JP2019000820A - Water vapor reforming catalyst and hydrogen production method - Google Patents
Water vapor reforming catalyst and hydrogen production method Download PDFInfo
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- JP2019000820A JP2019000820A JP2017118796A JP2017118796A JP2019000820A JP 2019000820 A JP2019000820 A JP 2019000820A JP 2017118796 A JP2017118796 A JP 2017118796A JP 2017118796 A JP2017118796 A JP 2017118796A JP 2019000820 A JP2019000820 A JP 2019000820A
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- catalyst
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- hydrogen
- gas
- perovskite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002407 reforming Methods 0.000 title abstract description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000470 constituent Substances 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 39
- 238000000629 steam reforming Methods 0.000 claims description 31
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 48
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000006057 reforming reaction Methods 0.000 description 4
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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
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、水蒸気改質触媒及び水素の製造方法に関する。 The present invention relates to a steam reforming catalyst and a method for producing hydrogen.
２０１５年は水素元年と位置づけられており、国内において、水素エネルギーの利用に対する期待が高まっている。燃料電池自動車の実用化に伴い、今後は、水素の需要が継続的に高まることが予想され、低コスト・低環境負荷な方法で水素を生産する手法の開発が求められている。 2015 is positioned as the first year of hydrogen, and expectations for the use of hydrogen energy are growing in Japan. With the commercialization of fuel cell vehicles, the demand for hydrogen is expected to increase continuously in the future, and the development of a method for producing hydrogen by a low cost and low environmental load method is required.
メタンやタールに代表される炭化水素から水素を製造する手法において、コストと環境負荷の観点から重視すべき課題は、大きく二つある。一つめは、反応ガスを８００℃程度に加熱する必要があることである。炭化水素を水蒸気や二酸化炭素により水素と一酸化炭素に改質する反応は吸熱反応であり、高温条件化でなければ反応を進行させることが困難であるからである。二つめは、プロセス全体で考えると、二酸化炭素発生量が増大してしまうことである。化石燃料のうち、例えばメタンを改質して水素を製造した場合には、メタンをそのまま燃料として用いた場合と比べて、水素製造時に消費されるエネルギーの分だけ二酸化炭素の排出量が増大することとなる。 There are two major issues to be emphasized from the viewpoint of cost and environmental impact in the method of producing hydrogen from hydrocarbons represented by methane and tar. The first is that the reaction gas needs to be heated to about 800 ° C. This is because the reaction of reforming hydrocarbons into hydrogen and carbon monoxide with water vapor or carbon dioxide is an endothermic reaction, and it is difficult to advance the reaction unless the conditions are high. Second, when considering the entire process, the amount of carbon dioxide generation increases. Among fossil fuels, for example, when hydrogen is produced by reforming methane, the amount of carbon dioxide emissions increases by the amount of energy consumed during hydrogen production, compared to the case where methane is used directly as fuel. It will be.
上記の二つの課題を解決するために、各種の技術開発が進められている。
例えば、製鉄プロセスのコークス炉から発生するコークス炉ガスを改質し、水素を製造する手法では、コークス炉から放出される高温のコークス炉ガスをそのまま触媒と接触させることにより、ガスの昇温に必要となるエネルギーを節約することができる（例えば、以下の特許文献１〜４を参照。）。また、バイオガス中のメタンを原料として用いる場合には、化石燃料由来のメタンを利用しなくて済むため、プロセス全体で二酸化炭素の排出量を増大させることなく、水素を製造することが可能となる。
In order to solve the above-mentioned two problems, various technological developments are underway.
For example, in the method of reforming the coke oven gas generated from the coke oven in the iron making process and producing hydrogen, the high temperature coke oven gas released from the coke oven is brought into contact with the catalyst as it is to increase the temperature of the gas. Necessary energy can be saved (see, for example, Patent Documents 1 to 4 below). In addition, when methane in biogas is used as a raw material, it is not necessary to use methane derived from fossil fuels, so that it is possible to produce hydrogen without increasing carbon dioxide emissions throughout the process. Become.
しかしながら、コークス炉ガスとバイオガスの双方共に１０００ｐｐｍ超の硫化水素を含み、接触した触媒が大きく活性低下することが知られている。硫化水素は、数ｐｐｍ等の低濃度しか含まれない場合においても、触媒の活性低下を引き起こすことが知られており、５００ｐｐｍ以上のような高濃度の硫化水素を含むガス中で、触媒活性を発揮する触媒の報告例は少ない。近年では、コークス炉ガスを対象としたニッケルベースの触媒研究（例えば、以下の特許文献１〜４を参照。）の他、チタン酸バリウムベースの触媒が、硫化水素含有ガス中でタール・メタン改質活性を示すことなどが報告されている（例えば、以下の特許文献５〜８を参照。）。また、一部の研究グループが、酸化セリウムを主体とする触媒が硫化水素存在条件でも高い活性を示すことを報告しているが、これらの触媒は、硫化水素濃度５００ｐｐｍ以上の領域では、触媒活性が徐々に低下すると報告されている（例えば、以下の非特許文献１〜２を参照。）。 However, it is known that both coke oven gas and biogas contain more than 1000 ppm of hydrogen sulfide, and the contacted catalyst is greatly reduced in activity. Hydrogen sulfide is known to cause a decrease in the activity of the catalyst even when only a low concentration such as several ppm is contained, and the catalytic activity is reduced in a gas containing a high concentration of hydrogen sulfide such as 500 ppm or more. There are few reports of the catalyst to exhibit. In recent years, in addition to research on nickel-based catalysts for coke oven gas (see, for example, Patent Documents 1 to 4 below), barium titanate-based catalysts have been developed for tar-methane modification in hydrogen sulfide-containing gases. It has been reported that it exhibits qualitative activity (see, for example, Patent Documents 5 to 8 below). Some research groups have reported that cerium oxide-based catalysts show high activity even in the presence of hydrogen sulfide, but these catalysts have catalytic activity in the region where the hydrogen sulfide concentration is 500 ppm or more. Has been reported to gradually decrease (see, for example, Non-Patent Documents 1 and 2 below).
しかしながら、本発明者の検討によれば、コークス炉ガスを対象として開発されたニッケル系触媒についても、メタンやタールの改質活性は不十分となることが確認されている。また、チタン酸バリウムは、有毒なバリウムを多量に含む物質であり、劇物指定されている。そのため、製造、保管、利用の際に、十分な安全対策が必要となるという課題がある。そこで、高濃度の硫化水素存在下においても、高い炭化水素改質活性を示し、更には、作業者への有毒性の低い触媒が熱望されていた。 However, according to the study by the present inventor, it has been confirmed that the reforming activity of methane and tar is insufficient even for nickel-based catalysts developed for coke oven gas. Barium titanate is a substance containing a large amount of toxic barium and has been designated as a deleterious substance. For this reason, there is a problem that sufficient safety measures are required during manufacture, storage, and use. Therefore, a catalyst that exhibits high hydrocarbon reforming activity even in the presence of a high concentration of hydrogen sulfide and has low toxicity to workers has been desired.
本発明は、上記事情を鑑みてなされたものであり、硫化水素存在下においても炭化水素の水蒸気改質活性に優れた触媒、及び、この触媒を用いた水素の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a catalyst excellent in steam reforming activity of hydrocarbons even in the presence of hydrogen sulfide, and a method for producing hydrogen using this catalyst. And
本発明者は、コークス炉ガスやバイオガスなどのような高濃度硫化水素を含むガス中で触媒反応を進行させることを前提として、触媒開発を行った。メタン改質触媒として広く利用されるニッケルやルテニウムを含む触媒は、硫化水素存在下で大幅に活性低下することが知られているため、酸化物のみで構成される触媒に着目した。
以下、本発明の技術的思想について説明を行う。
The present inventor has developed a catalyst on the premise that the catalytic reaction proceeds in a gas containing high-concentration hydrogen sulfide such as coke oven gas or biogas. Catalysts containing nickel and ruthenium that are widely used as methane reforming catalysts are known to have a significant decrease in activity in the presence of hydrogen sulfide.
The technical idea of the present invention will be described below.
酸化物それ自体が触媒活性を発現させる場合、結晶格子に含まれる酸素の振る舞いが重要となる場合が多い。例えば、酸化銅と酸化マンガンとを主体とするホプカライト触媒では、結晶中の酸素イオンの拡散により、反応質に酸素が供給されるＭａｒｓ ｖａｎ Ｋｒｅｖｅｌｅｎ機構により、一酸化炭素酸化反応が進行する。また、酸化セリウムでは、一酸化炭素により酸化セリウム表面の酸素が奪われる還元と、水分子の酸素による再酸化との繰り返しによるレドックス機構によって、水性シフト反応が進行することが知られている。炭化水素の水蒸気改質は、上記いずれの機構も重要となる反応である。そこで、本発明者は、結晶内での酸素イオン伝導度が高い酸化物を利用することで、高い水蒸気改質触媒活性が得られるものと考察した。 When the oxide itself exhibits catalytic activity, the behavior of oxygen contained in the crystal lattice is often important. For example, in a hopcalite catalyst mainly composed of copper oxide and manganese oxide, a carbon monoxide oxidation reaction proceeds by a Mars van Krebelen mechanism in which oxygen is supplied to the reactant by diffusion of oxygen ions in the crystal. In cerium oxide, it is known that an aqueous shift reaction proceeds by a redox mechanism in which reduction of oxygen on the surface of cerium oxide is deprived by carbon monoxide and reoxidation of water molecules by oxygen. Hydrocarbon steam reforming is a reaction in which any of the above mechanisms is important. Therefore, the present inventor has considered that high steam reforming catalytic activity can be obtained by using an oxide having high oxygen ion conductivity in the crystal.
かかる考察に基づき、本発明者は、酸素イオン伝導性を示す複数の酸化物に着目し、調査・検討を行った。水蒸気改質反応においては、触媒が強い還元雰囲気に曝されるため、還元雰囲気における安定性に着目し、固体電解質型燃料電池のアノード触媒として報告のあるペロブスカイト型触媒について、鋭意検討を行った。 Based on this consideration, the present inventor paid attention to a plurality of oxides exhibiting oxygen ion conductivity and investigated and examined them. In the steam reforming reaction, since the catalyst is exposed to a strong reducing atmosphere, paying attention to the stability in the reducing atmosphere, the perovskite type catalyst that has been reported as the anode catalyst of the solid oxide fuel cell has been studied earnestly.
ペロブスカイト型酸化物は、ＡＢＯ３の一般式で示される酸化物であり、ＡとＢを占める元素を変更することで、さまざまな物性が変化する。酸素イオン伝導性を向上させるには、酸素が出入りすることに伴うカチオンの酸化数変化が許容されることが重要であり、また、そうしたカチオンの酸化数変化が生じたとしても、結晶構造が安定に維持されることが重要である。本発明者は、これらの知見に基づき鋭意検討を行って、高濃度の硫化水素存在下においても高い水蒸気改質活性を示すペロブスカイト型酸化物についての知見を得ることができた。
本発明は、上記の知見に基づいてなされたものであり、その要旨は以下の通りである。
The perovskite oxide is an oxide represented by the general formula of ABO 3 , and various physical properties change by changing elements occupying A and B. In order to improve oxygen ion conductivity, it is important that the change in the oxidation number of the cation due to the entry and exit of oxygen is allowed, and even if such a change in the oxidation number of the cation occurs, the crystal structure is stable. It is important to be maintained. The present inventor has conducted extensive studies based on these findings, and has been able to obtain knowledge on perovskite oxides that exhibit high steam reforming activity even in the presence of a high concentration of hydrogen sulfide.
This invention is made | formed based on said knowledge, The summary is as follows.
（１）構成元素として、ランタン、ストロンチウム、クロム及び酸素を含有し、更に、マンガン及び鉄の少なくとも何れかを一方を含有する、ペロブスカイト型酸化物からなる、水蒸気改質触媒。
（２）前記ランタン及び前記ストロンチウムの合計モル数と、前記クロム、前記マンガン及び前記鉄の合計モル数との比が、１．００：０．９５〜１．００：１．０５である、（１）に記載の水蒸気改質触媒。
（３）前記ランタンと前記ストロンチウムとのモル比が、５：５〜９：１であり、かつ、前記クロムのモル数と、前記マンガン及び前記鉄の合計モル数との比が、３：７〜７：３である、（１）又は（２）に記載の水蒸気改質触媒。
（４）（１）〜（３）の何れか一つに記載の水蒸気改質触媒に、水蒸気と炭化水素と硫化水素とを含むガスを接触させる、水素の製造方法。
（５）前記ガスに含有される硫化水素の濃度が、５００ｐｐｍ以上２０００ｐｐｍ以下である、（４）に記載の水素の製造方法。
(1) A steam reforming catalyst comprising a perovskite oxide containing lanthanum, strontium, chromium and oxygen as constituent elements, and further containing at least one of manganese and iron.
(2) The ratio of the total number of moles of the lanthanum and the strontium to the total number of moles of the chromium, the manganese and the iron is 1.00: 0.95 to 1.00: 1.05. The steam reforming catalyst according to 1).
(3) The molar ratio of the lanthanum to the strontium is 5: 5 to 9: 1, and the ratio of the number of moles of chromium to the total number of moles of manganese and iron is 3: 7. The steam reforming catalyst according to (1) or (2), which is -7: 3.
(4) A method for producing hydrogen, wherein the steam reforming catalyst according to any one of (1) to (3) is contacted with a gas containing steam, hydrocarbons, and hydrogen sulfide.
(5) The method for producing hydrogen according to (4), wherein the concentration of hydrogen sulfide contained in the gas is 500 ppm or more and 2000 ppm or less.
本発明に係る水蒸気改質触媒を用いることで、炭化水素ガス中に高濃度の硫化水素を含む場合であっても、水蒸気改質反応によって水素を製造することができる。 By using the steam reforming catalyst according to the present invention, hydrogen can be produced by the steam reforming reaction even when the hydrocarbon gas contains a high concentration of hydrogen sulfide.
以下に、本発明の好適な実施の形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
上述の通り、以下で詳述する本発明は、硫化物の触媒活性に着眼してなされたものであり、例えば５００ｐｐｍ以上という高濃度の硫化水素を含むガスを用いる炭化水素の水蒸気改質反応に対しても、適用することができる。 As described above, the present invention, which will be described in detail below, has been made with a focus on the catalytic activity of sulfides. For example, in the steam reforming reaction of hydrocarbons using a gas containing hydrogen sulfide at a high concentration of 500 ppm or more. It can also be applied to.
（水蒸気改質触媒について）
本発明の実施形態に係る水蒸気改質触媒は、ペロブスカイト型酸化物からなる触媒（以下、「ペロブスカイト型触媒」とも呼称する。）であり、かかるペロブスカイト型酸化物の他に、本発明の効果を損なわない範囲で各種の不純物を含有しうる。本実施形態に係るペロブスカイト型触媒は、一般式ＡＢＯ３で表されるＡサイトが、ランタンとストロンチウムとで構成され、一般式ＡＢＯ３で表されるＢサイトが、クロムと、マンガン及び／又は鉄と、で構成されている。換言すれば、本実施形態に係るペロブスカイト型触媒は、その構成元素として、ランタン、ストロンチウム、クロム及び酸素を少なくとも含有し、更に、マンガン及び鉄の少なくとも何れか一方を含有する。
(About steam reforming catalyst)
The steam reforming catalyst according to the embodiment of the present invention is a catalyst comprising a perovskite oxide (hereinafter also referred to as “perovskite catalyst”), and in addition to such a perovskite oxide, the effects of the present invention can be obtained. Various impurities can be contained as long as they are not impaired. Perovskite catalyst according to this embodiment, A-site of the general formula ABO 3 is constituted by lanthanum and strontium, B site of the general formula ABO 3 includes a chromium, manganese and / or iron And is composed of. In other words, the perovskite catalyst according to the present embodiment contains at least lanthanum, strontium, chromium and oxygen as its constituent elements, and further contains at least one of manganese and iron.
まず、本実施形態に係るペロブスカイト型触媒における各構成元素の比率について、説明する。
本実施形態に係るペロブスカイト型触媒において、Ａサイトの構成元素とＢサイトの構成元素の割合は、一般式から明らかなように、モル比で１：１であることが好ましい。しかしながら、原料組成の厳密な制御は困難であることから、Ａサイトの構成元素とＢサイトの構成元素とのモル比は、１．００：０．９５〜１．００：１．０５の範囲で変化することが許容される。
First, the ratio of each constituent element in the perovskite catalyst according to this embodiment will be described.
In the perovskite-type catalyst according to this embodiment, the ratio of the constituent elements of the A site and the B site is preferably 1: 1 in terms of molar ratio, as is apparent from the general formula. However, since it is difficult to strictly control the raw material composition, the molar ratio between the constituent elements of the A site and the constituent elements of the B site is in the range of 1.00: 0.95 to 1.00: 1.05. It is allowed to change.
次に、各サイトを占める構成元素のモル比について説明する。
Ａサイトの構成元素のモル比については、Ｌａ：Ｓｒ＝５：５〜９：１である（換言すれば、Ｌａのモル数が、Ｌａ＋Ｓｒの合計モル数に対して、５０％以上９０％以下である）ことが好ましく、Ｌａ：Ｓｒ＝７：３〜８：２であることが特に好ましい。
Next, the molar ratio of the constituent elements occupying each site will be described.
The molar ratio of the constituent elements of the A site is La: Sr = 5: 5 to 9: 1 (in other words, the number of moles of La is 50% or more and 90% or less with respect to the total number of moles of La + Sr). It is preferable that La: Sr = 7: 3 to 8: 2.
また、Ｂサイトを占める構成元素のモル比については、Ｃｒ：（Ｍｎ＋Ｆｅ）＝３：７〜７：３である（換言すれば、Ｃｒのモル数が、Ｃｒ＋Ｍｎ＋Ｆｅの合計モル数に対して、３０％以上７０％以下である）ことが好ましく、Ｃｒ：（Ｍｎ＋Ｆｅ）＝４：６〜６：４であることが特に好ましい。 The molar ratio of the constituent elements occupying the B site is Cr: (Mn + Fe) = 3: 7 to 7: 3 (in other words, the number of moles of Cr is 30 with respect to the total number of moles of Cr + Mn + Fe). %: 70% or less), and Cr: (Mn + Fe) = 4: 6 to 6: 4 is particularly preferable.
サイト間での構成元素のモル比の範囲、及び、サイト内での構成元素のモル比の範囲が上記の範囲から外れた触媒は、そもそもペロブスカイト型構造を取りにくいか、又は、反応条件で分解してしまう可能性が高い。従って、反応条件下でも安定なペロブスカイト型の酸化物を得るためには、生成する触媒の組成比を、上述の組成範囲内とすることが好ましい。組成範囲は、製造方法によらず同一である。ただし、製造方法ごとに、製品内における組成の不均一性や、組成の制御のしやすさは異なるため、注意が必要である。 A catalyst whose molar ratio of constituent elements between sites and the molar ratio of constituent elements within the site deviates from the above range is difficult to take a perovskite structure in the first place, or decomposes under reaction conditions. There is a high possibility that Therefore, in order to obtain a perovskite oxide that is stable even under reaction conditions, it is preferable that the composition ratio of the produced catalyst be within the above-described composition range. The composition range is the same regardless of the production method. However, care must be taken because the composition non-uniformity in the product and the ease of control of the composition differ depending on the manufacturing method.
本実施形態に係るペロブスカイト型触媒を構成する金属元素の酸化物は、いずれも沸点が高いため、後述のいずれの方法を用いて本実施形態に係るペロブスカイト型触媒を製造した場合においても、原料に含まれる金属元素量と製品中の金属元素量とが、ほぼ一致する。従って、本実施形態に係るペロブスカイト型触媒の製造に際して求められる精度であれば、製造原料の組成によって触媒の組成を計算することが可能である。ただし、目的の触媒が得られていることを確認する目的で、得られた触媒について詳細に組成分析を行っても構わない。 Since all the metal element oxides constituting the perovskite catalyst according to the present embodiment have a high boiling point, even when the perovskite catalyst according to the present embodiment is manufactured using any of the methods described later, The amount of metal element contained and the amount of metal element in the product are almost the same. Therefore, the composition of the catalyst can be calculated from the composition of the production raw material with the accuracy required for the production of the perovskite catalyst according to the present embodiment. However, the composition of the obtained catalyst may be analyzed in detail for the purpose of confirming that the target catalyst is obtained.
ここで、得られた触媒がペロブスカイト型構造を有しているか否かは、Ｘ線回折測定を行うことで判別することが可能である。ペロブスカイト型の酸化物は、空間群Ｐｍ−３ｍで表わされる非常に高い対称性を有している。このため、多種類の金属元素を含む複雑な組成の場合においても、Ｘ線回折パターンに現れるピークの数は少なく、容易に不純物の有無を判別することができる。データベース上には、様々なペロブスカイト型構造の酸化物について、Ｘ線回折測定の結果が登録されているため、それらと比較することによって、目的のペロブスカイト型化合物が得られているかを確認することが可能である。また、データベース上に、目的のペロブスカイト型化合物のＸ線回折スペクトルが見当たらない場合においても、ベガード則を仮定することで、類似組成のペロブスカイト型化合物のスペクトルを参考にして、目的化合物のスペクトルを推定することが可能である。Ｘ線回折スペクトルのデータベースとしては、任意のものが利用可能であるが、例えば物質・材料研究機構が提供するＭａｔＮａｖｉ等が挙げられる。 Here, whether or not the obtained catalyst has a perovskite structure can be determined by performing X-ray diffraction measurement. The perovskite oxide has very high symmetry represented by the space group Pm-3m. For this reason, even in the case of a complicated composition containing many kinds of metal elements, the number of peaks appearing in the X-ray diffraction pattern is small, and the presence or absence of impurities can be easily determined. In the database, the results of X-ray diffraction measurement are registered for various oxides of perovskite structure. By comparing with the results, it is possible to confirm whether the target perovskite compound is obtained. Is possible. In addition, even if the X-ray diffraction spectrum of the target perovskite compound is not found on the database, the spectrum of the target compound is estimated with reference to the spectrum of the perovskite compound of similar composition by assuming Vegard's law. Is possible. Any database of X-ray diffraction spectra can be used, and examples thereof include MatNavi provided by the National Institute for Materials Science.
また、試料の組成分析には、任意の方法が利用可能であるが、本発明を実行するうえで必要となる精度で成分分析を行うにあたっては、Ｘ線蛍光分析を行うことが簡便である。より正確な濃度を知りたい場合には、ＩＣＰ発光分析を行ってもよい。いずれの分析手法で組成分析を行った場合においても、標準的な市販装置には、含まれる金属元素のモル比を出力する機能が含まれており、触媒を構成する金属元素のモル比を直ちに得ることができる。 Although any method can be used for the composition analysis of the sample, it is convenient to perform X-ray fluorescence analysis when performing component analysis with the accuracy required for carrying out the present invention. When it is desired to know a more accurate concentration, ICP emission analysis may be performed. Regardless of which analysis method is used, standard commercial equipment includes a function to output the molar ratio of the contained metal elements. Can be obtained.
本実施形態に係るペロブスカイト型触媒は、任意の方法で生成可能である。具体的には、本実施形態に係るペロブスカイト型触媒の製造方法として、各酸化物を混合し焼成することで反応させる固相反応法、前駆体溶液のｐＨを変化させて沈殿物を得る共沈法、前駆体溶液に有機分子を添加してゾル状とし焼成するゾルゲル法、前駆体試薬を酸化物担体へ含浸させる含浸法などを利用することが可能である。以下で、各方法に関する注意点などを示す。 The perovskite catalyst according to this embodiment can be generated by any method. Specifically, as a method for producing a perovskite-type catalyst according to the present embodiment, a solid-phase reaction method in which each oxide is mixed and calcined, a coprecipitation to obtain a precipitate by changing the pH of the precursor solution It is possible to use a method, a sol-gel method in which an organic molecule is added to a precursor solution to form a sol, and an impregnation method in which an oxide carrier is impregnated with a precursor reagent. The following are points to note regarding each method.
固相反応法は、得られる酸化物の比表面積が小さくなりやすいということが課題となることがある。原料の酸化物粉末を混合し、焼成することで目的物を得る本手法は、粉末同士が十分に反応するために元素の拡散が必要となり、高温・長時間の焼成が必要となる場合が多い。よって、得られるペロブスカイト型触媒の比表面積が小さくなりやすく、高い活性を得ることが難しくなることがある。 In the solid phase reaction method, the problem is that the specific surface area of the obtained oxide tends to be small. This method of obtaining the target product by mixing raw material oxide powder and firing requires diffusion of elements in order for the powders to sufficiently react with each other, often requiring firing at a high temperature for a long time . Therefore, the specific surface area of the obtained perovskite catalyst tends to be small, and it may be difficult to obtain high activity.
共沈法は、前駆体溶液のｐＨを変化させて沈殿物を得る手法であり、比較的簡便に均一な組成で、高比表面積な触媒を得ることが可能である。しかしながら、本実施形態に係るペロブスカイト型触媒を生成する際には、いくつか注意すべき点がある。 The coprecipitation method is a technique for obtaining a precipitate by changing the pH of a precursor solution, and it is possible to obtain a catalyst having a high specific surface area with a uniform composition relatively easily. However, there are some points to be noted when generating the perovskite catalyst according to this embodiment.
第一に、共沈操作の際に用いる塩基性試薬の種類に注意すべきである。
本実施形態に係るペロブスカイト型触媒に含まれるストロンチウムは、非常に安定な炭酸塩を形成することが知られており、一般的には、分解に１０００℃超の高温が必要となるとされている。従って、塩基性物質として炭酸水素ナトリウムなどのように炭酸イオンを含む物質を利用すると、不純物として炭酸ストロンチウムが多量に残存してしまうこととなる。多量の不純物の残存を避けるためには、焼成時間を長くすることや、焼成温度を１０００℃超とすることが望まれる。
First, attention should be paid to the type of basic reagent used in the coprecipitation operation.
Strontium contained in the perovskite catalyst according to the present embodiment is known to form a very stable carbonate, and it is generally said that a high temperature exceeding 1000 ° C. is required for decomposition. Therefore, when a substance containing carbonate ions such as sodium bicarbonate is used as a basic substance, a large amount of strontium carbonate remains as an impurity. In order to avoid a large amount of impurities remaining, it is desirable to lengthen the baking time and to set the baking temperature to over 1000 ° C.
第二に、水酸化ストロンチウムが比較的高い溶解度を持つことが挙げられる。
水酸化ストロンチウムは、室温で水１００ｇあたりに１．０ｇ程度溶解することが知られており、共沈操作の際にも溶液中に一部が残存してしまう。これにより、原料と生成物との間に、組成ずれが生じることとなる。更に、共沈物をろ過やデカンテーションなどの方法で分取後に洗浄操作を行うと、ストロンチウムが選択的に溶出することとなり、これも組成ずれの原因となる。従って、分取後に洗浄操作が必要となる塩基性試薬を用いて共沈を行うことは、避けるべきである。具体的には、水酸化ナトリウムや水酸化カリウムなどを用いることは、好ましくない。
Secondly, strontium hydroxide has a relatively high solubility.
It is known that about 1.0 g of strontium hydroxide dissolves per 100 g of water at room temperature, and a part of the strontium hydroxide remains in the solution during the coprecipitation operation. Thereby, a composition shift occurs between the raw material and the product. Furthermore, when the coprecipitate is subjected to a washing operation after separation by a method such as filtration or decantation, strontium is selectively eluted, which also causes a compositional deviation. Therefore, coprecipitation using a basic reagent that requires a washing operation after fractionation should be avoided. Specifically, it is not preferable to use sodium hydroxide or potassium hydroxide.
以上より、共沈法を用いる場合には、ストロンチウムの溶出を抑制するために用いる水の量を少なめに設定することや、塩基性試薬としては、一部残存しても問題とならないような、アンモニア水などを用いることが好ましい。このとき、焼成時のシンタリングに伴う比表面積の低下を抑制するため、インヒビターとしてアルミナのゾルを添加しても構わない。 From the above, when using the coprecipitation method, setting a small amount of water to be used for suppressing elution of strontium, or as a basic reagent, there is no problem even if some remain, It is preferable to use ammonia water or the like. At this time, an alumina sol may be added as an inhibitor in order to suppress a decrease in specific surface area accompanying sintering during firing.
ゾルゲル法は、前駆体溶液に錯形成を起こす有機化合物を添加したうえで、蒸発乾固し、焼成して酸化物を得る手法である。この手法では、ストロンチウムの溶出による組成ずれを避けることができるという利点がある。錯形成させるための有機物には、クエン酸、ＥＤＴＡ、エチレンジアミンなどの多座配位子を用いることができる。加える配位子のモル数は、少なくとも前駆体溶液中に含まれる金属イオンの量よりも多いことが重要であるが、あまりに多すぎると、焼成時に有機物の燃焼に伴い発生する二酸化炭素量が増大し、炭酸ストロンチウムが生成する原因となる。配位子と金属イオンとのモル比は、配位子：金属イオン＝１：１〜３：１とすることが好ましい。このとき、焼成時のシンタリングに伴う比表面積の低下を抑制するため、インヒビターとしてアルミナのゾルを添加しても構わない。 The sol-gel method is a technique in which an organic compound that causes complex formation is added to a precursor solution, followed by evaporation to dryness and baking to obtain an oxide. This technique has the advantage that compositional deviation due to elution of strontium can be avoided. As the organic substance for complex formation, a multidentate ligand such as citric acid, EDTA, or ethylenediamine can be used. It is important that the number of moles of ligand to be added is at least larger than the amount of metal ions contained in the precursor solution, but if it is too large, the amount of carbon dioxide generated due to the combustion of organic substances during firing increases. However, this causes strontium carbonate to be generated. The molar ratio of the ligand to the metal ion is preferably ligand: metal ion = 1: 1 to 3: 1. At this time, an alumina sol may be added as an inhibitor in order to suppress a decrease in specific surface area accompanying sintering during firing.
含浸法を用いる場合には、担体と、加える前駆体試薬の組み合わせが多数考えられる。例えば、アルミナに代表される高比表面積・高耐熱性の担体に、前駆体試薬を含浸させ、焼成するという方法が挙げられる。この手法は、用いる水溶液の量が少なく、組成ずれも生じにくいというメリットがあるが、場合によっては、触媒全体に占めるペロブスカイト型触媒の割合が小さくなったり、ペロブスカイト型触媒中にアルミナが一部固溶してしまったりする可能性がある。 When the impregnation method is used, many combinations of a carrier and a precursor reagent to be added are conceivable. For example, a method of impregnating a precursor reagent into a carrier having a high specific surface area and a high heat resistance typified by alumina and firing it may be mentioned. This method has the merit that the amount of aqueous solution used is small and composition deviation hardly occurs. However, in some cases, the ratio of the perovskite type catalyst to the whole catalyst is reduced, or alumina is partially solidified in the perovskite type catalyst. There is a possibility of melting.
以上、本実施形態に係るペロブスカイト型触媒について、詳細に説明した。 Heretofore, the perovskite catalyst according to the present embodiment has been described in detail.
（水素の製造方法について）
続いて、以上説明したような水蒸気改質触媒を用いた水素の製造方法について説明する。
本実施形態に係る水素の製造方法は、以上説明したようなペロブスカイト型酸化物からなる水蒸気改質触媒に、水蒸気と炭化水素と硫化水素とを含むガスを接触させることで水蒸気改質反応を進行させて、被処理ガス中の炭化水素を水蒸気改質して水素を発生する方法である。
(About hydrogen production method)
Subsequently, a method for producing hydrogen using the steam reforming catalyst as described above will be described.
The method for producing hydrogen according to the present embodiment proceeds with a steam reforming reaction by bringing a gas containing steam, hydrocarbons, and hydrogen sulfide into contact with a steam reforming catalyst composed of a perovskite oxide as described above. Thus, the hydrocarbon in the gas to be treated is steam reformed to generate hydrogen.
ここで、本実施形態に係るペロブスカイト型触媒を用いて水蒸気改質反応を進行させる場合、反応温度の選定は重要である。反応温度が低く、例えば７００℃未満である場合には、反応速度が下がり、水素製造効率が低下するため、好ましくない。一方、反応温度が高く、例えば９００℃よりも高い場合には、触媒の比表面積低下が進行し、活性低下が進行する他、被処理ガスを加熱するために必要となるエネルギー量が増大するため、好ましくない。以上より、反応速度を高め、かつ、触媒活性が低下しないようにするためには、反応温度を適切な温度範囲内にすることが好ましい。本実施形態に係る水素の製造方法において、反応温度は、７００℃以上９００℃以下であることが好ましく、７５０℃以上８５０℃以下であることが一層好ましい。 Here, when the steam reforming reaction proceeds using the perovskite catalyst according to this embodiment, the selection of the reaction temperature is important. When the reaction temperature is low, for example, lower than 700 ° C., the reaction rate decreases and the hydrogen production efficiency decreases, which is not preferable. On the other hand, when the reaction temperature is high, for example, higher than 900 ° C., the specific surface area of the catalyst is decreased, the activity is decreased, and the amount of energy required for heating the gas to be processed is increased. It is not preferable. From the above, it is preferable to set the reaction temperature within an appropriate temperature range in order to increase the reaction rate and prevent the catalyst activity from decreasing. In the hydrogen production method according to this embodiment, the reaction temperature is preferably 700 ° C. or higher and 900 ° C. or lower, and more preferably 750 ° C. or higher and 850 ° C. or lower.
なお、ペロブスカイト型触媒と被処理ガスとの反応温度を上記のような温度範囲まで昇温する際の加熱手段については、特に限定されるものではなく、公知の加熱手段を利用することが可能である。 The heating means for raising the reaction temperature between the perovskite catalyst and the gas to be treated to the above temperature range is not particularly limited, and a known heating means can be used. is there.
＜被処理ガスについて＞
また、本実施形態に係るペロブスカイト型触媒を用いて水蒸気改質反応を進行させる際、被処理ガス中には、炭化水素及び水蒸気が含有されている。また、被処理ガスは、水蒸気と炭化水素中の炭素原子とのモル比を示すスチーム／カーボン比が１以上であると好ましい。更に、被処理ガス中に硫化水素が含有されていると、より高い触媒活性が得られ、より好ましい。具体的には、被処理ガス中の硫化水素濃度は、１００ｐｐｍ以上３０００ｐｐｍ以下であると好ましく、５００ｐｐｍ以上２０００ｐｐｍ以下であるとより一層好ましい。
<About treated gas>
Further, when the steam reforming reaction proceeds using the perovskite catalyst according to the present embodiment, the gas to be treated contains hydrocarbons and steam. Further, the gas to be treated preferably has a steam / carbon ratio of 1 or more indicating a molar ratio of water vapor to carbon atoms in the hydrocarbon. Furthermore, it is more preferable that hydrogen sulfide is contained in the gas to be treated because higher catalytic activity can be obtained. Specifically, the hydrogen sulfide concentration in the gas to be treated is preferably 100 ppm or more and 3000 ppm or less, and more preferably 500 ppm or more and 2000 ppm or less.
本実施形態に係るペロブスカイト型触媒を用いた改質反応において、対象となる被処理ガス中の炭化水素には、以下の実施例に示されるメタンと１−メチルナフタレンに限られず、炭素数１１以下の非芳香族炭化水素、炭素数１１以下の芳香族炭化水素、更には炭素数１１以上のタール成分が含まれうる。その理由は、以下の通りである。 In the reforming reaction using the perovskite catalyst according to the present embodiment, the hydrocarbons in the target gas to be treated are not limited to methane and 1-methylnaphthalene shown in the following examples, and have 11 or less carbon atoms. Non-aromatic hydrocarbons, aromatic hydrocarbons having 11 or less carbon atoms, and tar components having 11 or more carbon atoms. The reason is as follows.
まず、メタンは、炭化水素の中で最も小さい分子であり、水蒸気改質反応による水素生成反応が進行し難いことが知られている。よって、メタン改質反応を進行させることのできる本実施形態に係る水素の製造方法は、エタン、エテン、プロパン、プロペン、ブタン、ブテン、ペンタン、ペンテン、ヘキサン、ヘキセン、ヘプタン、ヘプテン、オクタン、オクテン、ノナン、ノネン、デカン、デケン、ウンデカン、ウンデケンなどの非芳香族性の炭化水素も水蒸気改質して、水素を製造することが可能である。非芳香族性の炭化水素は、一般的に、芳香族炭化水素類と比較して水蒸気改質中に炭素析出が生じ難いことから、１−メチルナフタレンを用いた場合にも炭素析出を抑制又は防止可能な本実施形態に係る水素の製造方法では、炭素数１１以下の非芳香族炭化水素を用いた場合にも炭素析出を防止することができ、安定して水素製造が可能となる。なお、炭素数１２以上の非芳香族炭化水素は、容易に熱分解したり酸化分解したりして、炭素数１１以下の化合物を生成する。よって、適切な反応条件、及び、被処理ガスの前処理条件を選択することによって、炭素数１２以上の非芳香族炭化水素に対しても、本実施形態に係る水素の製造方法を適用することが可能である。 First, methane is the smallest molecule among hydrocarbons, and it is known that the hydrogen generation reaction by the steam reforming reaction is difficult to proceed. Therefore, the method for producing hydrogen according to the present embodiment capable of causing the methane reforming reaction to proceed is ethane, ethene, propane, propene, butane, butene, pentane, pentene, hexane, hexene, heptane, heptene, octane, octene. Non-aromatic hydrocarbons such as nonane, nonene, decane, decene, undecane and undecane can also be steam reformed to produce hydrogen. Non-aromatic hydrocarbons generally inhibit carbon deposition even when 1-methylnaphthalene is used because carbon deposition is less likely to occur during steam reforming compared to aromatic hydrocarbons. In the hydrogen production method according to the present embodiment, which can be prevented, carbon deposition can be prevented even when a non-aromatic hydrocarbon having 11 or less carbon atoms is used, and hydrogen production can be stably performed. Note that non-aromatic hydrocarbons having 12 or more carbon atoms are easily pyrolyzed or oxidatively decomposed to produce compounds having 11 or less carbon atoms. Therefore, the method for producing hydrogen according to this embodiment is applied to non-aromatic hydrocarbons having 12 or more carbon atoms by selecting appropriate reaction conditions and pretreatment conditions for the gas to be treated. Is possible.
また、１−メチルナフタレンは、タールに分類される物質の一つとして選択されている。タールとは、非常に多くの物質を含む総称であり、その具体的な物質の例は、文献に記載されている（上記非特許文献３を参照。）。タールの多くは、複数の芳香環が連結したものや、また、その芳香環に置換基が付いたものであり、最大で芳香環を４つ含むものまでがタール成分として列挙されている。その中でも最も含有比が高いのは、芳香環２つの物質であり、１−メチルナフタレンはまさにタール成分を代表させるのに適した物質である。また、１−メチルナフタレンは、芳香環に置換基が付いた構造をしており、他の多くのタール成分が持つ特徴を備えている。よって、１−メチルナフタレンを用いた水蒸気改質試験で効率的な水素製造を確認した本実施形態に係る水素の製造方法は、他のタール成分に対しても適用することが可能である。また、芳香環を１つのみ含む炭化水素類は、芳香環を２つ含む物質よりも一般に反応性に富むことが知られているため、１−メチルナフタレンを用いた水蒸気改質試験で効率的な水素製造を確認した本実施形態に係る水素の製造方法は、芳香環を１つのみ含む芳香族炭化水素類に対しても、同様に適用可能であると考えられる。 Further, 1-methylnaphthalene is selected as one of substances classified as tar. Tar is a generic name including a great number of substances, and examples of specific substances are described in the literature (see Non-Patent Document 3 above). Most of tars are those in which a plurality of aromatic rings are connected, or those aromatic rings having substituents, and those containing up to four aromatic rings are listed as tar components. Among them, the substance having the highest content ratio is a substance having two aromatic rings, and 1-methylnaphthalene is a substance suitable for representing a tar component. Moreover, 1-methylnaphthalene has a structure in which a substituent is attached to an aromatic ring, and has characteristics of many other tar components. Therefore, the method for producing hydrogen according to the present embodiment in which efficient hydrogen production is confirmed by a steam reforming test using 1-methylnaphthalene can be applied to other tar components. Also, since hydrocarbons containing only one aromatic ring are known to be generally more reactive than substances containing two aromatic rings, they are more efficient in steam reforming tests using 1-methylnaphthalene. It is considered that the hydrogen production method according to the present embodiment, which has confirmed the production of hydrogen, can be similarly applied to aromatic hydrocarbons containing only one aromatic ring.
本発明の触媒を適用可能な硫化水素を含有する炭化水素ガスとしては、例えば、天然ガス、コークス炉ガス、バイオガスなどが挙げられる。バイオガスは、バイオマスをメタン発酵によって分解する際に発生するガスであり、家畜の排泄物や下水汚泥などから発生している。バイオガスでは、酸素源として二酸化炭素も含まれていることから、ガス中の二酸化炭素を活用することで、より一層水素製造効率が高まると考えられる。 Examples of the hydrocarbon gas containing hydrogen sulfide to which the catalyst of the present invention can be applied include natural gas, coke oven gas, and biogas. Biogas is a gas generated when biomass is decomposed by methane fermentation, and is generated from livestock excrement and sewage sludge. Since biogas also contains carbon dioxide as an oxygen source, it is considered that hydrogen production efficiency is further increased by utilizing carbon dioxide in the gas.
以上、本実施形態に係る水素の製造方法について、詳細に説明した。 Heretofore, the method for producing hydrogen according to the present embodiment has been described in detail.
以下では、試験例を示しながら本発明を具体的に説明するが、本発明は、下記に示す試験例により何ら限定されるものではない。 Below, although this invention is demonstrated concretely, showing a test example, this invention is not limited at all by the test example shown below.
［触媒調製］
（比較例１：ニッケル系触媒）
共沈法により、ニッケル担持触媒を生成した。
２０００ｍｌビーカーに１０００ｍｌの純水、１０００ｍｌのビーカーに５００ｍｌの純水をそれぞれ入れ、マグネチックスターラーで攪拌しながら、６０℃に昇温した。硝酸ニッケル・６水和物（関東化学、純度＞９８．０％）１３．３０ｇと、硝酸マグネシウム・６水和物（和光純薬、純度＞９９．０％）１０５．５１ｇとを秤取り、６０℃に維持した純水１０００ｍｌに溶解させた。また、炭酸カリウム（関東化学、純度＞９９．５％）を６３．１９ｇ秤取り、６０℃に維持された５００ｍｌの純水に溶解した。硝酸塩を溶解した１０００ｍｌの溶液を、温度計で溶液の温度を測定しながら、メカニカルスターラーで攪拌した。メカニカルスターラーでの攪拌を継続しながら、５００ｍｌの炭酸カリウム水溶液を、１０００ｍｌの硝酸塩水溶液に入れ、温度を６０℃に保持したまま１時間攪拌を行った。攪拌後、得られたゾルを、吸引濾過して沈殿物を分取した。得られた沈殿物を、８０℃に熱した５００ｍｌの純水で洗浄し、再度吸引濾過することを４回繰り返し、カリウムを除去した。洗浄の終わった沈殿物を、５００ｍｌの純水に入れ、ペースト状となるまで練り、メカニカルスターラーで攪拌しながら、アルミナゾル（日産化学工業製、アルミナゾル５２０）を９５．２４ｇ投入し、更に３０分間攪拌を行った。全体が均一になったことを目視確認した後、一晩静置し、熟成させた。再度撹拌した後に、ロータリーエバポレーターに移し、水分を除去し、得られた固形物を、乾燥機内にて１２０℃で更に２０時間乾燥させた。乾燥機から固形物を取り出し、メノウ乳鉢で粉砕した。得られた粉末を、アルミナるつぼに移し、電気炉中で９５０℃にて２０時間焼成処理を行った。冷却後、得られた触媒を触媒Ａとした。触媒Ａの組成は、質量比で５０％のアルミナを含み、残部の５０質量％は、マグネシアとニッケル酸化物とをモル比で９：１含む。
[Catalyst preparation]
(Comparative Example 1: Nickel catalyst)
A nickel-supported catalyst was produced by the coprecipitation method.
1000 ml of pure water was put into a 2000 ml beaker, and 500 ml of pure water was put into a 1000 ml beaker, and the temperature was raised to 60 ° C. while stirring with a magnetic stirrer. Weigh 13.30 g of nickel nitrate hexahydrate (Kanto Chemical, purity> 98.0%) and 105.51 g of magnesium nitrate hexahydrate (Wako Pure Chemical, purity> 99.0%), It was dissolved in 1000 ml of pure water maintained at 60 ° C. In addition, 63.19 g of potassium carbonate (Kanto Chemical, purity> 99.5%) was weighed and dissolved in 500 ml of pure water maintained at 60 ° C. A 1000 ml solution in which nitrate was dissolved was stirred with a mechanical stirrer while measuring the temperature of the solution with a thermometer. While stirring with a mechanical stirrer, 500 ml of potassium carbonate aqueous solution was put into 1000 ml of nitrate aqueous solution, and stirred for 1 hour while maintaining the temperature at 60 ° C. After stirring, the resulting sol was filtered with suction to collect a precipitate. The obtained precipitate was washed with 500 ml of pure water heated to 80 ° C. and suction filtered again four times to remove potassium. The washed precipitate is put into 500 ml of pure water, kneaded until it becomes a paste, and 95.24 g of alumina sol (Nissan Chemical Industries, Alumina Sol 520) is added while stirring with a mechanical stirrer, and further stirred for 30 minutes. Went. After visually confirming that the whole was uniform, it was allowed to stand overnight and aged. After stirring again, it moved to the rotary evaporator, the water | moisture content was removed, and the obtained solid substance was further dried at 120 degreeC in the dryer for 20 hours. The solid matter was taken out from the dryer and pulverized in an agate mortar. The obtained powder was transferred to an alumina crucible and fired at 950 ° C. for 20 hours in an electric furnace. After cooling, the resulting catalyst was designated as Catalyst A. The composition of the catalyst A contains 50% alumina by mass, and the remaining 50% by mass contains 9: 1 magnesia and nickel oxide in a molar ratio.
（比較例２：Ｌａ０．７Ｓｒ０．３ＶＯｘ触媒）
固体電解質型燃料電池の電極触媒として研究報告のある、ランタンバナジウム系の触媒を、クエン酸法にて生成した。
硝酸ランタン６水和物（関東化学、純度＞９９．０％）を２．５６０４ｇ、硝酸ストロンチウム（関東化学、純度＞９８．０％）を０．５３８５ｇ、メタバナジン酸アンモニウム（関東化学、純度＞９９．０％）を０．９９０５ｇそれぞれ秤取り、１６０ｍｌの純水に加えた。得られた溶液に、クエン酸１水和物（関東化学、純度＞９９．５％）を７．１２２３ｇ加えた。クエン酸と全金属イオンの量比は、モル比で２：１である。目視で解け残りがなくなるまで攪拌した。アンモニア水（関東化学、純度２８．０〜３０．０％）を滴下し、ｐＨ８とし、７０℃で保温して、ゲル状となるまで水分を蒸発させた。得られたゲル状物質を、るつぼに移して電気炉中１５０℃で乾燥し、固化したことを確認したうえで、マッフル炉で窒素フロー下にて焼成処理を行った。室温から３０分で１１０℃まで昇温し、４時間更に乾燥させたうえで、７００℃まで４時間かけて昇温し、１時間焼成してから１時間かけて室温まで冷却し、１．８３２１ｇの黒色粉末を得た。得られた触媒を比較例２とする。比較例２の触媒のＸ線回折測定を行うと、酸化ランタンや酸化ストロンチウム等を含む複数の相の混合物となっており、ペロブスカイト型構造をなしていなかった。
(Comparative Example 2: La 0.7 Sr 0.3 VO x catalyst)
A lanthanum vanadium-based catalyst, which has been reported as an electrode catalyst for solid oxide fuel cells, was produced by the citric acid method.
2.5604 g of lanthanum nitrate hexahydrate (Kanto Chemical, purity> 99.0%), 0.5385 g of strontium nitrate (Kanto Chemical, purity> 98.0%), ammonium metavanadate (Kanto Chemical, purity> 99) 0.9%) was weighed and added to 160 ml of pure water. To the resulting solution, 7.1223 g of citric acid monohydrate (Kanto Chemical, purity> 99.5%) was added. The molar ratio of citric acid to all metal ions is 2: 1 in molar ratio. The mixture was stirred until there was no undissolved residue. Aqueous ammonia (Kanto Chemical Co., Inc., purity: 28.0 to 30.0%) was added dropwise to adjust the pH to 8, kept at 70 ° C., and water was evaporated until a gel was formed. The obtained gel-like substance was transferred to a crucible, dried at 150 ° C. in an electric furnace and solidified, and then baked in a muffle furnace under a nitrogen flow. The temperature was raised from room temperature to 110 ° C. in 30 minutes, further dried for 4 hours, then heated to 700 ° C. over 4 hours, baked for 1 hour, cooled to room temperature over 1 hour, 1.8321 g Of black powder was obtained. The obtained catalyst is referred to as Comparative Example 2. When the X-ray diffraction measurement of the catalyst of Comparative Example 2 was performed, it was a mixture of a plurality of phases containing lanthanum oxide, strontium oxide, etc., and did not have a perovskite structure.
（比較例３：Ｌａ０．７Ｓｒ０．３ＶＯｘ触媒）
比較例２を、０．８９４６ｇ秤取り、石英ガラス管に充填した。１０％水素、アルゴンバランスのガスを７０ｃｍ３／分でフローさせつつ、管状電気炉にて焼成処理を行った。室温から３時間で９００℃まで昇温し、６時間還元処理を行い、１時間かけて室温まで冷却し、０．７５９７ｇの黒色粉末を得た。得られた触媒を、比較例３とする。比較例３のの触媒のＸ線回折測定を行うと、少量の不純物ピークを含むものの、ほぼペロブスカイト型構造の単相となっていた。
(Comparative Example 3: La 0.7 Sr 0.3 VO x catalyst)
Comparative Example 2 was weighed 0.8946 g and filled into a quartz glass tube. While a 10% hydrogen / argon balance gas was allowed to flow at 70 cm 3 / min, firing treatment was performed in a tubular electric furnace. The temperature was raised from room temperature to 900 ° C. in 3 hours, subjected to reduction treatment for 6 hours, and cooled to room temperature over 1 hour to obtain 0.7597 g of black powder. The obtained catalyst is referred to as Comparative Example 3. When the X-ray diffraction measurement of the catalyst of Comparative Example 3 was performed, a single phase having a perovskite structure was obtained although a small amount of impurity peak was included.
（実施例１：ＬａＳｒＣｒＭｎ系触媒）
ＬａＳｒＣｒＭｎ系の触媒を、クエン酸法にて作成した。
硝酸ランタン６水和物（関東化学、純度＞９９．０％）を２．８２９８ｇ、硝酸ストロンチウム（関東化学、純度＞９８．０％）を０．４６１８ｇ、硝酸クロム９水和物（関東化学、純度 ９８．０〜１０３．０％）を１．７４３６ｇ、硝酸マンガン６水和物（関東化学、純度＞９８．０％）を１．２５０１ｇ秤取り、５０ｍｌの純水に加えた。得られた溶液に、クエン酸１水和物（関東化学、純度＞９９．５％）を６．６９６１ｇ加え、目視で解け残りがなくなるまで攪拌した。クエン酸と全金属イオンの量比は、モル比で２：１である。アンモニア水（関東化学、純度２８．０〜３０．０％）を滴下し、ｐＨ７とした。ナスフラスコに移し、ロータリーエバポレーターを用いて、ゲル状となるまで水分を蒸発させた。得られたゲル状物質を、るつぼに移してホットスターラー上にて１００℃で乾燥し、固化したことを確認したうえで、マッフル炉にて焼成処理を行った。室温から３０分で１１０℃まで昇温し、４時間更に乾燥させたうえで、７００℃まで３時間かけて昇温し、５時間焼成してから１時間かけて室温まで冷却し、１．８２０３ｇの黒色粉末を得た。得られた触媒を、実施例１とする。実施例１のＸ線回折測定を行うと、少量の不純物ピークを含むものの、ほぼペロブスカイト型構造の単相となっていた。なお、実施例１の触媒は、モル比で、Ｌａ：Ｓｒ：Ｃｒ：Ｍｎ＝０．７５：０．２５：０．５：０．５を含んでいる。
(Example 1: LaSrCrMn catalyst)
A LaSrCrMn-based catalyst was prepared by the citric acid method.
Lanthanum nitrate hexahydrate (Kanto Chemical, purity> 99.0%) 2.8298 g, Strontium nitrate (Kanto Chemical, purity> 98.0%) 0.4618 g, Chromium nitrate nonahydrate (Kanto Chemical, Purity 98.0-103.0%) 1.7436 g and manganese nitrate hexahydrate (Kanto Chemical, purity> 98.0%) were weighed 1.2501 g and added to 50 ml of pure water. To the obtained solution, 66961 g of citric acid monohydrate (Kanto Kagaku, purity> 99.5%) was added, and stirred until there was no undissolved residue visually. The molar ratio of citric acid to all metal ions is 2: 1 in molar ratio. Ammonia water (Kanto Chemical, purity 28.0 to 30.0%) was added dropwise to adjust the pH to 7. It moved to the eggplant flask, and the water | moisture content was evaporated until it became gel form using the rotary evaporator. The obtained gel-like substance was transferred to a crucible, dried on a hot stirrer at 100 ° C. and confirmed to be solidified, and then baked in a muffle furnace. The temperature was raised from room temperature to 110 ° C. in 30 minutes, further dried for 4 hours, heated to 700 ° C. over 3 hours, baked for 5 hours, cooled to room temperature over 1 hour, 1.8203 g Of black powder was obtained. The obtained catalyst is referred to as Example 1. When the X-ray diffraction measurement of Example 1 was performed, it was a single phase having a perovskite structure, although it contained a small amount of impurity peaks. In addition, the catalyst of Example 1 contains La: Sr: Cr: Mn = 0.75: 0.25: 0.5: 0.5 by molar ratio.
（実施例２：ＬａＳｒＣｒＦｅ系触媒）
ＬａＳｒＣｒＦｅ系の触媒を、クエン酸法にて作成した。
硝酸ランタン６水和物（関東化学、純度＞９９．０％）を２．８７４６ｇ、硝酸ストロンチウム（関東化学、純度＞９８．０％）を０．４６８１ｇ、硝酸クロム９水和物（関東化学、純度 ９８．０〜１０３．０％）を１．７７０７ｇ、硝酸鉄９水和物（関東化学、純度＞９９．０％）を１．７８７４ｇ量り取り、５０ｍｌの純水に加えた。得られた溶液に、クエン酸１水和物（関東化学、純度＞９９．５％）を６．８００４ｇ加え、目視で解け残りがなくなるまで攪拌した。クエン酸と全金属イオンの量比は、モル比で２：１である。その後、アンモニア水を用いたｐＨ調製、乾燥と焼成について、実施例１と同様に実施した。冷却後、２．０１０６ｇの黒色粉末を得た。得られた触媒を実施例２とする。実施例２のＸ線回折測定を行うと、少量の不純物ピークを含むものの、ほぼペロブスカイト型構造の単相となっていた。なお、実施例２の触媒は、モル比で、Ｌａ：Ｓｒ：Ｃｒ：Ｆｅ＝０．７５：０．２５：０．５：０．５を含んでいる。
(Example 2: LaSrCrFe-based catalyst)
A LaSrCrFe-based catalyst was prepared by the citric acid method.
2.8746 g of lanthanum nitrate hexahydrate (Kanto Chemical, purity> 99.0%), 0.4681 g of strontium nitrate (Kanto Chemical, purity> 98.0%), chromium nitrate nonahydrate (Kanto Chemical, 1.7707 g of 99.0 to 103.0% purity) and 1.7874 g of iron nitrate nonahydrate (Kanto Chemical, purity> 99.0%) were weighed and added to 50 ml of pure water. To the resulting solution, 6.8004 g of citric acid monohydrate (Kanto Chemical, purity> 99.5%) was added and stirred until there was no undissolved residue visually. The molar ratio of citric acid to all metal ions is 2: 1 in molar ratio. Thereafter, pH adjustment using ammonia water, drying and firing were carried out in the same manner as in Example 1. After cooling, 2.0106 g of black powder was obtained. The obtained catalyst is referred to as Example 2. When the X-ray diffraction measurement of Example 2 was performed, although it contained a small amount of impurity peaks, it was almost a single phase of a perovskite structure. In addition, the catalyst of Example 2 contains La: Sr: Cr: Fe = 0.75: 0.25: 0.5: 0.5 by molar ratio.
［メタン改質反応試験］
（試験例１）
比較例１の触媒を０．１０ｇ秤取り、石英ガラス製の反応管に充填した。前処理として、水素ガス５０ｃｍ３／分を流通させながら、８００℃まで３０分で昇温し、３０分間還元処理を行った。その後、以下の表１に示す反応ガスを流通させて、反応を開始した。
[Methane reforming reaction test]
(Test Example 1)
0.10 g of the catalyst of Comparative Example 1 was weighed and filled in a reaction tube made of quartz glass. As pretreatment, the temperature was raised to 800 ° C. in 30 minutes while flowing hydrogen gas at 50 cm 3 / min, and reduction treatment was performed for 30 minutes. Thereafter, the reaction gas shown in Table 1 below was circulated to start the reaction.
ここで、特に断りがある場合を除き、流量は、標準状態における流量であり、濃度は、理想気体近似での体積比率（すなわちモル比）である。ただし硫化水素濃度は、反応開始後１時間までを０ｐｐｍ、反応開始１時間後から２時間までを５００ｐｐｍ、反応開始２時間後から３時間までを１０００ｐｐｍ、反応開始３時間後から４時間までを２０００ｐｐｍとし、段階的に硫化水素濃度を上昇させた。各硫化水素濃度における反応の後半３０分のメタン転化率を用いて、活性を評価した。 Here, unless otherwise specified, the flow rate is a flow rate in a standard state, and the concentration is a volume ratio (that is, a molar ratio) in an ideal gas approximation. However, the hydrogen sulfide concentration was 0 ppm for 1 hour after the start of the reaction, 500 ppm for 1 hour to 2 hours after the start of the reaction, 1000 ppm for 2 hours to 3 hours after the start of the reaction, and 2000 ppm for 3 hours to 4 hours after the start of the reaction. The hydrogen sulfide concentration was increased step by step. Activity was evaluated using the methane conversion in the second half of the reaction at each hydrogen sulfide concentration.
反応ガスの分析には、ガスクロマトグラフ（島津製作所、ＧＣ−２０１４）を用い、１５分おきに分析を行った。また、メタン転化率の計算には、以下の式１を用い、各硫化水素濃度でのメタン転化率を、以下の表２にまとめて示した。以下、全ての試料で、炭素数２、炭素数３以上の有機物の生成量は非常に少なかった。また、反応後試料の熱重量分析を行ったが、いずれの試料でも析出炭素の酸化燃焼による重量減少は観測されず、炭素析出量は非常に少ないと考えられ、式１を用いてメタン転化率を評価することは妥当と考えられる。 The reaction gas was analyzed using a gas chromatograph (Shimadzu Corporation, GC-2014) every 15 minutes. Moreover, the following formula 1 was used for calculation of the methane conversion rate, and the methane conversion rate at each hydrogen sulfide concentration is shown in Table 2 below. Hereinafter, in all samples, the amount of organic substances having 2 carbon atoms and 3 or more carbon atoms was very small. In addition, the thermogravimetric analysis of the sample after the reaction was carried out, but no weight loss due to oxidative combustion of the precipitated carbon was observed in any sample, and the amount of precipitated carbon is considered to be very small. It is considered reasonable to evaluate
（メタン転化率）＝（一酸化炭素濃度＋二酸化炭素濃度）／（一酸化炭素濃度＋二酸化炭素濃度＋メタン濃度）×１００（％） ・・・（式１）
ただし、上記（式１）において、いずれのガス濃度も、反応後ガスの濃度を示す。
(Methane conversion rate) = (carbon monoxide concentration + carbon dioxide concentration) / (carbon monoxide concentration + carbon dioxide concentration + methane concentration) × 100 (%) (Equation 1)
However, in the above (Formula 1), any gas concentration indicates the concentration of the post-reaction gas.
（試験例２）
比較例２、３、実施例１、２をそれぞれ０．１０ｇ秤取り、石英ガラス製の反応管に充填した。還元処理を行わず、窒素フロー下で８００℃まで３０分かけて昇温して反応を開始したことを除いては、試験例１と同様に反応試験を行った。また、メタン転化率の計算についても、上記試験例１と同様に実施し、各触媒について、反応試験結果を以下の表２にまとめて示した。
(Test Example 2)
0.10 g of each of Comparative Examples 2 and 3 and Examples 1 and 2 was weighed and filled in a reaction tube made of quartz glass. A reaction test was conducted in the same manner as in Test Example 1 except that the reaction was started by raising the temperature to 800 ° C. over 30 minutes under a nitrogen flow without performing a reduction treatment. The calculation of the methane conversion rate was also carried out in the same manner as in Test Example 1, and the reaction test results for each catalyst were summarized in Table 2 below.
以下、全ての試料で、炭素数２、炭素数３以上の有機物の生成量は非常に少なかった。また、反応後試料の熱重量分析を行ったが、いずれの試料でも析出炭素の酸化燃焼による重量減少は観測されず、炭素析出量は非常に少ないと考えられ、上記式１を用いてメタン転化率を評価することは妥当と考えられる。 Hereinafter, in all samples, the amount of organic substances having 2 carbon atoms and 3 or more carbon atoms was very small. In addition, thermogravimetric analysis of the samples after the reaction was carried out, but no weight loss due to oxidative combustion of the precipitated carbon was observed in any sample, and it is considered that the amount of deposited carbon is very small. It is considered reasonable to evaluate the rate.
上記表２に示す通り、実施例１と実施例２の触媒は、比較例１、２の触媒と比べて高いメタン転化率を示しており、特に、硫化水素濃度が高い条件にて、その差は顕著であった。比較例２、３と実施例１、２の触媒は、いずれも固体電解質型燃料電池の電極触媒として活性があることが知られているが、比較例２の触媒では、全くメタン改質活性が得られていないことから、固体電解質型燃料電池の電極触媒は、水蒸気メタン改質活性を必ずしも発揮しないと言え、更には、硫化水素が含まれていないガス中よりも、高濃度の硫化水素存在下で高い活性が発揮されるとも限らないと言える。 As shown in Table 2 above, the catalysts of Example 1 and Example 2 showed a higher methane conversion rate than the catalysts of Comparative Examples 1 and 2, and the difference was particularly high under conditions of high hydrogen sulfide concentration. Was remarkable. Although the catalysts of Comparative Examples 2 and 3 and Examples 1 and 2 are all known to be active as electrode catalysts for solid oxide fuel cells, the catalyst of Comparative Example 2 has no methane reforming activity. Therefore, it can be said that the electrode catalyst of the solid oxide fuel cell does not necessarily exhibit the steam methane reforming activity, and moreover, the presence of hydrogen sulfide at a higher concentration than in the gas not containing hydrogen sulfide. It can be said that high activity is not necessarily demonstrated below.
［タール改質反応試験］
（試験例３：実施例）
実施例１を圧縮成型し、篩を用いて、粒子径を１．０ｍｍ〜２．０ｍｍとした。メスシリンダーを用いて、各触媒を３．２ｃｍ３秤取り、反応管に充填した。窒素ガス５０ｃｍ３／分を流通させながら、８００℃まで３０分で昇温し、その後、以下の表３に示す反応ガスと、スチーム／カーボン比（Ｓ／Ｃ）＝０．８、１．２、１．６とする量の水蒸気と、を導入し、それぞれ反応を開始した。反応ガス流量は、全体で８０ｃｍ３とし、反応時間は６時間とした。空間速度（ＳＶ）は、１５００時間−１である。
[Tar reforming reaction test]
(Test Example 3: Example)
Example 1 was compression-molded and the particle diameter was adjusted to 1.0 mm to 2.0 mm using a sieve. Using a graduated cylinder, 3.2 cm 3 of each catalyst was weighed and filled into a reaction tube. While circulating nitrogen gas at 50 cm 3 / min, the temperature was raised to 800 ° C. in 30 minutes, and then the reaction gas shown in Table 3 below and the steam / carbon ratio (S / C) = 0.8, 1.2 1.6 and 1.6 were introduced to initiate the reaction. The reaction gas flow rate was 80 cm 3 as a whole, and the reaction time was 6 hours. The space velocity (SV) is 1500 hours- 1 .
反応ガスの分析には、ガスクロマトグラフ（島津製作所、ＧＣ−２０１４）を用い、１５分おきに分析を行った。分析したガス成分は、水素、窒素、メタン、一酸化炭素、二酸化炭素、エチレン、エタン、プロピレン、プロパンである。反応前後で、窒素流量が変化しないと仮定して、窒素濃度との相対濃度を用いて反応後ガスの各成分流量を計算した。 The reaction gas was analyzed using a gas chromatograph (Shimadzu Corporation, GC-2014) every 15 minutes. The analyzed gas components are hydrogen, nitrogen, methane, carbon monoxide, carbon dioxide, ethylene, ethane, propylene, and propane. Assuming that the nitrogen flow rate does not change before and after the reaction, the flow rate of each component of the post-reaction gas was calculated using the relative concentration with the nitrogen concentration.
本試験例では、以下の（式２）に示す水素増幅率と、（式３）に示すガス化収率と、を用いて、反応活性を評価した。水素増幅率は、反応前後で水素のモル量が何倍となったかを示す値であり、水素製造効率を示す値である。一方、ガス化収率は、１−メチルナフタレンに含まれる炭素のうち、ガスに変換された割合を示す値であり、値が大きいほど、優れた改質触媒といえる。各値について、反応開始から２〜３時間の平均値と、５〜６時間の平均値をそれぞれ計算し、反応の安定性を評価した。 In this test example, the reaction activity was evaluated using the hydrogen amplification factor shown in the following (Formula 2) and the gasification yield shown in the (Formula 3). The hydrogen amplification factor is a value indicating how many times the molar amount of hydrogen has increased before and after the reaction, and is a value indicating the efficiency of hydrogen production. On the other hand, the gasification yield is a value indicating the ratio of carbon contained in 1-methylnaphthalene converted to gas, and the larger the value, the better the reforming catalyst. About each value, the average value of 2-3 hours from the start of reaction and the average value of 5-6 hours were calculated, respectively, and the stability of reaction was evaluated.
また、反応試験後に、乾燥空気フロー下で各触媒の熱重量分析を行い、質量減少量を炭素析出量とした。得られた結果を、以下の表４にまとめて示した。 Further, after the reaction test, thermogravimetric analysis of each catalyst was performed under a dry air flow, and the amount of mass reduction was defined as the amount of carbon deposition. The results obtained are summarized in Table 4 below.
（水素増幅率）＝水素流量（反応後）／水素流量（反応前） ・・・（式２） (Hydrogen amplification factor) = hydrogen flow rate (after reaction) / hydrogen flow rate (before reaction) (Equation 2)
（ガス化収率）＝１００×（メタン流量（反応後）＋一酸化炭素流量（反応後）＋二酸化炭素流量（反応後）＋エチレン流量（反応後）×２＋エタン流量（反応後）×２＋プロピレン流量（反応後）×３＋プロパン流量（反応後）×３）／（１−メチルナフタレン流量（反応前）×１１） ・・・（式３） (Gasification yield) = 100 × (methane flow rate (after reaction) + carbon monoxide flow rate (after reaction) + carbon dioxide flow rate (after reaction) + ethylene flow rate (after reaction) × 2 + ethane flow rate (after reaction) × 2 + Propylene flow rate (after reaction) × 3 + propane flow rate (after reaction) × 3) / (1-methylnaphthalene flow rate (before reaction) × 11) (Equation 3)
上記表４から明らかなように、いずれの条件においても、水蒸気改質反応が進行し、水素が増加したことが確認された。また、Ｓ／Ｃが高いものほど水蒸気改質反応がより効率よく進行し、特に、Ｓ／Ｃ＝１．６において高い水素増幅率とガス化収率が得られた。 As apparent from Table 4 above, it was confirmed that the steam reforming reaction proceeded and hydrogen increased under any condition. In addition, the higher the S / C, the more efficiently the steam reforming reaction proceeded. In particular, a high hydrogen amplification rate and gasification yield were obtained at S / C = 1.6.
なお、反応前後の触媒それぞれについて、Ｘ線回折法により結晶構造の分析を行った。その結果、各触媒は、反応前後の双方でペロブスカイト構造を保持しており、反応中に触媒の構造変化は生じていないことが確認された。 In addition, about each catalyst before and behind reaction, the crystal structure was analyzed by the X ray diffraction method. As a result, each catalyst retained a perovskite structure both before and after the reaction, and it was confirmed that no structural change of the catalyst occurred during the reaction.
以上、本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。
As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to this example. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Claims (5)
The method for producing hydrogen according to claim 4, wherein the concentration of hydrogen sulfide contained in the gas is 500 ppm or more and 2000 ppm or less.
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