JP2010188238A - Catalyst for production of hydrogen and method of producing hydrogen using the same - Google Patents
Catalyst for production of hydrogen and method of producing hydrogen using the same Download PDFInfo
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- JP2010188238A JP2010188238A JP2009033156A JP2009033156A JP2010188238A JP 2010188238 A JP2010188238 A JP 2010188238A JP 2009033156 A JP2009033156 A JP 2009033156A JP 2009033156 A JP2009033156 A JP 2009033156A JP 2010188238 A JP2010188238 A JP 2010188238A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 122
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 122
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 76
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 60
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002902 bimodal effect Effects 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000004215 Carbon black (E152) Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000002407 reforming Methods 0.000 claims description 19
- 238000006057 reforming reaction Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
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- 238000000629 steam reforming Methods 0.000 claims description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 12
- 239000008158 vegetable oil Substances 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
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- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
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- 238000002453 autothermal reforming Methods 0.000 claims description 6
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- 238000012986 modification Methods 0.000 abstract 1
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- 238000003786 synthesis reaction Methods 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 7
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- 229910000510 noble metal Inorganic materials 0.000 description 3
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
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- 238000004868 gas analysis Methods 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
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- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Catalysts (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
本発明は、水素製造用触媒及び水素製造方法に関し、さらに詳しくは、特定の細孔を有する水素製造用触媒であって、植物油脂の改質にも有効な水素製造用触媒及び該触媒を用いた水素製造方法に関するものである。 The present invention relates to a hydrogen production catalyst and a hydrogen production method. More specifically, the present invention relates to a hydrogen production catalyst having specific pores, which is effective for reforming vegetable oils and fats, and uses the catalyst. The present invention relates to a conventional hydrogen production method.
新エネルギーである燃料電池は、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、産業用あるいは自動車用などとして、実用化研究が積極的になされている。
燃料電池に用いる水素は、通常、炭化水素などの水素源を水蒸気改質処理、自己熱改質処理、部分酸化改質処理などの改質処理を行って製造されている。したがって、改質処理に用いる改質触媒の性能が重要である。
炭化水素などの改質触媒としては、従来、ルテニウムや、白金、ロジウム、パラジウム、イリジウム、ニッケルなどをベースにした触媒の研究もなされていて、より活性の高い触媒の開発が進められている。
例えば、特許文献１には、マイクロメートル領域の細孔径を有するマクロ細孔と、ナノメートル領域の細孔径を有するメソ細孔との二種類のタイプの細孔を有する二元細孔シリカに、Ｎｉを担持したＮｉ／ＳiＯ2触媒が開示されており、メタンのＣＯ2改質反応に効果が高いことが記載されている。
また、特許文献２には、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一種の貴金属元素を含む触媒が、灯油のような炭素数５以上で、かつ、常温常圧で液状の炭化水素または酸素を含む炭化水素を改質処理する水素含有ガスの製造方法が記載されている。
Fuel cells, a new energy, convert chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and are characterized by high energy use efficiency. Research into practical use has been actively conducted for industrial use or automobile use.
Hydrogen used in fuel cells is usually produced by subjecting a hydrogen source such as hydrocarbons to reforming treatment such as steam reforming treatment, autothermal reforming treatment, and partial oxidation reforming treatment. Therefore, the performance of the reforming catalyst used for the reforming process is important.
As reforming catalysts such as hydrocarbons, studies on catalysts based on ruthenium, platinum, rhodium, palladium, iridium, nickel, and the like have been made, and development of more active catalysts has been promoted.
For example, in
Patent Document 2 discloses that a catalyst containing Ni, Mg and Al and containing at least one noble metal element selected from Pt, Pd, Ir, Rh and Ru has 5 or more carbon atoms such as kerosene, In addition, a method for producing a hydrogen-containing gas is described in which a hydrocarbon or oxygen-containing hydrocarbon that is liquid at normal temperature and pressure is reformed.
ところで、燃料電池システムに利用する水素源としては、これまでメタノールや、液化天然ガス、都市ガス、石油系ＬＰＧ、ナフサ及び灯油などの石油系炭化水素を用いる研究がなされている。
一方、近年地球温暖化対策やエネルギーの安定供給の確保、地域分散型電源の確保といった観点から生物由来の有機性資源であるバイオマスがクリーンなエネルギー源として注目されている。このバイオマスとは、エネルギー源又は工業原料として利用することのできる生物体（例えば農業生産物又は副生成物、植物、油脂等）をいい、太陽エネルギー、空気、水、土壌等の作用により生成されるので無限に再生可能な資源である。また、現在バイオマスの中の油脂類などが廃棄されるなど、廃棄物処理問題が顕在化しつつあることに伴い、資源を有効利用し循環型社会を構築することにより環境保全及び省資源化を図ることが推奨されており、バイオマスを、エネルギー源や工業原料として総合的に利活用する技術が要望されている。
したがって、このバイオマスを将来需要が拡大することが予測される燃料電池システムの水素源として使用することは望まれるところである。
しかしながら、油脂類などのバイオマスは、炭素鎖が長い炭化水素類であることから、それを水素源とする改質反応が困難であり、従来の改質触媒では、触媒の活性や寿命（耐久性）などの点で不充分であった。
このようなことから、触媒性能のさらなる向上が求められている。
By the way, research using petroleum hydrocarbons such as methanol, liquefied natural gas, city gas, petroleum LPG, naphtha, and kerosene has been made as a hydrogen source used in the fuel cell system.
On the other hand, in recent years, biomass, which is an organic resource derived from living organisms, has attracted attention as a clean energy source from the viewpoints of global warming countermeasures, ensuring a stable supply of energy, and securing a regional distributed power source. Biomass refers to organisms that can be used as energy sources or industrial raw materials (for example, agricultural products or by-products, plants, oils and fats), and are produced by the action of solar energy, air, water, soil, etc. So it is an infinitely recyclable resource. In addition, due to the fact that waste disposal problems such as oils and fats in biomass are now becoming apparent, we aim to conserve the environment and save resources by building a recycling society by effectively using resources. Therefore, there is a demand for a technology that comprehensively utilizes biomass as an energy source and industrial raw material.
Therefore, it is desirable to use this biomass as a hydrogen source for a fuel cell system where future demand is expected to expand.
However, biomass, such as fats and oils, is a hydrocarbon with a long carbon chain, so it is difficult to perform a reforming reaction using it as a hydrogen source. With conventional reforming catalysts, the activity and life of the catalyst (durability) ) And the like.
For these reasons, further improvement in catalyst performance is required.
このような状況下で、本発明は、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、優れた改質活性及び耐久性を示す水素製造用触媒を提供することを目的とするものである。
また、本発明は、上記水素製造用触媒を用いて、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、効率的に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 provides hydrogen having excellent reforming activity and durability even when a hydrocarbon containing a long carbon chain such as vegetable oil or fat or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source. An object of the present invention is to provide a production catalyst.
In addition, the present invention efficiently produces hydrogen using the hydrogen production catalyst even when a hydrocarbon containing a long carbon chain such as vegetable oil or fat or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source. It is intended to provide a method.
本発明者は、前記の好ましい水素製造用触媒を開発すべく鋭意研究を重ねた結果、多孔質担体にジルコニウムが含まれるとともに、多孔質担体を特定の細孔直径の細孔を有するバイモーダル構造である触媒が、前記目的に適合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 studies to develop the above-mentioned preferred catalyst for hydrogen production, the present inventor has found that the porous support contains zirconium, and the porous support has a bimodal structure having pores having a specific pore diameter. It has been found that a catalyst which is The present invention has been completed based on such findings.
すなわち、本発明は、
（１）多孔質担体に活性金属を担持した触媒であって、当該多孔質担体が、ジルコニウムを含み、かつ細孔直径が２〜１０ｎｍの細孔と２０〜２００ｎｍの細孔を有するバイモーダル構造を有することを特徴とする水素製造用触媒、
（２）多孔質担体が細孔直径２〜８ｎｍの細孔および２０〜１００ｎｍの細孔を有することを特徴とする（１）に記載の水素製造用触媒、
（３）多孔質担体が細孔直径２〜７ｎｍの細孔および２０〜５０ｎｍの細孔を有することを特徴とする（１）に記載の水素製造用触媒、
（４）多孔質担体が、ジルコニウム以外に、シリカ、アルミナ、及びチタニアから選ばれる少なくとも一種を含むものである（１）〜（３）のいずれかに記載の水素製造用触媒、
（５）活性金属が、Ｎｉ、Ｃｏ、Ｒｕ、Ｒｈ、Ｉｒ、Ｐｔ、及びＰｄから選ばれる少なくとも一種である（１）〜（４）のいずれかに記載の水素製造用触媒、
（６）活性金属がＮｉである（５）に記載の水素製造用触媒、
（７）さらに希土類金属を含む（１）〜（６）のいずれかに記載の水素製造用触媒、
（８）希土類金属がセリウムである（７）の水素製造用触媒、
（９）炭化水素もしくは酸素を含有する炭化水素と（１）〜（８）いずれかに記載の水素製造用触媒を接触させる工程を含む、水素製造方法、
（１０）（９）における炭化水素もしくは酸素を含有する炭化水素と水素製造用触媒を接触させる工程において、水蒸気改質反応、自己熱改質反応、部分酸化改質反応又は炭酸ガス改質反応のいずれかの改質反応が行われることを特徴とする（９）に記載の炭化水素改質による水素製造方法、
（１１）（１０）において、酸素を含有する炭化水素が植物油脂である水素製造方法、
（１２）（１１）において、植物油脂が菜種油、ごま油、ひまわり油から選ばれる少なくとも一種である水素製造方法、
を提供するものである。
That is, the present invention
(1) A catalyst in which an active metal is supported on a porous carrier, wherein the porous carrier contains zirconium and has a pore diameter of 2 to 10 nm and a pore of 20 to 200 nm. A catalyst for hydrogen production, comprising:
(2) The catalyst for hydrogen production according to (1), wherein the porous carrier has pores having a pore diameter of 2 to 8 nm and pores of 20 to 100 nm,
(3) The catalyst for hydrogen production according to (1), wherein the porous carrier has pores having a pore diameter of 2 to 7 nm and pores of 20 to 50 nm,
(4) The catalyst for hydrogen production according to any one of (1) to (3), wherein the porous carrier contains at least one selected from silica, alumina, and titania in addition to zirconium.
(5) The catalyst for hydrogen production according to any one of (1) to (4), wherein the active metal is at least one selected from Ni, Co, Ru, Rh, Ir, Pt, and Pd,
(6) The catalyst for hydrogen production according to (5), wherein the active metal is Ni,
(7) The catalyst for hydrogen production according to any one of (1) to (6), further comprising a rare earth metal,
(8) The catalyst for hydrogen production according to (7), wherein the rare earth metal is cerium,
(9) A hydrogen production method comprising a step of bringing a hydrocarbon or a hydrocarbon containing oxygen into contact with the hydrogen production catalyst according to any one of (1) to (8),
(10) In the step of bringing the hydrocarbon or oxygen-containing hydrocarbon into contact with the hydrogen production catalyst in (9), the steam reforming reaction, autothermal reforming reaction, partial oxidation reforming reaction or carbon dioxide reforming reaction The method for producing hydrogen by hydrocarbon reforming according to (9), wherein any reforming reaction is performed,
(11) In (10), the hydrogen production method wherein the hydrocarbon containing oxygen is vegetable oil or fat,
(12) The method for producing hydrogen according to (11), wherein the vegetable oil is at least one selected from rapeseed oil, sesame oil, and sunflower oil,
Is to provide.
本発明によれば、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、優れた改質活性及び耐久性を示す水素製造用触媒を提供することができる。
また、本発明は、上記水素製造用触媒を用いて、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、効率的に水素を製造する方法を提供することができる。
According to the present invention, there is provided a hydrogen production catalyst that exhibits excellent reforming activity and durability even when a hydrocarbon containing a long carbon chain or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source, such as vegetable oils and fats. can do.
In addition, the present invention efficiently produces hydrogen using the hydrogen production catalyst even when a hydrocarbon containing a long carbon chain such as vegetable oil or fat or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source. A method can be provided.
以下に、本発明の水素製造用触媒及び水素製造方法を詳細に述べる。
［水素製造用触媒］
本発明の水素製造用触媒は、多孔質担体に活性金属を担持した触媒であって、当該多孔質担体が、ジルコニウムを含み、かつ細孔直径が２〜１０ｎｍの細孔と２０〜２００ｎｍの細孔を有するバイモーダル構造を有することを特徴とする水素製造用触媒である。
前記多孔質担体が有するバイモーダル構造とは、細孔直径が相対的に大きいメソポア又はマクロポアと相対的に小さなメソポアとを併せて有する二元細孔構造を有する多孔質担体のことである。
本発明のバイモーダル構造を有する多孔質体は、通常第１の多孔質体、及び該第１の多孔質体の表面に形成される第２の成分からなる多孔質部位（第２の多孔質体）を有する。すなわち、本発明のバイモーダル多孔質体は、第１の多孔質体を第２の成分により修飾して得られたバイモーダル多孔質体であることが好ましい。
The hydrogen production catalyst and the hydrogen production method of the present invention are described in detail below.
[Catalyst for hydrogen production]
The catalyst for hydrogen production of the present invention is a catalyst in which an active metal is supported on a porous carrier, and the porous carrier contains zirconium, and has a pore diameter of 2 to 10 nm and a pore diameter of 20 to 200 nm. It is a hydrogen production catalyst characterized by having a bimodal structure having pores.
The bimodal structure possessed by the porous carrier refers to a porous carrier having a binary pore structure having both mesopores or macropores having relatively large pore diameters and relatively small mesopores.
The porous body having a bimodal structure according to the present invention is usually a first porous body and a porous portion (second porous body) composed of the second component formed on the surface of the first porous body. Body). That is, the bimodal porous body of the present invention is preferably a bimodal porous body obtained by modifying the first porous body with the second component.
まず、前記第１の多孔質体について説明する。
第１の多孔質体は、第１の成分を有している。
第１の成分としては、例えば、シリカ、アルミナ、ジルコニア、チタニア、マグネシアなどが挙げられる。中でも、耐熱性や触媒強度の観点から、シリカ、アルミナ、ジルコニア、チタニアが好ましい。第１の成分としては、これらの中の一種を用いてもよいし、二種以上を併用して用いてもよい。
このような第１の成分から成る第１の多孔質体は、細孔直径が２０〜２００ｎｍ、好ましくは２０〜１００ｎｍ、特に好ましくは２０〜５０ｎｍであり、このような細孔が、バイモーダル多孔質体において相対的に大きなメソポア又はマクロポアに相当する。
First, the first porous body will be described.
The first porous body has a first component.
Examples of the first component include silica, alumina, zirconia, titania, magnesia and the like. Among these, silica, alumina, zirconia, and titania are preferable from the viewpoint of heat resistance and catalyst strength. As the first component, one of these may be used, or two or more may be used in combination.
The first porous body composed of such a first component has a pore diameter of 20 to 200 nm, preferably 20 to 100 nm, particularly preferably 20 to 50 nm, and such pores are bimodal porous. It corresponds to a relatively large mesopore or macropore in the mass.
一方、第２の多孔質体である多孔質部位は、第１の多孔質体の表面に形成される。第１の多孔質体の表面とは、第１の多孔質体を構成する粒子の外表面と細孔表面を併せたものである。
当該多孔質部位は、第２の成分を有している。本発明においては、該第２の成分としては、ジルコニアを含む成分を用いる。ジルコニアを用いることによって、前記バイモーダル構造を有する担体を形成することができ、目的とする改質効果を有する触媒を得ることができる。
前記ジルコニアを含む成分は、ジルコニアを主成分とするものが好ましい。すなわち、ジルコニア単独にとどまらず、ジルコニアとともにジルコニア以外の成分を用いてもよい。ここで、主成分とは、第２の成分全量規準で５０質量％以上、好ましく７０質量％以上、特に９０質量％以上であることを意味する。
前記ジルコニアとともに用いてもよいジルコニア以外の成分としては、特に制限はないが、シリカ、アルミナ、チタニアの中から選ばれる一種又は二種以上のものを用いることが好ましい。
このような第２の成分からなる多孔質部位は、細孔直径が２〜１０ｎｍ、好ましくは２〜８ｎｍ、特に好ましくは２〜７ｎｍであり、この細孔が、バイモーダル多孔質体において、相対的に小さなメソポアに相当する。
On the other hand, the porous portion which is the second porous body is formed on the surface of the first porous body. The surface of the first porous body is a combination of the outer surface of the particles constituting the first porous body and the surface of the pores.
The porous portion has a second component. In the present invention, a component containing zirconia is used as the second component. By using zirconia, a carrier having the bimodal structure can be formed, and a catalyst having a target reforming effect can be obtained.
The component containing zirconia is preferably composed mainly of zirconia. That is, not only zirconia but also components other than zirconia may be used together with zirconia. Here, the main component means 50% by mass or more, preferably 70% by mass or more, and particularly 90% by mass or more, based on the second component total amount standard.
The component other than zirconia that may be used together with the zirconia is not particularly limited, but it is preferable to use one or more selected from silica, alumina, and titania.
Such a porous part composed of the second component has a pore diameter of 2 to 10 nm, preferably 2 to 8 nm, particularly preferably 2 to 7 nm. It corresponds to a small mesopore.
以上のような第１の多孔質体及び第２の多孔質体（多孔質部位）を有する本発明のバイモーダル多孔質体は、例えば以下の方法によって得ることができる。
すなわち、上述した第１の多孔質体を用意し、これとは別に第２の成分、すなわちジルコニアを含有する液体を準備する。この液体は、ゾルであることが好ましい。
ジルコニアを含有する液体の具体例としては、例えば、以下に示すジルコニウム原料をエタノールや水に溶解したエタノール溶液や水溶液が挙げられる。
ここで、ジルコニウム原料としては、例えば、ジルコニアゾル、ＺｒＯ（ＯＨ）Ｃｌ、ＺｒＯＣｌ2・ｎＨ2Ｏ、Ｚｒ2Ｏ3Ｃｌ2、ＺｒＣｌ4、ＺｒＣｌ3、ＺｒＣｌ2、ＺｒＢｒ4、ＺｒＢｒ3、ＺｒＢｒ2、ＺｒＩ4、ＺｒＩ3、ＺｒＩ2、ＺｒＦ4、ＺｒＦ3、ＺｒＦ2等のハロゲン化物塩類、Ｚｒ（ＮＯ3）4・ｎＨ2Ｏ、ＺｒＯ（ＮＯ3）2・ｎＨ2Ｏ、Ｚｒ（ＳＯ4）2、Ｚｒ（ＳＯ4）2・ｎＨ2Ｏ、ＺｒＯ（ＳＯ4）、Ｚｒ（Ｈ2ＰＯ4）2、ＺｒＰ2Ｏ7、ＺｒＳｉＯ4、ＺｒＯ（ＣＯ3）2・ｎＨ2Ｏ、ＺｒＯ（ＯＨ）2・ｎＨ2Ｏ等のオキソ酸塩類、酢酸ジルコニウム、乳酸ジルコニル、ステアリン酸ジルコニル等の有機酸塩類等が挙げられる。ジルコニウム原料としては、これらの中から選ばれる一種を用いてもよいし、二種以上を併用してもよい。
The bimodal porous body of the present invention having the first porous body and the second porous body (porous portion) as described above can be obtained, for example, by the following method.
That is, the first porous body described above is prepared, and separately from this, a liquid containing the second component, that is, zirconia is prepared. This liquid is preferably a sol.
Specific examples of the liquid containing zirconia include, for example, ethanol solutions and aqueous solutions obtained by dissolving the following zirconium raw materials in ethanol and water.
Here, examples of the zirconium raw material include zirconia sol, ZrO (OH) Cl, ZrOCl 2 · nH 2 O, Zr 2 O 3 Cl 2 , ZrCl 4 , ZrCl 3 , ZrCl 2 , ZrBr 4 , ZrBr 3 , ZrBr 2. , ZrI 4 , ZrI 3 , ZrI 2 , ZrF 4 , ZrF 3 , ZrF 2 and other halide salts, Zr (NO 3 ) 4 .nH 2 O, ZrO (NO 3 ) 2 .nH 2 O, Zr (SO 4 ) 2 , Zr (SO 4 ) 2 .nH 2 O, ZrO (SO 4 ), Zr (H 2 PO 4 ) 2 , ZrP 2 O 7 , ZrSiO 4 , ZrO (CO 3 ) 2 .nH 2 O, ZrO ( OH) 2 · nH 2 O and the like, and organic acid salts such as zirconium acetate, zirconyl lactate, zirconyl stearate and the like. As a zirconium raw material, 1 type chosen from these may be used, and 2 or more types may be used together.
次いで得られた第２成分を含む液体を第１の多孔質体に含浸する。具体的には、ジルコニウム原料のゾルの水溶液を第１の多孔質体の担体であるシリカやアルミナ等に含浸する。
ここで、第２の成分として、ジルコニアとともに、シリカ、アルミナ、チタニア中から選ばれる一種又は二種以上を併用して用いる場合は、例えば、前述のジルコニウムゾルに、併用するシリカ、アルミ、チタンなどを含むゾルを混合した混合溶液を用いればよい。
前記の含浸方法は、とくに制限はなく、公知の方法で行えばよい。例えば、担持操作については、加熱含浸法，常温含浸法，真空含浸法，常圧含浸法，含浸乾固法，ポアファイリング法等の各種含浸法、浸漬法、軽度浸潤法、湿式吸着法、スプレー法、塗布法などを用いることができる。
ここで、担持操作の条件については、大気圧下または減圧下で行うことができる。その際の操作温度としては特に制限はないが、例えば室温〜１５０℃程度の温度で行うことが好ましい。また、接触時間は、通常１分間〜１０時間である。
Next, the liquid containing the obtained second component is impregnated into the first porous body. Specifically, an aqueous solution of a zirconium raw material sol is impregnated into silica, alumina, or the like, which is a carrier of the first porous body.
Here, as the second component, together with zirconia, when used in combination with one or more kinds selected from silica, alumina, and titania, for example, silica, aluminum, titanium, etc. used in combination with the aforementioned zirconium sol A mixed solution in which a sol containing is mixed may be used.
The impregnation method is not particularly limited and may be performed by a known method. For example, with regard to the supporting operation, various impregnation methods such as heat impregnation method, room temperature impregnation method, vacuum impregnation method, atmospheric pressure impregnation method, impregnation drying method, pore filing method, immersion method, mild infiltration method, wet adsorption method, spray A method, a coating method, or the like can be used.
Here, the loading operation can be performed under atmospheric pressure or reduced pressure. Although there is no restriction | limiting in particular as operation temperature in that case, For example, it is preferable to carry out at the temperature of about room temperature-150 degreeC. The contact time is usually 1 minute to 10 hours.
その後、第２の成分である液状物が含浸された第１の多孔質体を乾燥、焼成してバイモーダル多孔質体を得ることができる。
乾燥の具体的方法としては、例えば、自然乾燥、ロータリーエバポレーター、アスピレーターもしくは送風乾燥機による乾燥が挙げられる。また、乾燥後行う焼成の具体的方法は、通常、空気中または不活性ガス（窒素、アルガン等）中で２００〜９００℃、好ましくは２５０〜８００℃の温度で、０．５〜６時間、好ましくは１〜４時間行う。
Thereafter, the first porous body impregnated with the liquid material as the second component can be dried and fired to obtain a bimodal porous body.
Specific examples of the drying method include natural drying, drying with a rotary evaporator, aspirator, or blower dryer. Moreover, the specific method of baking performed after drying is normally 200-900 degreeC in the air or inert gas (nitrogen, argan, etc.), Preferably it is the temperature of 250-800 degreeC, 0.5-6 hours, Preferably it is carried out for 1 to 4 hours.
このようにして得られたバイモーダル多孔質体は、ジルコニウムを含み、かつ細孔直径が２〜１０ｎｍの細孔と２０〜２００ｎｍの細孔を有するバイモーダル構造を有するものである。 The bimodal porous body thus obtained has a bimodal structure containing zirconium and having a pore diameter of 2 to 10 nm and a pore of 20 to 200 nm.
本発明の水素製造用触媒は、バイモーダル多孔質体を担体とし、これに活性金属を担持した触媒である。
本発明に用いる活性金属は、特に制限はないが、好ましい活性金属としては、Ｎｉ、Ｃｏ、Ｒｕ、Ｒｈ、Ｉｒ、Ｐｔ、Ｐｄなど挙げられる。中でも性能の観点から、Ｎｉが好ましい。これらの活性金属の中から選ばれる一種を用いてもよいし、二種以上を併用して用いてもよい。この活性金属の含有量は、触媒（水素製造用触媒）全量基準で、酸化物として０．０５〜２０質量％が好ましく、１〜１５質量％がより好ましい。活性金属の含有量が０．０５質量％以上であれば、水素化改質効果が認められ、２０質量％以下であれば、改質性能が低下する恐れがなく、担持量に見合った活性の向上効果が期待できる。
これらの活性金属の担持方法は、特に制限はなく、公知の方法で行えばよい。
The catalyst for producing hydrogen of the present invention is a catalyst in which a bimodal porous material is used as a support and an active metal is supported on the support.
The active metal used in the present invention is not particularly limited, but preferred active metals include Ni, Co, Ru, Rh, Ir, Pt, Pd and the like. Among these, Ni is preferable from the viewpoint of performance. One kind selected from these active metals may be used, or two or more kinds may be used in combination. The content of the active metal is preferably 0.05 to 20% by mass, more preferably 1 to 15% by mass as an oxide, based on the total amount of the catalyst (hydrogen production catalyst). If the content of the active metal is 0.05% by mass or more, a hydrogenation reforming effect is recognized, and if it is 20% by mass or less, the reforming performance does not deteriorate, and the activity corresponding to the supported amount is obtained. An improvement effect can be expected.
The method for supporting these active metals is not particularly limited and may be carried out by a known method.
上記触媒を構成する各活性金属の原料化合物としては、以下に示す化合物を挙げることができる。すなわち、
Ｎｉの原料化合物としては、例えばＮｉ（ＮＯ3）2・6Ｈ2Ｏ、ＮｉＯ、Ｎｉ（ＯＨ）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。
Ｃｏの原料化合物としては、Ｃｏ（ＮＯ3）2、Ｃｏ（ＯＨ）2、ＣｏＣｌ2、ＣｏＳＯ4、Ｃｏ2（ＳＯ4）3、ＣｏＦ3などを挙げることができる。
Ｒｕの原料化合物としては、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。中でも、取扱い上の観点からＲｕＣｌ3・ｎＨ2Ｏ、Ｒｕ（ＮＯ3）3、Ｒｕ2（ＯＨ）2Ｃｌ4・７ＮＨ3・３Ｈ2Ｏが好ましく用いられる。
Ｒｈの原料化合物としては、例えば、Ｎａ3ＲｈＣｌ6、（ＮＨ4）2ＲｈＣｌ6、Ｒｈ（ＮＨ3）5Ｃｌ3、Ｒｈ（ＮＯ3）3、ＲｈＣｌ3等を挙げることができる。
Examples of the raw material compound for each active metal constituting the catalyst include the following compounds. That is,
Examples of Ni raw material compounds include Ni (NO 3 ) 2 .6H 2 O, NiO, Ni (OH) 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 can be mentioned.
Examples of the Co raw material compound include Co (NO 3 ) 2 , Co (OH) 2 , CoCl 2 , CoSO 4 , Co 2 (SO 4 ) 3 , and CoF 3 .
Examples of Ru raw material compounds 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 , [Ru (NO) (edta )] - ruthenium salt, and the like can be given. Of these, RuCl 3 .nH 2 O, Ru (NO 3 ) 3 , Ru 2 (OH) 2 Cl 4 .7NH 3 .3H 2 O are preferably used from the viewpoint of handling.
Examples of the raw material compound for Rh 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.
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。
Ｐｄの原料化合物としては、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 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 raw material compound of Pd 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.
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.
本発明の水素製造用触媒は、上記活性金属とともに、希土類金属を担持することが好ましい。これによって水素の製造効率（水素収率）がさらに向上する。
希土類金属としては、イットリウム，ランタン，セリウムなどが挙げられる。中でも効果の点でセリウムが好ましい。
希土類金属を担持する際に用いられる希土類の原料化合物としては、Ｙ2（ＳＯ4）3、ＹＣｌ3、Ｙ（ＯＨ）3、Ｙ2（ＣＯ3）3、Ｙ（ＮＯ3）3、Ｌａ2（ＳＯ4）3、Ｌａ（ＮＯ3）3、ＬａＣｌ3、Ｌａ（ＯＨ）3、Ｌａ2（ＣＯ3）3、Ｌａ（ＣＨ3ＣＯＯ）3、Ｃｅ（ＯＨ）3、ＣｅＣｌ3、Ｃｅ2（ＳＯ4）3、Ｃｅ2（ＣＯ3）3、Ｃｅ（ＮＯ3）3等を挙げることができる。
本発明の水素製造用触媒における希土類金属の含有量は、特に制限されないが、水素の製造効率と経済性のバランスから、通常、触媒（水素製造用触媒）全量基準で、酸化物として１〜２０質量％、さらには、２〜１５質量％の範囲が好ましい。
The hydrogen production catalyst of the present invention preferably supports a rare earth metal together with the active metal. This further improves the hydrogen production efficiency (hydrogen yield).
Examples of the rare earth metal include yttrium, lanthanum, and cerium. Of these, cerium is preferable from the viewpoint of effects.
Examples of the rare earth raw material compound used for supporting the rare earth metal include Y 2 (SO 4) 3 , YCl 3 , Y (OH) 3 , Y 2 (CO 3 ) 3 , Y (NO 3 ) 3 , La 2 ( SO4) 3, La (NO 3 ) 3, LaCl 3, La (OH) 3, La 2 (CO 3) 3, La (CH 3 COO) 3, Ce (OH) 3, CeCl 3, Ce 2 (SO 4 ) 3 , Ce 2 (CO 3 ) 3 , Ce (NO 3 ) 3 and the like.
The content of the rare earth metal in the hydrogen production catalyst of the present invention is not particularly limited, but is usually 1 to 20 as an oxide based on the total amount of the catalyst (hydrogen production catalyst) from the balance of hydrogen production efficiency and economy. A range of 2% to 15% by mass is preferred.
上記希土類金属を担持する工程は、バイモーダル多孔質体を製造した後であれば、担持手順は限定されるものではない。したがって、例えば、ニッケルなどの前記活性金属と共含浸（同時に含浸）により担持しても良いし、先に希土類金属を担持した後にニッケルなどの活性金属を含浸担持しても良い。 As long as the step of supporting the rare earth metal is after the bimodal porous body is manufactured, the supporting procedure is not limited. Therefore, for example, the active metal such as nickel may be supported by co-impregnation (simultaneously impregnated), or the rare earth metal may be supported first and then the active metal such as nickel may be impregnated and supported.
このようにして得られた本発明の水素製造用触媒は、以下に示すような触媒である。すなわち、
多孔質担体に活性金属を担持した触媒であって、当該多孔質担体が、ジルコニウムを含み、かつ細孔直径が２〜１０ｎｍの細孔（第２の細孔）と２０〜２００ｎｍの細孔（第１の細孔）を有するバイモーダル構造を有することを特徴とする水素製造用触媒である。
前記触媒は、通常、細孔分布に関し、第１の細孔を有する第１の多孔質体と、これを修飾して得られ、前記第１の細孔又は該第１の細孔近傍に該第１の細孔径よりも小さな第２の細孔径を有する多孔質部位を有する触媒である。
The hydrogen production catalyst of the present invention thus obtained is a catalyst as shown below. That is,
A catalyst in which an active metal is supported on a porous carrier, the porous carrier containing zirconium and a pore having a pore diameter of 2 to 10 nm (second pore) and a pore having a diameter of 20 to 200 nm ( A hydrogen production catalyst having a bimodal structure having first pores).
The catalyst is usually obtained by modifying the first porous body having the first pores and modifying the first porous body with respect to the pore distribution, in the first pores or in the vicinity of the first pores. It is a catalyst having a porous portion having a second pore diameter smaller than the first pore diameter.
［水素製造方法］
本発明の水素製造方法は、上記水素製造用触媒を水素源である炭化水素もしくは酸素を含有する炭化水素などの炭化水素類と接触させる工程を含む、水素製造方法である。
具体的には、上記の方法で得られた水素製造用触媒を好ましくは前処理し、該水素製造用触媒を炭化水素もしくは酸素を含有する炭化水素と接触させて改質反応を行う。具体的方法には以下に示す方法が好ましい。
[Hydrogen production method]
The hydrogen production method of the present invention is a hydrogen production method including a step of bringing the hydrogen production catalyst into contact with a hydrocarbon such as a hydrocarbon which is a hydrogen source or a hydrocarbon containing oxygen.
Specifically, the hydrogen production catalyst obtained by the above method is preferably pretreated, and the reforming reaction is carried out by bringing the hydrogen production catalyst into contact with a hydrocarbon or a hydrocarbon containing oxygen. The specific method is preferably the following method.
上記調製された触媒は還元を行わずに使用することもできるが、触媒活性の面では還元処理を行う方が好ましい。この還元処理には、通常水素を含む気流中で処理する気相還元法、又は還元剤で処理する湿式還元法が用いられる。
前者の気相還元処理は、通常、水素を含む気流下、２５０〜８００℃、好ましくは３００〜７００℃の温度で、１〜２４時間、好ましくは３〜１２時間行うものである。また後者の湿式還元法は、液体アンモニア／アルコール／Ｎａ，液体アンモニア／アルコール／Ｌｉを用いるＢｉｒｃｈ還元、メチルアミン／Ｌｉ等を用いるＢｅｎｋｅｓｅｒ還元、Ｚｎ／ＨＣｌ，Ａｌ／ＮａＯＨ／Ｈ2Ｏ，ＮａＨ，ＬｉＡｌＨ4及びその置換体、ヒドロシラン類、水素化ホウ素ナトリウム及びその置換体、ジボラン、蟻酸、ホルマリン、ヒドラジン等の還元剤で処理する方法がある。還元処理条件は、通常、室温〜１００℃で、１０分〜２４時間、好ましくは、３０分〜１０時間行うものである。
Although the prepared catalyst can be used without reduction, it is preferable to perform a reduction treatment in terms of catalytic activity. For this reduction treatment, a gas phase reduction method in which treatment is usually performed in an air stream containing hydrogen or a wet reduction method in which treatment is performed with a reducing agent is used.
The former gas phase reduction treatment is usually carried out at 250 to 800 ° C., preferably 300 to 700 ° C., for 1 to 24 hours, preferably 3 to 12 hours in an air stream containing hydrogen. The latter wet reduction methods include liquid ammonia / alcohol / Na, Birch reduction using liquid ammonia / alcohol / Li, Benkeser reduction using methylamine / Li, etc., Zn / HCl, Al / NaOH / H 2 O, NaH, There is a method of treating with a reducing agent such as LiAlH 4 and substituted products thereof, hydrosilanes, sodium borohydride and substituted products thereof, diborane, formic acid, formalin, and hydrazine. The reduction treatment is usually performed at room temperature to 100 ° C. for 10 minutes to 24 hours, preferably 30 minutes to 10 hours.
まず、本発明の水素製造用触媒を用いた炭化水素や酸素を含有する炭化水素などの炭化水素類の水蒸気改質反応について説明する。
この反応に用いられる水素源であ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１〜２０程度の直鎖状又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、単環及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。
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、事前に脱硫工程を通して、通常、硫黄分が０．１ｐｐｍ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０．１ｐｐｍ程度より多いと、水蒸気改質触媒が失活する原因になることがある。この場合の脱硫方法は特に限定されないが、水添脱硫、吸着脱硫などを適宜採用することができる。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。
また、この反応に用いられる原料の酸素を含有する炭化水素としては、メタノールなどのアルコールの他、油脂類、例えば、菜種油、ごま油、ひまわり油、大豆油、ツバキ油、オリーブ油、ヒマシ油、などの植物油脂が挙げられる。中でも、菜種油、ごま油、ひまわり油が好適である。
本発明においては、灯油あるいはそれ以上の沸点を有する、炭素鎖が長い炭化水素や酸素を含有する炭化水素であっても良好な水素化改質を行うことができる。
First, the steam reforming reaction of hydrocarbons such as hydrocarbons and hydrocarbons containing oxygen using the hydrogen production catalyst of the present invention will be described.
Examples of the raw material hydrocarbon which is a hydrogen source used in this reaction include straight chain having about 1 to 20 carbon atoms such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, etc. Various saturated hydrocarbons such as branched saturated aliphatic hydrocarbons, cycloaliphatic saturated hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane, monocyclic and polycyclic aromatic hydrocarbons, city gas, LPG, naphtha, kerosene, etc. Can be mentioned.
Generally, when a sulfur content is present in these raw material hydrocarbons, it is usually preferable to perform desulfurization through a desulfurization process in advance until the sulfur content is 0.1 ppm or less. When the sulfur content in the raw material hydrocarbon is more than about 0.1 ppm, the steam reforming catalyst may be deactivated. The desulfurization method in this case is not particularly limited, but hydrodesulfurization, adsorptive desulfurization and the like can be appropriately employed. The steam used for the steam reforming reaction is not particularly limited.
The hydrocarbon containing oxygen as a raw material used in this reaction includes alcohols such as methanol and fats and oils such as rapeseed oil, sesame oil, sunflower oil, soybean oil, camellia oil, olive oil and castor oil. Examples include vegetable oils and fats. Among them, rapeseed oil, sesame oil and sunflower oil are preferable.
In the present invention, it is possible to perform good hydrogenation reforming even with kerosene or a hydrocarbon having a boiling point higher than that, such as a hydrocarbon having a long carbon chain or a hydrocarbon containing oxygen.
水蒸気改質の反応条件としては、通常、スチーム／カーボン（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（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２５０〜８５０℃、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。
As reaction conditions for steam reforming, the amount of hydrocarbon and the amount of steam are usually adjusted so that the steam / carbon (molar ratio) is 1.5 to 10, preferably 1.5 to 5, more preferably 2 to 4. Just decide. By adjusting the steam / carbon (molar ratio) in this way, a product gas having a high hydrogen content can be obtained efficiently.
The reaction temperature is usually 200 to 900 ° C, preferably 250 to 850 ° C, more preferably 300 to 800 ° C. The reaction pressure is usually 0 to 3 MPa · G, preferably 0 to 1 MPa · G.
灯油あるいはそれ以上の沸点を有する炭化水素や酸素を含有する炭化水素を原料とする場合、水蒸気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ことが好ましい。入口温度が６３０℃以下であれば、炭化水素類の熱分解が促進され、触媒あるいは反応管壁に炭素が析出して、運転が困難になる恐れがない。また、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。６５０℃以上であれば水素の生成量が充分保たれ、８００℃以下であれば、反応装置は耐熱材料であることを必要とせず、経済的に好ましい。
なお、水素製造の場合と合成ガス製造とでは反応条件が若干異なる。水素製造の場合は、水蒸気は多めに入れ、反応温度は低めで、反応圧力は低めであることが好ましい。逆に、合成ガス製造の場合は、水蒸気は少なめ、反応温度は高め、反応圧力は高めにして行うことが好ましい。
When using kerosene or a hydrocarbon having a boiling point higher than that or a hydrocarbon containing oxygen, steam reforming is performed with the inlet temperature of the steam reforming catalyst layer kept at 630 ° C or lower, preferably 600 ° C or lower. Is preferred. When the inlet temperature is 630 ° C. or lower, the thermal decomposition of hydrocarbons is promoted, and there is no fear that the operation is difficult because carbon is deposited on the catalyst or the reaction tube wall. The catalyst layer outlet temperature is not particularly limited, but is preferably in the range of 650 to 800 ° C. If it is 650 degreeC or more, the production amount of hydrogen is fully maintained, and if it is 800 degreeC or less, the reaction apparatus does not need to be a heat-resistant material, and is economically preferable.
The reaction conditions are slightly different between hydrogen production and synthesis gas production. In the case of hydrogen production, it is preferable that a large amount of steam is added, the reaction temperature is low, and the reaction pressure is low. On the other hand, in the case of synthesis gas production, it is preferable to carry out with less water vapor, higher reaction temperature, and higher reaction pressure.
次に、本発明の改質触媒を用いた炭化水素類の自己熱改質反応、部分酸化改質反応、炭酸ガス改質反応について説明する。
自己熱改質反応は、炭化水素類の酸化反応と炭化水素類と水蒸気の反応が同一リアクター内又は連続したリアクター内で起こる。この反応における水素製造と合成ガス製造では反応条件は若干異なるが、通常反応温度は２００〜１，３００℃が好ましく、さらには４００〜１，２００℃、特に５００〜９００℃が好ましい。スチーム／カーボン（モル比）は、通常、０．１〜１０、さらには０．４〜４であることが好ましい。酸素／カーボン（モル比）は、通常、０．１〜１、さらには０．２〜０．８であることが好ましい。反応圧力について、通常、０〜１０ＭＰａ・Ｇ、さらには０〜５ＭＰａ・Ｇ、特に０〜３ＭＰａ・Ｇであることが好ましい。
Next, the autothermal reforming reaction, partial oxidation reforming reaction, and carbon dioxide reforming reaction of hydrocarbons using the reforming catalyst of the present invention will be described.
In the autothermal reforming reaction, the oxidation reaction of hydrocarbons and the reaction of hydrocarbons and steam occur in the same reactor or in a continuous reactor. The reaction conditions for hydrogen production and synthesis gas production in this reaction are slightly different, but usually the reaction temperature is preferably 200 to 1,300 ° C, more preferably 400 to 1,200 ° C, and particularly preferably 500 to 900 ° C. The steam / carbon (molar ratio) is usually 0.1 to 10, more preferably 0.4 to 4. The oxygen / carbon (molar ratio) is usually preferably 0.1 to 1, and more preferably 0.2 to 0.8. The reaction pressure is usually 0 to 10 MPa · G, more preferably 0 to 5 MPa · G, and particularly preferably 0 to 3 MPa · G.
部分酸化改質反応は、炭化水素類の部分酸化反応が起こり、水素製造と合成ガス製造では反応条件は若干異なるが、通常、反応温度は３５０〜１，２００℃、さらには４５０〜９００℃が好ましい。酸素／カーボン（モル比）は、通常、０．４〜０．８、さらには０．４５〜０．６５が好ましい。反応圧力は、通常、０〜３０ＭＰａ・Ｇ、さらには０〜５ＭＰａ・Ｇ、特に０〜３ＭＰａ・Ｇであることが好ましい。
炭酸ガス改質反応は、炭化水素類と炭酸ガスの反応が起こり、水素製造と合成ガス製造では反応条件は若干異なるが、通常、反応温度は２００〜１，３００℃、さらには４００〜１，２００℃、特に５００〜９００℃であることが好ましい。炭酸ガス／カーボン（モル比）は、通常、０．１〜５、さらには０．１〜３であることが好ましい。水蒸気を入れる場合には、スチーム／カーボン（モル比）は、通常、０．１〜１０、さらには０．４〜４が好ましい。酸素を入れる場合には、酸素／カーボン（モル比）は、通常、０．１〜１、さらには０．２〜０．８が好ましい。反応圧力は、通常、０〜１０ＭＰａ・Ｇ、さらには０〜５ＭＰａ・Ｇ、特に０〜３ＭＰａ・Ｇであることが好ましい。
In the partial oxidation reforming reaction, a partial oxidation reaction of hydrocarbons occurs, and the reaction conditions are slightly different between hydrogen production and synthesis gas production, but the reaction temperature is usually 350 to 1,200 ° C., further 450 to 900 ° C. preferable. The oxygen / carbon (molar ratio) is usually preferably 0.4 to 0.8, more preferably 0.45 to 0.65. The reaction pressure is usually preferably 0 to 30 MPa · G, more preferably 0 to 5 MPa · G, and particularly preferably 0 to 3 MPa · G.
In the carbon dioxide reforming reaction, a reaction between hydrocarbons and carbon dioxide occurs, and the reaction conditions are slightly different between hydrogen production and synthesis gas production. Usually, the reaction temperature is 200 to 1,300 ° C., further 400 to 1, It is preferable that it is 200 degreeC, especially 500-900 degreeC. The carbon dioxide gas / carbon (molar ratio) is usually preferably 0.1 to 5, more preferably 0.1 to 3. When steam is added, the steam / carbon (molar ratio) is usually 0.1 to 10, more preferably 0.4 to 4. When oxygen is added, the oxygen / carbon (molar ratio) is usually preferably 0.1 to 1, and more preferably 0.2 to 0.8. The reaction pressure is usually 0 to 10 MPa · G, more preferably 0 to 5 MPa · G, and particularly preferably 0 to 3 MPa · G.
以上の各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、炭化水素類の液空間速度（ＬＨＳＶ）は、通常、０．１〜１０ｈｒ-1、さらには０．２５〜５ｈｒ-1であることが好ましい。また、炭化水素類としてメタンなどのガスを用いる場合は、ガス空間速度（ＧＨＳＶ）は、通常、２００〜１００，０００ｈｒ-1であることが好ましい。
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。
The reaction system for each reforming reaction described above may be either a continuous flow system or a batch system, but a continuous flow system is preferred. When adopting the continuous flow type, the liquid space velocity (LHSV) of hydrocarbons is usually 0.1 to 10 hr −1 , more preferably 0.25 to 5 hr −1 . Moreover, when gas, such as methane, is used as hydrocarbons, it is preferable that gas space velocity (GHSV) is 200-100,000 hr < -1 > normally.
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 preferred. There is no restriction | limiting in particular also as a form of a reactor, For example, a tubular reactor etc. can be used.
上記のような条件で本発明の改質触媒を用いて、炭化水素類の水蒸気改質反応、自己熱改質反応、部分酸化反応、炭酸ガス改質反応を行なわせることにより水素を得ることができ、燃料電池の水素製造プロセスに好適に使用される。また、メタノール合成、オキソ合成、ジメチルエーテル合成、フィッシャー・トロプッシュ合成用の合成ガスも効率よく得ることができる。 Hydrogen can be obtained by performing a steam reforming reaction, autothermal reforming reaction, partial oxidation reaction, carbon dioxide gas reforming reaction of hydrocarbons using the reforming catalyst of the present invention under the above conditions. And is suitably used in a hydrogen production process of a fuel cell. In addition, synthesis gas for methanol synthesis, oxo synthesis, dimethyl ether synthesis, and Fischer-Tropsch synthesis can also be obtained efficiently.
以下に本発明の実施例及び比較例を挙げて更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、触媒の構造分析、水素製造実験における生成ガス分析等は、以下の方法で行った。
（１）触媒の構造分析方法
下記の窒素吸着測定方法によって、触媒の細孔径分布、細孔直径［ｄ］、指数細孔分布関数（Ｄｖ（ｌｏｇｄ））、及び細孔容積を測定した。
＜窒素吸着測定方法＞
・使用装置：ユアサアイオニクス株式会社「定容法化学吸着測定装置ＡＵＴＯＳＯＲＢ−１−Ｃ」
・測定方式：定容量法ガス吸着法
・前処理条件：２００℃真空排気処理
・サンプル量：５０ｍｇ
・測定プログラム ：吸脱着等温線測定
・比表面積の算出法：ＢＥＴ法
・細孔径分布の算出法：ＢＪＨ法
・測定相対圧範囲 ：１０-7〜１．０
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
In addition, the structural analysis of the catalyst, the generated gas analysis in the hydrogen production experiment, and the like were performed by the following methods.
(1) Structure analysis method of catalyst The pore diameter distribution, pore diameter [d], exponential pore distribution function (Dv (logd)), and pore volume of the catalyst were measured by the following nitrogen adsorption measurement method.
<Nitrogen adsorption measurement method>
・ Applied equipment: Yuasa Ionics Co., Ltd. “Constant volume chemical adsorption measurement device AUTOSORB-1-C”
・ Measurement method: constant volume gas adsorption method ・ Pretreatment conditions: 200 ° C. vacuum exhaust treatment ・ Sample amount: 50 mg
・ Measurement program: Adsorption / desorption isotherm measurement ・ Specific surface area calculation method: BET method ・ Pore diameter distribution calculation method: BJH method ・ Measurement relative pressure range: 10 −7 to 1.0
（２）水素製造実験における生成ガスの分析、選択率、ｏｉｌ転化率の測定方法
水素製造実験により生成されたガスの分析は、オンラインでガスクロマトグラフ分析を行った。このガス分析から、Ｈ2発生速度、及び各炭素含有ガス成分（Ｃ成分）の選択率を求めた。また、ｏｉｌ転化率は、水素製造実験で流した油の総量と設置したアイストラップに溜まった未反応油の総量の関係より求めた。なお、各ガス成分の生成量は標準ガスと出口流速と合わせて気体の状態方程式より導いた。具体的には、以下のとおりである。
＜ガスクロマトグラフ分析方法＞
（ｉ）生成した炭素含有ガスの分析
島津製ガスクロマトグラフＧＣ−９Ａ（ＦＩＤ、メタナイザー使用：５質量％、Ｒｕ／Ａｌ2Ｏ3 ０．５０ｇ充填）を下記の条件で用い、２時間ごとに炭化水素などの分析を行った。
ＦＩＤ昇温プログラム：７０℃１０分保持→７０℃〜２５０℃まで８℃／ｍｉｎで昇温→２５０℃で６０分保持
（ii）生成した水素の分析
島津製ガスクロマトグラフＧＣ−１４Ｂ（ＴＣＤ、キャリアー：Ａｒ、プログラム：ＩＮＪ １００℃ ＣＯＬ：７０℃）にて３０分ごと分析した。
＜Ｃ成分の各選択率＞
各Ｃ成分の選択率（％）＝｛（各Ｃ成分流量）／（全Ｃ成分流量）｝×１００
＜ｏｉｌ転化率の算出方法＞
(2) Analysis of produced gas in hydrogen production experiment, measurement method of selectivity and oil conversion rate The gas produced in the hydrogen production experiment was analyzed online by gas chromatograph analysis. From this gas analysis, the H 2 generation rate and the selectivity of each carbon-containing gas component (C component) were determined. The oil conversion was determined from the relationship between the total amount of oil flowed in the hydrogen production experiment and the total amount of unreacted oil accumulated in the installed ice strap. The amount of each gas component produced was derived from the gas equation of state, together with the standard gas and the outlet flow velocity. Specifically, it is as follows.
<Gas chromatograph analysis method>
(I) Analysis of produced carbon-containing gas Shimadzu gas chromatograph GC-9A (FID, using a metanizer: 5% by mass, filled with 0.50 g of Ru / Al 2 O 3 ) was used under the following conditions and carbonized every 2 hours. Analyzes such as hydrogen were conducted.
FID temperature rising program: 70 ° C. 10 min hold → temperature rising from 70 ° C. to 250 ° C. at 8 ° C./min→Holding at 250 ° C. for 60 min (ii) Analysis of produced hydrogen Shimadzu gas chromatograph GC-14B (TCD, carrier : Ar, program:
<Each selectivity of C component>
Selectivity of each C component (%) = {(each C component flow rate) / (total C component flow rate)} × 100
<Oil conversion rate calculation method>
上記式中のアイストラップにて回収した油量、アイストラップにて回収した油の測定方法は以下の通りである。
アイストラップにて回収した油量
＝反応終了後トラップ重量−（反応前トラップ重量＋トラップ内の水重量）
＜アイストラップにて回収した油の定量方法＞
反応前のトラップの重量を測定し、さらに反応終了後のトラップの全重量を測定した。その後、分液漏斗を用いて溶液から水層のみを取り出し、水層の重量を測定した。反応終了後のトラップの重量から反応前のトラップの重量および水層の重量を引いた値をアイストラップにて回収された量とした。
The amount of oil recovered by the eye strap in the above formula and the method of measuring the oil recovered by the eye strap are as follows.
Oil amount recovered by eye strap = Trap weight after reaction-(Trap weight before reaction + Water weight in trap)
<Quantification method of oil recovered with ice strap>
The weight of the trap before the reaction was measured, and the total weight of the trap after the completion of the reaction was further measured. Thereafter, only the aqueous layer was taken out from the solution using a separatory funnel, and the weight of the aqueous layer was measured. A value obtained by subtracting the weight of the trap before the reaction and the weight of the aqueous layer from the weight of the trap after the reaction was regarded as the amount recovered by the ice strap.
［触媒の調製］
実施例１
〔５ｗｔ％Ｎｉ／２０ｗｔ％ＺｒＯ2／ＳｉＯ2の調製（１）〕
シリカ［「ＣＡＲｉＡＣＴ Ｑ−５０」、富士シリシア化学社製、ｐａｒｔｉｃｌｅ ｓｉｚｅ：７５−５００μｍ（３０−２００ｍｅｓｈ）］３ｇにジルコニアゾル［「セラミカ 品番：Ｇ−４０１」（日板研究所製、（溶媒：エタノール、ＺｒＯ2：１６％）］４．６８８ｇをＩｎｃｉｐｉｅｎｔ−Ｗｅｔｎｅｓｓ（ＩＷ）法で含浸した。その後、アスピレーターを用い１時間減圧し、４００℃まで１時間で昇温、２時間保持の条件で焼成し、バイモーダル担体を調製した。
次いで、上記バイモーダル担体３ｇにＮｉ（ＮＯ3）2・６Ｈ2Ｏ（関東化学、特級）０．７８２ｇをＩＷ法で含浸し、１２０℃で１２時間乾燥させた後、４００℃まで３時間で昇温、２時間保持して焼成することにより、５ｗｔ％Ｎｉ／２０ｗｔ％／ＺｒＯ2／ＳｉＯ2（触媒１）を得た。
この触媒１のＮｉ未含浸（Ｎｉ含浸前）の担体について構造分析を窒素吸着測定法によって行った。その細孔径分布は、図１に示す。細孔直径が４．２１ｎｍと５６．８ｎｍにピークを有し、細孔容積は、０．８３ｍｌ／ｇ、表面積は３０５ｍ2／ｇであった。
[Preparation of catalyst]
Example 1
[Preparation of 5 wt% Ni / 20 wt% ZrO 2 / SiO 2 (1)]
Silica [“CARIACT Q-50”, manufactured by Fuji Silysia Chemical Co., Ltd., particle size: 75-500 μm (30-200 mesh)] to 3 g of zirconia sol [“Ceramica product number: G-401” (manufactured by Nippon Sheet Laboratory, (solvent: Ethanol, ZrO 2 : 16%)] was impregnated by the Incipient-Wetness (IW) method, then reduced in pressure using an aspirator for 1 hour, heated to 400 ° C. for 1 hour, and calcined for 2 hours. Then, a bimodal carrier was prepared.
Next, 3 g of the above bimodal carrier was impregnated with 0.782 g of Ni (NO 3 ) 2 .6H 2 O (Kanto Chemical Co., Ltd., special grade) by the IW method, dried at 120 ° C. for 12 hours, and then up to 400 ° C. in 3 hours. By heating and holding for 2 hours, 5 wt% Ni / 20 wt% / ZrO 2 / SiO 2 (Catalyst 1) was obtained.
The structure of the
実施例２
〔５ｗｔ％Ｎｉ−１０ｗｔ％ＣｅＯ2／２０ｗｔ％ＺｒＯ2／ＳｉＯ2の調製〕
実施例１と同様の方法でバイモーダル担体を調製した。次いで、該バイモーダル担体３ｇにＮｉ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を０．７８２ｇおよびＣｅ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を１．０３４ｇ混合させた水溶液をＩＷ法で含浸し、１２０℃で１２時間乾燥させた後、４００℃まで３時間で昇温、２時間保持することにより５ｗｔ％Ｎｉ−１０ｗｔ％ＣｅＯ2／２０ｗｔ％ＺｒＯ2／ＳｉＯ2（触媒２）を得た。
また、Ｎｉを担持しないこと以外は上記実施例２と同様にして得られた「１０ｗｔ％ＣｅＯ2／２０ｗｔ％ＺｒＯ2／ＳｉＯ2」（触媒２のＮｉ未含浸の担体）について構造分析を窒素吸着測定法によって行った。その細孔径分布を図２に示す。細孔直径が３．６ｎｍと６１．５ｎｍにピークを有し、細孔容積は、０．８１ｍｌ／ｇ、表面積は２６９ｍ2／ｇであった。
Example 2
Preparation of 5wt% Ni-10wt% CeO 2 / 20wt% ZrO 2 / SiO 2 ]
A bimodal carrier was prepared in the same manner as in Example 1. Next, 0.782 g of Ni (NO 3 ) 2 · 6H 2 O (manufactured by Kanto Chemical Co., Ltd., special grade) and Ce (NO 3 ) 2 · 6H 2 O (made by Kanto Chemical Co., Ltd., special grade) are added to 3 g of the bimodal carrier. the aqueous solution obtained by 1.034g mixed impregnated with IW method, after drying for 12 hours at 120 ° C., heated at 3 hours 400 ℃, 5wt% Ni-10wt % by 2 hours CeO 2/20 wt% ZrO 2 / SiO 2 (Catalyst 2) was obtained.
Further, except that it bears no Ni was obtained in the same manner as in Example 2 "10wt% CeO 2 / 20wt% ZrO 2 / SiO 2 " (Ni unimpregnated catalyst support 2) nitrogen adsorption structural analysis of The measurement was performed. The pore size distribution is shown in FIG. The pore diameters had peaks at 3.6 nm and 61.5 nm, the pore volume was 0.81 ml / g, and the surface area was 269 m 2 / g.
実施例３
〔５ｗｔ％Ｎｉ／２０ｗｔ％ＺｒＯ2／ＳｉＯ2の調製（２）〕
シリカとして「ＣＡＲｉＡＣＴ Ｑ−５０」（富士シリシア化学社製、ｐａｒｔｉｃｌｅ ｓｉｚｅ：７５−５００μｍ（３０−２００ｍｅｓｈ）に換えて「ＣＡＲｉＡＣＴ Ｑ−３０」（富士シリシア化学社製、ｐａｒｔｉｃｌｅ ｓｉｚｅ：７５〜５００μｍ（３０〜２００ｍｅｓｈ）］を用いたこと以外は、実施例１と同様の方法で５ｗｔ％Ｎｉ／２０ｗｔ％／ＺｒＯ2／ＳｉＯ2（触媒３）を得た。この触媒３のＮｉ未含浸（Ｎｉ含浸前）の担体について構造分析を窒素吸着測定法によって行った。その細孔径分布を図３に示す。細孔直径が４．７３ｎｍと３４．８ｎｍにピークを有し、細孔容積は０．８８ｍｌ／ｇ、表面積は２６６ｍ2／ｇであった。
比較例１
〔５ｗｔ％Ｎｉ／ＳｉＯ2シングルモーダルの調製〕
実施例１で用いたシリカ３ｇにＮｉ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を０．７８２ｇ、ＩＷ法で含浸し、１２０℃で１２時間乾燥させた後、４００℃まで３時間で昇温、２時間保持することにより５ｗｔ％Ｎｉ／ＳｉＯ2（比較触媒１）を得た。この比較触媒１のＮｉ未含浸（Ｎｉ含浸前）の担体について構造分析を窒素吸着測定法によって行った。その細孔径分布を図４に示す。細孔直径が６３．８ｎｍにピークを有し、細孔容積は１．２９ｍｌ／ｇ、表面積は８４ｍ2／ｇであった。
Example 3
[Preparation of 5 wt% Ni / 20 wt% ZrO 2 / SiO 2 (2)]
Instead of “CAriACT Q-50” (manufactured by Fuji Silysia Chemical Co., Ltd., particle size: 75-500 μm (30-200 mesh) as silica, “CALiACT Q-30” (manufactured by Fuji Silysia Chemical Co., Ltd., particle size: 75-500 μm (30 -200 mesh)] was used to obtain 5 wt% Ni / 20 wt% / ZrO 2 / SiO 2 (catalyst 3) in the same manner as in Example 1. Ni impregnation of the catalyst 3 (before Ni impregnation) ) Was analyzed by nitrogen adsorption measurement, and the pore size distribution is shown in Fig. 3. The pore diameters had peaks at 4.73 nm and 34.8 nm, and the pore volume was 0.88 ml / g, The surface area was 266 m 2 / g.
Comparative Example 1
[Preparation of 5 wt% Ni / SiO 2 single modal]
After impregnating 0.72 g of Ni (NO 3 ) 2 .6H 2 O (manufactured by Kanto Chemical Co., Ltd., special grade) into 3 g of silica used in Example 1 by the IW method and drying at 120 ° C. for 12 hours, 400 ° C. The temperature was raised to 3 hours and maintained for 2 hours to obtain 5 wt% Ni / SiO 2 (Comparative Catalyst 1). The structural analysis of the Ni-unimpregnated support (before Ni impregnation) of the
比較例２
〔５ｗｔ％Ｎｉ／２０ｗｔ％Ａｌ2Ｏ3／ＳｉＯ2・バイモーダル（Ｚｒを含まない）の調製〕
実施例１で用いたシリカ３ｇにアルミナゾル（日産化学工業製、「品番 アルミナゾル５２０」（Ａｌ2Ｏ3：２１％）を４．６８８ｇ、Ｉｎｃｉｐｉｅｎｔ−Ｗｅｔｎｅｓｓ（ＩＷ）法で含浸した。その後、アスピレーターを用い１時間減圧し、４００℃まで１時間で昇温、２時間保持の条件で焼成し、バイモーダル担体を調製した。次いで、該バイモーダル担体３ｇにＮｉ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を０．７８２ｇ、ＩＷ法で含浸し、１２０℃で１２時間乾燥させた後、４００℃まで３時間で昇温、２時間保持して焼成することにより、５ｗｔ％Ｎｉ／２０ｗｔ％Ａｌ2Ｏ3／ＳｉＯ2（比較触媒２）得た。この比較触媒２のＮｉ未含浸（Ｎｉ含浸前）の担体について構造分析を窒素吸着測定法によって行った。その細孔径分布を、図５に示す。細孔直径が７．４３ｎｍと６０ｎｍにピークを有し、細孔容積は、０．９１ｍｌ／ｇ、表面積は１１２ｍ2／ｇであった。
Comparative Example 2
[Preparation of 5 wt% Ni / 20 wt% Al 2 O 3 / SiO 2 .bimodal (not including Zr)]
4.688 g of alumina sol (manufactured by Nissan Chemical Industries, “Product No. Alumina Sol 520” (Al 2 O 3 : 21%), impregnated by Incipient-Wetness (IW) method on 3 g of silica used in Example 1. Thereafter, an aspirator was used. The pressure was reduced for 1 hour, heated to 400 ° C. for 1 hour, and calcined under the condition of holding for 2 hours to prepare a bimodal carrier, and then Ni (NO 3 ) 2 .6H 2 O ( 3 g) was added to 3 g of the bimodal carrier. 5 wt% Ni by impregnating 0.782 g of Kanto Chemical Co., Ltd., special grade) by IW method, drying at 120 ° C. for 12 hours, heating to 400 ° C. in 3 hours, holding for 2 hours and firing. / 20wt% Al 2 O 3 / SiO 2 ( Comparative catalyst 2) was obtained. the carrier of the Ni unimpregnated comparative catalyst 2 (Ni before impregnation) the structural analysis was carried out by the nitrogen adsorption measurement method. As The pore size distribution, is. Pore diameter shown in FIG. 5 has a peak at 7.43nm and 60 nm, pore volume, 0.91 ml / g, surface area was 112m 2 / g.
比較例３
〔５ｗｔ％Ｎｉ−１０ｗｔ％ＣｅＯ2／２０ｗｔ％Ａｌ2Ｏ3／ＳｉＯ2の調製〕
比較例２と同様の方法でバイモーダル担体を調製した。次いで、該バイモーダル担体３ｇにＮｉ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を０．７８２ｇおよびＣｅ（ＮＯ3）2・６Ｈ2Ｏ（関東化学社製、特級）を１．０３４ｇ混合させた水溶液をＩＷ法で含浸し、１２０℃で１２時間乾燥させた後、４００℃まで３時間で昇温、２時間保持することにより５ｗｔ％Ｎｉ−１０ｗｔ％ＣｅＯ2／２０ｗｔ％Ａｌ2Ｏ3／ＳｉＯ2（比較触媒３）を得た。
Comparative Example 3
Preparation of 5wt% Ni-10wt% CeO 2 / 20wt% Al 2 O 3 / SiO 2 ]
A bimodal carrier was prepared in the same manner as in Comparative Example 2. Next, 0.782 g of Ni (NO 3 ) 2 · 6H 2 O (manufactured by Kanto Chemical Co., Ltd., special grade) and Ce (NO 3 ) 2 · 6H 2 O (made by Kanto Chemical Co., Ltd., special grade) are added to 3 g of the bimodal carrier. the aqueous solution obtained by 1.034g mixed impregnated with IW method, after drying for 12 hours at 120 ° C., heated at 3 hours 400 ℃, 5wt% Ni-10wt % by 2 hours CeO 2/20 wt% Al 2 O 3 / SiO 2 (Comparative catalyst 3) was obtained.
[水素製造実験]
実施例４，５、比較例４〜６
水蒸気改質の原料として表−１に示す菜種油を用い、以下に示す触媒の還元不動化処理及び前処理をした後に、表−２の反応条件Ｉで水蒸気改質反応を行
った。表３に、使用した触媒、反応温度及び結果を示す。また、水素生成量の経時変化を図６に示す。
[Hydrogen production experiment]
Examples 4 and 5 and Comparative Examples 4 to 6
The rapeseed oil shown in Table-1 was used as a raw material for steam reforming, and after the reduction-immobilization treatment and pretreatment of the catalyst shown below, the steam reforming reaction was performed under the reaction condition I shown in Table-2. Table 3 shows the catalysts used, reaction temperatures and results. Further, FIG. 6 shows the change over time in the amount of hydrogen produced.
（１）触媒還元不動化処理
まずＮ2ガスを４０ｍｌ／ｍｉｎで１時間かけて流し不純物を取り除いた。その後、室温から４００℃まで３時間で昇温させ、途中１００℃を越えたところでＨ2ガスを４０ｍｌ／ｍｉｎで流した。その後４００℃を１０時間保持した。還元が終わった後、室温まで冷まし、Ｎ2ガスを４０ｍｌ／ｍｉｎで１時間かけて流しライン内のＨ2ガスを取り除いた。１％Ｏ2ガス（Ｎ2ガス希釈）を１０ｍｌ／ｍｉｎで一晩かけて流し、触媒表面上の不動化処理を行った。
（２）前処理及び改質反応処理
上と同様、Ｎ2ガスによる１時間前処理を行った。その後４００℃まで昇温し、途中１００℃超えで水素に切り替えた。還元はすでに還元不動化してあるので４００℃で１時間行った。その後、反応温度である６００℃、又は７００℃まで昇温した。安定後、まず水素を窒素（４０ｍｌ／ｍｉｎ）に切り替え、スチームを０．１７５ｍｌ／ｍｉｎ流し、５分後に原料の菜種油を０．００５０ｇ／ｍｉｎ流した。リアクター温度が安定した時点で反応開始とした（窒素はキャリアーとして油と水の安定化のため添加した）。
(1) Catalyst reduction immobilization treatment First, N 2 gas was flowed at 40 ml / min over 1 hour to remove impurities. Thereafter, the temperature was raised from room temperature to 400 ° C. over 3 hours, and when the temperature exceeded 100 ° C., H 2 gas was flowed at 40 ml / min. Thereafter, 400 ° C. was maintained for 10 hours. After the reduction was completed, the mixture was cooled to room temperature, and N 2 gas was flowed at 40 ml / min for 1 hour to remove H 2 gas in the line. 1% O 2 gas (diluted with N 2 gas) was allowed to flow overnight at 10 ml / min to carry out immobilization treatment on the catalyst surface.
(2) Pretreatment and reforming reaction treatment As above, pretreatment with N 2 gas was performed for 1 hour. Thereafter, the temperature was raised to 400 ° C., and the hydrogen was switched to 100 ° C. during the course. The reduction was already carried out at 400 ° C. for 1 hour since the reduction was immobilized. Then, it heated up to 600 degreeC which is reaction temperature, or 700 degreeC. After stabilization, first, hydrogen was switched to nitrogen (40 ml / min), steam was flowed at 0.175 ml / min, and after 5 minutes, rapeseed oil as a raw material was flowed at 0.0050 g / min. The reaction was started when the reactor temperature was stabilized (nitrogen was added as a carrier to stabilize oil and water).
表３に示されるように、本発明の水素製造用触媒を用いた水素製造実験では、転化率、Ｈ2発生速度、ＣＯ、ＣＯ2の選択率がいずれも良好である。この効果は、反応温度が６００℃のより、７００℃の場合の方が良好である（実施例４，５）。また、実施例４，５はメタン選択率が低く、ＣＯ、ＣＯ2の選択率が高いことから、メタンリフォーム活性にも優れることが判る。これに対し、本発明以外の水素製造用触媒を用いた場合は、これらの効果は、いずれも実施例４，５より劣っている（比較例４〜６）。
また、図６よれば、本発明の触媒である、触媒１，２を用いた場合、Ｈ2発生量が多く、かつ、それが経時変化することなく安定している（実施例４（Ｄ），５（Ｅ））。これに対し、本発明以外の比較触媒１，２，３を用いた場合は、Ｈ2発生量は実施例１，２より少なく、しかも経時変化して減少することが確認できる（比較例４（Ａ）、５（Ｂ）、６（Ｃ））。
As shown in Table 3, in the hydrogen production experiment using the hydrogen production catalyst of the present invention, the conversion rate, H 2 generation rate, CO and CO 2 selectivity are all good. This effect is better when the reaction temperature is 700 ° C. than when the reaction temperature is 600 ° C. (Examples 4 and 5). Moreover, since Examples 4 and 5 have low methane selectivity and high CO and CO 2 selectivity, it can be seen that methane reforming activity is also excellent. On the other hand, when the hydrogen production catalyst other than the present invention is used, these effects are inferior to those of Examples 4 and 5 (Comparative Examples 4 to 6).
Further, according to FIG. 6, when the
実施例６，７、及び比較例７
表４に示すように触媒１，３及び比較触媒１を用いて実施例４と同様の水素製造実験を行った。但し反応条件は表２の反応条件IIで行った。結果を表４に示す。
Examples 6 and 7 and Comparative Example 7
As shown in Table 4, the same hydrogen production experiment as in Example 4 was performed using
表４より、本発明の触媒１，３を用いると比較触媒１を用いた場合に比較してＨ2発生速度が高いことが分る（実施例６，７比較例７）。また、触媒３を用いると６時間反応後においてもＣ2以上の炭化水素の発生を大幅に抑制されることから、該触媒は、高活性かつ高安定性を有することが分る。
From Table 4, it can be seen that when the
本発明によれば、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、優れた改質活性及び耐久性を示す水素製造用触媒を提供することができる。
また、本発明は、上記水素製造用触媒を用いて、植物油脂など炭素鎖が長い炭化水素や炭素鎖が長い酸素を含有する炭化水素を水素源とする場合でも、効率的に水素を製造する方法を提供することができる。したがって、水素燃料は燃料電池用水素の製造に有効に利用することができる。
According to the present invention, there is provided a hydrogen production catalyst that exhibits excellent reforming activity and durability even when a hydrocarbon containing a long carbon chain or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source, such as vegetable oils and fats. can do.
In addition, the present invention efficiently produces hydrogen using the hydrogen production catalyst even when a hydrocarbon containing a long carbon chain such as vegetable oil or fat or a hydrocarbon containing oxygen having a long carbon chain is used as a hydrogen source. A method can be provided. Therefore, hydrogen fuel can be effectively used for the production of hydrogen for fuel cells.
図６のＡ 比較例４
図６のＢ 比較例５
図６のＣ 比較例６
図６のＤ 実施例４
図６のＥ 実施例５
FIG. 6A Comparative Example 4
B in FIG. 6 Comparative Example 5
FIG. 6C Comparative Example 6
FIG. 6D Example 4
FIG. 6E Example 5
Claims (12)
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