxidation reforming reaction]
In the partial oxidation reforming reaction, a partial oxidation reaction of hydrocarbon occurs, and the reaction temperature is usually 350 to 1,200 ° C, preferably 450 to 900 ° C. The oxygen / carbon ratio (molar ratio) is usually 0.4 to 0.8, preferably 0.45 to 0.65.
The reaction pressure is usually 0 to 30 MPa · G, preferably 0 to 5 MPa · G, more preferably 0 to 3 MPa · G.
As the hydrocarbon, those similar to the steam reforming reaction are used.
以上の改質反応の反応方式としては、連続流通式、回分式のいずれの方式であってもよいが、連続流通式が好ましい。
連続流通式を採用する場合、炭化水素の液時空間速度（ＬＨＳＶ）は、通常、０．１〜１０ｈ-1、好ましくは、０．２５〜５ｈ-1である。
また、炭化水素としてメタン等のガスを用いる場合は、ガス時空間速度（ＧＨＳＶ）は、通常、２００〜１００，０００ｈ-1である。
反応形式としては、特に制限はなく、固定床式、移動床式、流動床式いずれも採用できるが、固定床式が好ましい。
反応器の形式としても特に制限はなく、例えば、管型反応器等を用いることができる。
上記のような条件で、還元−酸化の繰り返し処理が施された炭化水素改質触媒を用いて、炭化水素の水蒸気改質反応、自己熱改質反応、部分酸化改質反応を行わせることにより水素を含む混合物を得ることができ、燃料電池の水素製造プロセスに好適に使用される。
本発明はまた、炭化水素を改質して水素含有ガスを製造するに際し、使用する触媒に、活性化前処理として、前述の還元−酸化の繰り返し処理を施すことを特徴とする燃料電池用水素の製造方法をも提供する。
The reaction system for the above reforming reaction may be either a continuous flow system or a batch system, but a continuous flow system is preferred.
When employing the continuous flow type, the liquid hourly space velocity (LHSV) of the hydrocarbon is usually 0.1 to 10 h −1 , preferably 0.25 to 5 h −1 .
When a gas such as methane is used as the hydrocarbon, the gas hourly space velocity (GHSV) is usually 200 to 100,000 h −1 .
The reaction format is not particularly limited, and any of a fixed bed type, a moving bed type, and a fluidized bed type can be adopted, but a fixed bed type is preferable.
There is no restriction | limiting in particular also as a form of a reactor, For example, a tubular reactor etc. can be used.
By performing hydrocarbon steam reforming reaction, autothermal reforming reaction, and partial oxidation reforming reaction using a hydrocarbon reforming catalyst that has been subjected to repeated reduction-oxidation treatment under the above conditions. A mixture containing hydrogen can be obtained and is suitably used in a hydrogen production process of a fuel cell.
The present invention also provides a hydrogen for a fuel cell, characterized by subjecting a catalyst to be used to the above-mentioned reduction-oxidation repeated treatment as a pre-activation treatment when reforming a hydrocarbon to produce a hydrogen-containing gas. A manufacturing method is also provided.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
比較調製例１
Ｎｉ（ＮＯ3）2・６Ｈ2Ｏの１６．４１４ｇ、Ｍｇ（ＮＯ3）2・６Ｈ2Ｏの７０．８１３ｇおよびＡｌ（ＮＯ3）3・９Ｈ2Ｏの４１．４９２ｇを、水１５０ｍリットルに溶解してＡ液を調製し、Ｎａ2ＣＯ3・１０Ｈ2Ｏの１５．８１６ｇを水１００ミリリットルに溶解してＢ液を調製した。
次いで、前記Ｂ液中にＡ液を滴下する。この際、液のｐＨが１０になるように、１モル/リットル濃度のＮａＯＨ水溶液を適宜滴下する。Ａ液の滴下が終了したのち、９０℃で４０分間攪拌し、その後９０℃にて２０時間静置後、放冷し、吸引ろ過により沈殿物を取り出した。
次に、沈殿物を２リットルの水で洗浄後、１０５℃にて９時間乾燥処理したのち、０．８３℃/分の速度で８５０℃まで昇温し、その温度で５時間焼成処理することにより、貴金属元素を含まない触媒Ｘ−１（ｓｐｃ−Ｎｉ/Ｍｇ−Ａｌ）を得た。
触媒Ｘ−１中のＮｉ含有量は１４質量％、Ｍｇ含有量は２８質量％、Ａｌ含有量は１６質量％であった。
なお、ｓｐｃはsolid phase crystallization（固相晶析法）の略である。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Comparative Preparation Example 1
16.414 g of Ni (NO 3 ) 2 · 6H 2 O, 70.813 g of Mg (NO 3 ) 2 · 6H 2 O and 41.492 g of Al (NO 3 ) 3 · 9H 2 O into 150 ml of water Solution A was prepared by dissolving, and solution B was prepared by dissolving 15.816 g of Na 2 CO 3 .10H 2 O in 100 ml of water.
Subsequently, A liquid is dripped in the said B liquid. At this time, a 1 mol / liter NaOH aqueous solution is appropriately added dropwise so that the pH of the solution is 10. After completion of dropping of the liquid A, the mixture was stirred at 90 ° C. for 40 minutes, then allowed to stand at 90 ° C. for 20 hours, allowed to cool, and the precipitate was taken out by suction filtration.
Next, the precipitate is washed with 2 liters of water, dried at 105 ° C. for 9 hours, heated to 850 ° C. at a rate of 0.83 ° C./minute, and baked at that temperature for 5 hours. Thus, catalyst X-1 (spc-Ni / Mg-Al) containing no noble metal element was obtained.
In the catalyst X-1, the Ni content was 14% by mass, the Mg content was 28% by mass, and the Al content was 16% by mass.
Note that spc is an abbreviation for solid phase crystallization.
調製例１
５０ｇ/リットル濃度のＲｕ（ＮＯ3）3水溶液０．５ミリリットルを、水２００ミリリットルで希釈して、Ｃ液を調製した。このＣ液に、比較調製例１で得た触媒Ｘ−１の５．０ｇを投入し、室温で１２時間攪拌したのち、攪拌しながら９０℃に加熱して沈殿物を蒸発乾固した。
次いで、乾固物を０．８３℃/分の速度で８５０℃まで昇温したのち、その温度で５時間焼成処理することにより、貴金属元素を含む触媒Ｙ−１（ｓｐｃ−Ｒｕ−Ｎｉ/Ｍｇ−Ａｌ）を得た。
触媒Ｙ−１中のＲｕ含有量は０．５質量％であった。
調製例２
調製例１における５０ｇ/リットル濃度のＲｕ（ＮＯ3）3水溶液０．５ミリリットルの替りに、４．５質量％濃度のＲｈ（ＮＯ3）3水溶液０．５５ミリリットルを用いた以外は、調製例１と同様な操作を行い、貴金属元素を含む触媒Ｙ−２（ｓｐｃ−Ｒｈ−Ｎｉ/Ｍｇ−Ａｌ）を得た。
触媒Ｙ−２中のＲｈ含有量は０．５質量％であった。
Preparation Example 1
Liquid C was prepared by diluting 0.5 ml of a 50 g / liter Ru (NO 3 ) 3 aqueous solution with 200 ml of water. To this liquid C, 5.0 g of the catalyst X-1 obtained in Comparative Preparation Example 1 was added, stirred for 12 hours at room temperature, and then heated to 90 ° C. with stirring to evaporate the precipitate.
Next, the dried product was heated to 850 ° C. at a rate of 0.83 ° C./minute, and then calcined at that temperature for 5 hours, whereby catalyst Y-1 containing noble metal element (spc-Ru—Ni / Mg -Al) was obtained.
The Ru content in the catalyst Y-1 was 0.5% by mass.
Preparation Example 2
Preparation example except that 0.55 ml of 4.5 mass% concentration of Rh (NO 3 ) 3 aqueous solution was used instead of 0.5 ml of 50 g / liter concentration Ru (NO 3 ) 3 aqueous solution in Preparation Example 1. The same operation as in No. 1 was performed to obtain catalyst Y-2 (spc-Rh-Ni / Mg-Al) containing a noble metal element.
The Rh content in the catalyst Y-2 was 0.5% by mass.
比較調製例２
（１）担体の調製
Ｍｎ（ＣＨ3ＣＯＯ）2・４Ｈ2Ｏの５．４５ｇを水１１．５ミリリットルに溶解し、含浸液Ａを調製した。次に、予め十分に乾燥させたγ−アルミナ担体３０ｇに前記含浸液Ａをポアフィリング法にて含浸させたのち、１２０℃で３時間乾燥処理し、次いで８００℃で３時間焼成処理することにより、Ｍｎ担持担体を得た。
（２）触媒の調製
ＲｕＣｌ3の０．３９ｇを水１．８ミリリットルに溶解し、含浸液Ｂを調製した。予め十分に乾燥させた前記（１）のＭｎ担持担体５．０ｇに、上記含浸液Ｂをポアフィリング法にて含浸させたのち、５モル/リットル濃度のＮａＯＨ水溶液１００ミリリットルで１時間アルカリ分解した。次いで、一昼夜かけて水洗後、１２０℃にて５時間乾燥処理することにより、貴金属元素を含む触媒Ｘ−２（Ｒｕ/Ｍｎ/Ａｌ2Ｏ3）を得た。
触媒Ｘ−２中のＲｕ含有量は３．０質量％、Ｍｎ含有量は３．７質量％であった。
Comparative Preparation Example 2
(1) Preparation of carrier 5.45 g of Mn (CH 3 COO) 2 .4H 2 O was dissolved in 11.5 ml of water to prepare an impregnating solution A. Next, after impregnating the impregnating solution A with 30 g of a sufficiently dried γ-alumina carrier by the pore filling method, drying treatment is performed at 120 ° C. for 3 hours, and then baking treatment is performed at 800 ° C. for 3 hours. A Mn-supported carrier was obtained.
(2) Preparation of catalyst 0.39 g of RuCl 3 was dissolved in 1.8 ml of water to prepare impregnation liquid B. The impregnating solution B was impregnated by the pore filling method in 5.0 g of the Mn-supported carrier (1) sufficiently dried in advance, and then alkali-decomposed with 100 ml of 5 mol / liter NaOH aqueous solution for 1 hour. . Next, after washing with water for a whole day and night, the catalyst X-2 (Ru / Mn / Al 2 O 3 ) containing a noble metal element was obtained by drying at 120 ° C. for 5 hours.
The Ru content in the catalyst X-2 was 3.0 mass%, and the Mn content was 3.7 mass%.
比較調製例３
５０ｇ/リットル濃度のＲｕ（ＮＯ3）3水溶液０．６０ｇと、Ｎｉ（ＮＯ3）2・６Ｈ2Ｏの４．１２ｇを極少量の水に溶解して含浸液Ｃを調製した。予め十分に乾燥させた比較調製例２の（１）で得たＭｎ担持担体５．０ｇに上記含浸液Ｃをポアフィリング法にて含浸させたのち、５モル/リットル濃度のＮａＯＨ水溶液１００ミリリットルで１時間アルカリ分解した。次いで一昼夜かけて水洗後、１２０℃にて５時間乾燥処理することにより、貴金属元素を含む触媒Ｘ−３（Ｒｕ−Ｎｉ/Ｍｎ/Ａｌ2Ｏ3）を得た。
触媒Ｘ−３中のＲｕ含有量は０．５質量％、Ｎｉ含有量は１４質量％、Ｍｎ含有量は２．８質量％であった。
Comparative Preparation Example 3
An impregnating solution C was prepared by dissolving 0.60 g of a 50 g / liter Ru (NO 3 ) 3 aqueous solution and 4.12 g of Ni (NO 3 ) 2 .6H 2 O in a very small amount of water. After impregnating the above impregnating solution C by the pore filling method with 5.0 g of the Mn-supported carrier obtained in (1) of Comparative Preparation Example 2 which was sufficiently dried in advance, 100 ml of 5 mol / liter NaOH aqueous solution was used. The alkali was decomposed for 1 hour. Next, after washing with water for a whole day and night, the catalyst X-3 (Ru—Ni / Mn / Al 2 O 3 ) containing a noble metal element was obtained by drying at 120 ° C. for 5 hours.
The Ru content in the catalyst X-3 was 0.5 mass%, the Ni content was 14 mass%, and the Mn content was 2.8 mass%.
比較調製例４
４．５質量％濃度のＲｈ（ＮＯ3）3水溶液０．６５ｇと、Ｎｉ（ＮＯ3）2・６Ｈ2Ｏの４．１２ｇを、極少量の水に溶解して含浸液Ｄを調製した。予め十分に乾燥させた比較調製例２の（１）で得たＭｎ担持担体５．０ｇに、上記含浸液Ｄをポアフィリング法にて含浸させたのち、５モル/リットル濃度のＮａＯＨ水溶液１００ミリリットルで１時間アルカリ分解した。次いで一昼夜かけて水洗後、１２０℃にて５時間乾燥処理することにより、貴金属元素を含む触媒Ｘ−４（Ｒｈ−Ｎｉ/Ｍｎ/Ａｌ2Ｏ3）を得た。
触媒Ｘ−４中のＲｈ含有量は０．５質量％、Ｎｉ含有量は１４質量％、Ｍｎ含有量は２．７質量％であった。
Comparative Preparation Example 4
An impregnating solution D was prepared by dissolving 0.65 g of a 4.5 mass% concentration Rh (NO 3 ) 3 aqueous solution and 4.12 g of Ni (NO 3 ) 2 .6H 2 O in a very small amount of water. After impregnating the above impregnating solution D with the pore filling method in 5.0 g of the Mn-supported carrier obtained in (1) of Comparative Preparation Example 2 which has been sufficiently dried in advance, 100 ml of an aqueous NaOH solution having a concentration of 5 mol / liter. For 1 hour. Next, after washing with water for a whole day and night, the catalyst X-4 (Rh—Ni / Mn / Al 2 O 3 ) containing a noble metal element was obtained by drying at 120 ° C. for 5 hours.
The Rh content in the catalyst X-4 was 0.5 mass%, the Ni content was 14 mass%, and the Mn content was 2.7 mass%.
実施例１、２および比較例１〜４
調製例１および２で得た触媒Ｙ−１およびＹ−２、並びに比較調製例１〜４で得た触媒Ｘ−１〜Ｘ−４を用い、以下に示す（１）〜（３）の操作を順次行い、水蒸気改質反応における触媒の酸化−還元処理繰り返しによる、高活性化と高耐久化を検討した。
（１）初期還元処理
各触媒を１６〜３２メッシュの大きさに成型し、それぞれ２００ｍｇを反応管に充填し、水素気流下で８５０℃にて１時間還元前処理を行う。
（２）酸化/還元処理
（ｉ）７００℃で空気導入を３時間継続、（ii）空気導入停止および（iii）８５０℃での還元処理を１サイクルとし、第2表に示すサイクル数の処理を繰り返す。
（３）水蒸気改質前後の反応評価
反応温度を５００℃に保持しながら、触媒層へ脱硫灯油（Ｓ：０．０２質量ｐｐｍ未満）と水を、同脱硫灯油の液時空間速度（ＬＨＳＶ）が１６．５ｈ-1、スチーム/カーボン（モル比）が３．０になるように供給して水蒸気改質反応を開始し、反応開始１時間後、得られたガスをサンプリングして灯油のＣ1転化率を求め、反応評価を行う。
この反応評価を、水蒸気改質前、水蒸気改質１回後および水蒸気改質２回後の各触媒（初期還元処理触媒、酸化−還元処理１〜２０回繰り返し触媒）について、それぞれ行う。
なお、灯油のＣ1転化率は、下記式より求める。
Ｃ1転化率（％）＝（Ａ/Ｂ）×１００
［上記式において、Ａ＝ＣＯモル流量＋ＣＯ2モル流量＋ＣＨ4モル流量（いずれも反応器出口における流量）、Ｂ＝反応器入口側の灯油の炭素モル流量である］
これらの結果を第１表および第２表に示す。
Examples 1 and 2 and Comparative Examples 1 to 4
The operations of (1) to (3) shown below using the catalysts Y-1 and Y-2 obtained in Preparation Examples 1 and 2 and the catalysts X-1 to X-4 obtained in Comparative Preparation Examples 1 to 4 In order to improve the activity and durability of the catalyst by repeated oxidation-reduction treatment of the catalyst in the steam reforming reaction.
(1) Initial reduction treatment Each catalyst is molded to a size of 16 to 32 mesh, 200 mg each is filled in a reaction tube, and reduction pretreatment is performed at 850 ° C. for 1 hour in a hydrogen stream.
(2) Oxidation / reduction treatment (i) Introducing air at 700 ° C for 3 hours, (ii) Stopping air introduction, and (iii) Reducing treatment at 850 ° C is one cycle, and the number of cycles shown in Table 2 repeat.
(3) Reaction evaluation before and after steam reforming While maintaining the reaction temperature at 500 ° C., desulfurized kerosene (S: less than 0.02 mass ppm) and water were supplied to the catalyst layer, and the liquid hourly space velocity (LHSV) of the desulfurized kerosene. Is 16.5 h −1 and steam / carbon (molar ratio) is 3.0 to start the steam reforming reaction. One hour after the start of the reaction, the obtained gas is sampled to obtain C1 of kerosene. Obtain the conversion and evaluate the reaction.
This reaction evaluation is performed for each catalyst (initial reduction treatment catalyst, oxidation-reduction treatment 1 to 20 times repeated catalyst) before steam reforming, after one steam reforming and after two steam reforming, respectively.
The C1 conversion rate of kerosene is obtained from the following formula.
C1 conversion (%) = (A / B) × 100
[In the above formula, A = CO molar flow rate + CO 2 molar flow rate + CH 4 molar flow rate (both flow rates at the reactor outlet), B = carbon molar flow rate of kerosene on the reactor inlet side]
These results are shown in Tables 1 and 2.
第２表から、実施例１および２においては、酸化−還元繰り返し処理により、以下に示すことが分かる。
（１）前処理後の活性が向上し、水蒸気改質前の活性は、酸化−還元を３回繰り返した時点が最も高い。
（２）水蒸気改質の耐久性が向上し、水蒸気改質後の活性は、４回〜６回繰り返した時点が最も高い。２０回繰り返しても、初期還元後（つまり、酸化−還元処理を行わないケース）よりも、高い活性を維持できる。
（３）活性金属元素であるＮｉとＲｕ、あるいはＮｉとＲｈの相互作用により、金属元素が高分散化する酸化−還元の繰り返し処理により、相互作用がより強くなり、高活性化および高耐久化をもたらす。一方、ある一定以上の回数を繰り返すと、活性金属元素の凝集が起こり、活性が低下する。
一方、比較例では、酸化−還元の繰り返し処理によっても、高活性化をもたらさない。また、アルミナ担体では、前記のような効果は期待できない。
From Table 2, it can be seen that in Examples 1 and 2, the following are shown by the oxidation-reduction repeated treatment.
(1) The activity after the pretreatment is improved, and the activity before the steam reforming is highest when the oxidation-reduction is repeated three times.
(2) The durability of steam reforming is improved, and the activity after steam reforming is highest when it is repeated 4 to 6 times. Even if it is repeated 20 times, a higher activity can be maintained than after the initial reduction (that is, the case where the oxidation-reduction treatment is not performed).
(3) The interaction between Ni and Ru, which are active metal elements, or Ni and Rh, the interaction is strengthened by repeated oxidation-reduction treatment in which the metal element is highly dispersed, resulting in high activation and high durability. Bring. On the other hand, if a certain number of times or more is repeated, aggregation of the active metal element occurs and the activity decreases.
On the other hand, in the comparative example, high activation is not brought about even by repeated oxidation-reduction treatment. In addition, the above-mentioned effects cannot be expected with an alumina support.
本発明の水素製造触媒の前処理方法は、特定の金属元素を含む炭化水素改質触媒、特にハイドロタルサイト状層状化合物を経由して得られる触媒に、活性化前処理として、還元−酸化の繰り返し処理を施すことにより、同触媒の活性を向上させる方法であって、燃料電池用水素の製造に適用することができる。 The pretreatment method for the hydrogen production catalyst of the present invention comprises a hydrocarbon reforming catalyst containing a specific metal element, particularly a catalyst obtained via a hydrotalcite-like layered compound. This is a method for improving the activity of the catalyst by repeated treatment, and can be applied to the production of hydrogen for fuel cells.
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