JP4918646B2 - Catalyst for hydrogen production from methanol comprising Ni3 (Si, Ti) intermetallic compound, hydrogen production method, hydrogen production apparatus - Google Patents
Catalyst for hydrogen production from methanol comprising Ni3 (Si, Ti) intermetallic compound, hydrogen production method, hydrogen production apparatus Download PDFInfo
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- JP4918646B2 JP4918646B2 JP2007192525A JP2007192525A JP4918646B2 JP 4918646 B2 JP4918646 B2 JP 4918646B2 JP 2007192525 A JP2007192525 A JP 2007192525A JP 2007192525 A JP2007192525 A JP 2007192525A JP 4918646 B2 JP4918646 B2 JP 4918646B2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 174
- 239000001257 hydrogen Substances 0.000 title claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 58
- 239000003054 catalyst Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 229910000765 intermetallic Inorganic materials 0.000 title claims description 17
- 239000011888 foil Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000005096 rolling process Methods 0.000 description 26
- 238000000137 annealing Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005097 cold rolling Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000265 homogenisation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000012795 verification Methods 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Description
本発明は，Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物からなるメタノールからの水素製造用触媒、及びこの触媒を用いた水素製造方法及び装置に関する。 The present invention relates to a catalyst for producing hydrogen from methanol comprising a Ni 3 (Si, Ti) intermetallic compound, and a hydrogen production method and apparatus using this catalyst.
水素は、燃料電池の燃料として注目されている。このような燃料としての水素の製造方法としては、これまでに様々なものが知られている。その一例は、触媒を用いて以下の式のようにメタノールを水素と一酸化炭素に分解する方法である。
ＣＨ3ＯＨ→２Ｈ2＋ＣＯ
Hydrogen has attracted attention as a fuel for fuel cells. Various methods for producing hydrogen as such a fuel have been known so far. One example is a method of decomposing methanol into hydrogen and carbon monoxide using a catalyst as shown in the following formula.
CH 3 OH → 2H 2 + CO
水素を分解する触媒としては様々の種類のものが知られているが、近年、金属間化合物であるＮｉ3Ａｌがメタノール分解反応に対して高い触媒活性を示すことが示され、この知見に基づき、Ｎｉ3Ａｌ箔からなる水素製造用触媒が提案された（例えば、特許文献１を参照。）。
特許文献１に記載のＮｉ3Ａｌ箔からなる水素製造用触媒は、高い触媒性能を示しているが、特許文献１では、Ｎｉ3Ａｌ箔は、Ｎｉ3Ａｌの単結晶塊を作製し、それを圧延するという、比較的製造コストが高い方法で作製されている。 The hydrogen production catalyst comprising Ni 3 Al foil described in Patent Document 1 shows high catalytic performance, but in Patent Document 1, Ni 3 Al foil produces a single crystal lump of Ni 3 Al, and Is produced by a method with a relatively high manufacturing cost.
本発明はこのような事情に鑑みてなされたものであり，高い触媒性能を示し且つ箔の製造が安価な、メタノールからの水素製造用触媒を提供するものである。 The present invention has been made in view of such circumstances, and provides a catalyst for producing hydrogen from methanol that exhibits high catalyst performance and is inexpensive to produce foil.
本発明によれば，Ｓｉ：７．５〜１２．５原子％，Ｔｉ：９．０〜１１．５原子％，残部はＮｉからなる組成の合計重量に対してＢ：２５〜５００重量ｐｐｍを含むＮｉ3（Ｓｉ，Ｔｉ）系金属間化合物からなることを特徴とするメタノールからの水素製造用触媒が提供される。 According to the present invention, Si is 7.5 to 12.5 atomic%, Ti is 9.0 to 11.5 atomic%, and the balance is B: 25 to 500 ppm by weight with respect to the total weight of the composition made of Ni. There is provided a catalyst for producing hydrogen from methanol, comprising a Ni 3 (Si, Ti) -based intermetallic compound.
本発明者らは，鋭意研究を行った結果，上記組成のＮｉ3（Ｓｉ，Ｔｉ）系金属間化合物は、メタノール分解反応に対して高い触媒性能を示し、Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物からなる水素製造用触媒を使えば高効率でメタノールを分解して水素を製造できることを見出した。 As a result of intensive studies, the inventors of the present invention have shown that the Ni 3 (Si, Ti) -based intermetallic compound having the above composition exhibits high catalytic performance for methanol decomposition reaction, and Ni 3 (Si, Ti) -based metal It has been found that hydrogen can be produced by efficiently decomposing methanol by using a hydrogen production catalyst comprising an intermetallic compound.
また、Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物は、好ましくは箔状にして使用されるが、Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物箔は、多結晶である鋳塊を圧延することによって容易に製造することができるので、単結晶塊を製造する必要がなく、安価に製造することができる。 The Ni 3 (Si, Ti) intermetallic compound is preferably used in the form of a foil, but the Ni 3 (Si, Ti) intermetallic compound foil is a rolled ingot that is polycrystalline. Therefore, it is not necessary to produce a single crystal lump, and it can be produced at low cost.
また、本発明は、上記水素製造用触媒を４００〜７００℃の温度に加熱し、加熱された触媒に対してガス状のメタノールを接触させることによって前記メタノールを分解して水素を生成する工程を備える水素製造方法も提供する。この方法によれば、高効率でメタノールを分解して水素を製造できる。 The present invention further includes a step of heating the hydrogen production catalyst to a temperature of 400 to 700 ° C. and bringing the gaseous catalyst into contact with the heated catalyst to decompose the methanol to generate hydrogen. A hydrogen production method is also provided. According to this method, hydrogen can be produced by efficiently decomposing methanol.
また、本発明は、上記水素製造用触媒と、前記触媒を加熱する加熱部と、前記触媒に対してガス状のメタノールを供給するメタノール供給部とを備える水素製造装置も提供する。この装置を用いれば、上記の水素製造方法を容易に実施することができる。
なお，本明細書において，「〜」は，端の点を含む。
The present invention also provides a hydrogen production apparatus comprising the hydrogen production catalyst, a heating unit for heating the catalyst, and a methanol supply unit for supplying gaseous methanol to the catalyst. If this apparatus is used, said hydrogen production method can be implemented easily.
In the present specification, “to” includes end points.
１．メタノールからの水素製造用触媒
本発明の一実施形態のメタノールからの水素製造用触媒は、Ｓｉ：７．５〜１２．５原子％，Ｔｉ：９．０〜１１．５原子％，残部はＮｉからなる組成の合計重量に対してＢ：２５〜５００重量ｐｐｍを含むＮｉ3（Ｓｉ，Ｔｉ）系金属間化合物からなることを特徴とする。
1. Catalyst for producing hydrogen from methanol The catalyst for producing hydrogen from methanol according to one embodiment of the present invention is composed of Si: 7.5 to 12.5 atomic%, Ti: 9.0 to 11.5 atomic%, and the balance is Ni. B relative to the total weight of the composition consisting of: 25 to 500 Ni 3 including weight ppm (Si, Ti) characterized by comprising the intermetallic compound.
１−１．Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物
以下，Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物に含まれる各元素について詳述する。
1-1. Ni 3 (Si, Ti) intermetallic compound Hereinafter, each element contained in the Ni 3 (Si, Ti) intermetallic compound will be described in detail.
Ｓｉの含有量は，７．５〜１２．５原子％であり，例えば，１０．０〜１２．０原子％である。Ｓｉの具体的な含有量は，例えば，７．５，８．０，８．５，９．０，９．５，１０．０，１０．５，１１．０，１１．５，１２．０又は１２．５原子％である。Ｓｉの含有量の範囲は，ここで例示した数値の何れか２つの間であってもよい。 The content of Si is 7.5 to 12.5 atomic%, for example, 10.0 to 12.0 atomic%. Specific contents of Si are, for example, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0. Or 12.5 atomic%. The range of the Si content may be between any two of the numerical values exemplified here.
Ｔｉの含有量は，９．０〜１１．５原子％であり，例えば，９．０〜１０．０原子％である。Ｔｉの具体的な含有量は，例えば，９．０，９．５，１０．０，１０．５，１１．０又は１１．５原子％である。Ｔｉの含有量の範囲は，ここで例示した数値の何れか２つの間であってもよい。 The Ti content is 9.0 to 11.5 atomic%, for example, 9.0 to 10.0 atomic%. The specific content of Ti is, for example, 9.0, 9.5, 10.0, 10.5, 11.0, or 11.5 atomic%. The range of the Ti content may be between any two of the numerical values exemplified here.
Ｎｉの含有量は，例えば，７８．５〜８１．０原子％であり、例えば，７９〜８０原子％である。Ｎｉの具体的な含有量は，例えば，７８．５，７９．０，７９．５，８０．０，８０．５又は８１．０原子％である。Ｎｉの含有量の範囲は，ここで例示した数値の何れか２つの間であってもよい。 The content of Ni is, for example, 78.5-81.0 atomic%, for example, 79-80 atomic%. The specific content of Ni is, for example, 78.5, 79.0, 79.5, 80.0, 80.5, or 81.0 atomic%. The range of the Ni content may be between any two of the numerical values exemplified here.
上記各元素の含有量は，Ｓｉ，Ｔｉ及びＮｉの含有量の合計が１００原子％になるように適宜調整される。 The content of each element is appropriately adjusted so that the total content of Si, Ti and Ni is 100 atomic%.
Ｂの含有量は，２５〜５００重量ｐｐｍ，例えば，２５〜１００重量ｐｐｍである。Ｂの具体的な含有量は，例えば，２５，４０，５０，６０，７５，１００，１５０，２００，３００，４００又は５００重量ｐｐｍである。Ｂの含有量の範囲は，ここで例示した数値の何れか２つの間であってもよい。 The content of B is 25 to 500 ppm by weight, for example, 25 to 100 ppm by weight. The specific content of B is, for example, 25, 40, 50, 60, 75, 100, 150, 200, 300, 400, or 500 ppm by weight. The range of the B content may be between any two of the numerical values exemplified here.
本実施形態の水素製造用触媒の具体的な組成は，例えば，表１に示す組成（又は表１に示す組成のうちの何れか２つの間の範囲の組成）に上記含有量のＢを添加したものである。 The specific composition of the hydrogen production catalyst of the present embodiment is, for example, adding B having the above content to the composition shown in Table 1 (or a composition in the range between any two of the compositions shown in Table 1). It is a thing.
１−２．Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物箔
Ｎｉ3（Ｓｉ，Ｔｉ）系金属間化合物箔（以下、「Ｎｉ3（Ｓｉ，Ｔｉ）箔」と称する。）は、好ましくは、厚さが２０〜２００μｍの箔である。
1-2. Ni 3 (Si, Ti) -based intermetallic compound foil Ni 3 (Si, Ti) -based intermetallic compound foil (hereinafter referred to as “Ni 3 (Si, Ti) foil”) preferably has a thickness of 20 ~ 200 μm foil.
Ｎｉ3（Ｓｉ，Ｔｉ）箔は、上記実施形態の組成のＮｉ3（Ｓｉ，Ｔｉ）系金属間化合物の鋳塊に対して均質化熱処理を行った後，圧延及び焼鈍を繰り返し行い，その後，冷間圧延を行うことによって製造することができる。 The Ni 3 (Si, Ti) foil is subjected to homogenization heat treatment for the ingot of the Ni 3 (Si, Ti) intermetallic compound having the composition of the above embodiment, and then repeatedly rolled and annealed, It can manufacture by performing cold rolling.
以下，各工程について詳細に説明する。 Hereinafter, each process will be described in detail.
１−２−１．鋳塊作製工程
まず，上記実施形態で示した組成の鋳塊からなる試料を作製する。一例では、Ｎｉ，Ｓｉ，Ｔｉの地金とＢを秤量したものをアーク溶解炉で溶解，鋳造した鋳塊からなる試料を作製することができる。
1-2-1. Ingot making process First, a sample made of an ingot having the composition shown in the above embodiment is made. In one example, a sample made of an ingot obtained by melting and casting a Ni, Si, Ti ingot and B measured in an arc melting furnace can be produced.
１−２−２．均質化熱処理
次に，得られた試料に対して均質化熱処理を施す。均質化熱処理の条件は，特に限定されない。均質化熱処理は，例えば，真空中９５０〜１１００℃で２４〜４８時間行うことができる。
1-2-2. Homogenization heat treatment Next, the obtained sample is subjected to homogenization heat treatment. The conditions for the homogenization heat treatment are not particularly limited. The homogenization heat treatment can be performed, for example, in vacuum at 950 to 1100 ° C. for 24 to 48 hours.
１−２−３．圧延及び焼鈍の繰り返し工程
次に，均質化熱処理の試料に対して圧延及び焼鈍を繰り返し行って試料を薄板に加工する。圧延後の焼鈍によって試料を再結晶化させて圧延による加工硬化を除去するとともに結晶粒を細粒化する工程を繰り返すことによって，比較的容易に薄板に加工することができる。
1-2-3. Rolling and Annealing Repeat Step Next, the sample is processed into a thin plate by repeatedly rolling and annealing the sample for homogenization heat treatment. By recrystallizing the sample by annealing after rolling to remove work hardening by rolling and refining the crystal grains, it can be processed into a thin plate relatively easily.
圧延は，例えば，３５０℃以下，好ましくは２５０〜３５０℃の温度で行うことができる。圧延は，１パスでの圧延率が０．５〜１．５％になるように行うことが好ましく，１０〜２０パスで行うことが好ましい。圧延は，圧延率が１０％以上，好ましくは１０〜５０％，さらに好ましくは１５〜３０％になるように行うことが好ましい。なお，本明細書において，「１パスでの」と明示しない場合は，「圧延率」とは，複数パスでの圧延による厚さの総減少量の割合を意味する。 Rolling can be performed at a temperature of 350 ° C. or less, preferably 250 to 350 ° C., for example. Rolling is preferably performed so that the rolling rate in one pass is 0.5 to 1.5%, and is preferably performed in 10 to 20 passes. The rolling is preferably performed so that the rolling rate is 10% or more, preferably 10 to 50%, more preferably 15 to 30%. In the present specification, unless it is clearly indicated as “in one pass”, the “rolling rate” means the ratio of the total thickness reduction due to rolling in a plurality of passes.
焼鈍の条件は，試料を再結晶化させることができるものであればよい。焼鈍の温度は，例えば，９００〜１１００℃にすることができる。焼鈍の時間は，例えば０．５〜５時間にすることができる。 Any annealing condition may be used as long as the sample can be recrystallized. The annealing temperature can be set to 900 to 1100 ° C., for example. The annealing time can be 0.5 to 5 hours, for example.
圧延及び焼鈍は，所望の厚さ（例えば２ｍｍ以下）の薄板が得られるまで繰り返す。具体的には，圧延及び焼鈍は，３回以上，好ましくは４回以上繰り返す。 Rolling and annealing are repeated until a thin plate having a desired thickness (for example, 2 mm or less) is obtained. Specifically, rolling and annealing are repeated 3 times or more, preferably 4 times or more.
１−２−４．冷間圧延工程
次に，得られた試料に対して圧延率９０％以上で冷間圧延を行う。この冷間圧延によって金属間化合物圧延箔が得られる。圧延及び焼鈍の繰り返し工程と冷間圧延工程は，得られる箔の厚さが２００μｍ以下，例えば２０〜２００μｍ以下になるように実施することが好ましい。
1-2-4. Cold rolling step Next, the obtained sample is cold rolled at a rolling rate of 90% or more. By this cold rolling, an intermetallic compound rolled foil is obtained. The repeated rolling and annealing steps and the cold rolling step are preferably performed so that the thickness of the obtained foil is 200 μm or less, for example, 20 to 200 μm or less.
また，一度の冷間圧延によって所望の厚さの箔が得られない場合は，冷間圧延の後に焼鈍を行ってその後再度冷間圧延を行うことによって箔の厚さをさらに薄くすることができる。この際の焼鈍の温度は，例えば８００〜１０００℃にすることができる。焼鈍の時間は，例えば０．５〜２時間にすることができる。 In addition, if a foil with a desired thickness cannot be obtained by a single cold rolling, the thickness of the foil can be further reduced by performing annealing after cold rolling and then performing cold rolling again. . The annealing temperature at this time can be set to 800 to 1000 ° C., for example. The annealing time can be 0.5 to 2 hours, for example.
２．水素製造方法
本発明の水素製造方法は、上記記載の水素製造用触媒を４００〜７００℃の温度に加熱し、加熱された触媒に対してガス状のメタノールを接触させることによって前記メタノールを分解して水素を生成する工程を備える。
2. Hydrogen production method The hydrogen production method of the present invention comprises heating the above-described hydrogen production catalyst to a temperature of 400 to 700 ° C., and contacting the heated catalyst with gaseous methanol to decompose the methanol. A step of generating hydrogen.
水素製造用触媒の温度は、４００〜７００℃であり、例えば、４４０〜６００℃である。この温度は、具体的には、例えば、４００，４１０，４２０，４３０、４４０，４５０，４６０，４７０，４８０，４９０，５００，５１０，５２０，５３０，５４０，５５０，５６０，５７０，５８０，５９０，６００，６１０，６２０，６３０，６４０，６５０，６６０，６７０，６８０，６９０又は７００℃である。この温度は、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The temperature of the catalyst for hydrogen production is 400 to 700 ° C, for example, 440 to 600 ° C. Specifically, this temperature is, for example, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590. , 600, 610, 620, 630, 640, 650, 660, 670, 680, 690 or 700 ° C. This temperature may be within a range between any two of the numerical values exemplified herein.
ガス状のメタノールは、液体状のメタノールを加熱することによって得られる。液体状のメタノールの供給速度ＬＨＳＶ（liquid hourly space velocity、１時間に供給される液体の体積／触媒の幾何学的表面積）は、特に限定されないが、例えば、０．００１〜０．０２ｍ3ｈ-1ｍ-2であり、具体的には、例えば、０．００１，０．００２，０．００３，０．００４，０．００５，０．００６，０．００７，０．００８，０．００９，０．０１０，０．０１１，０．０１２，０．０１３，０．０１４，０．０１５，０．０１６，０．０１７，０．０１８，０．０１９又は０．０２０ｍ3ｈ-1ｍ-2である。メタノールの供給速度ＬＨＳＶは、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Gaseous methanol is obtained by heating liquid methanol. The liquid methanol supply rate LHSV (liquid hourly space velocity, volume of liquid supplied per hour / geometric surface area of the catalyst) is not particularly limited, but is, for example, 0.001 to 0.02 m 3 h −. 1 m −2 , specifically, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.020 m 3 h −1 m −2 It is. The methanol supply rate LHSV may be within a range between any two of the numerical values exemplified here.
また、ガス状のメタノールは、キャリアガスとともに触媒に接触させることが好ましい。キャリアガスの種類は、特に限定されないが、窒素等の不活性ガスが好ましい。 Moreover, it is preferable to make gaseous methanol contact a catalyst with carrier gas. The type of carrier gas is not particularly limited, but an inert gas such as nitrogen is preferable.
水素は、ＣＨ3ＯＨ→２Ｈ2＋ＣＯという反応によってメタノールが分解されることによって得られるので、分解反応によって得られるガスは少なくとも水素と一酸化炭素を含む混合ガスである。混合ガスからの水素の分離方法は、特に限定されないが、一例では、混合ガスに水素透過フィルターを通過させることによって水素を分離することができる。 Since hydrogen is obtained by decomposing methanol by a reaction of CH 3 OH → 2H 2 + CO, the gas obtained by the decomposition reaction is a mixed gas containing at least hydrogen and carbon monoxide. The method for separating hydrogen from the mixed gas is not particularly limited. In one example, hydrogen can be separated by passing the mixed gas through a hydrogen permeation filter.
３．水素製造装置
図１を用いて、本発明の一実施形態の水素製造装置について説明する。図１は、本実施形態の水素製造装置の構成を示す。
本実施形態の水素製造装置は、上記記載の水素製造用触媒１と、触媒１を加熱する加熱部３と、触媒１に対してガス状メタノールを供給するメタノール供給部５とを備える。この装置を用いることによって上記の水素製造方法を容易に実施することができる。
3. Hydrogen production apparatus The hydrogen production apparatus of one Embodiment of this invention is demonstrated using FIG. FIG. 1 shows the configuration of the hydrogen production apparatus of this embodiment.
The hydrogen production apparatus of the present embodiment includes the above-described hydrogen production catalyst 1, a heating unit 3 that heats the catalyst 1, and a methanol supply unit 5 that supplies gaseous methanol to the catalyst 1. By using this apparatus, the above hydrogen production method can be easily carried out.
加熱部３の構成は、特に限定されないが、一例では、加熱部３には、アルミニウムブロック炉を用いることができる。加熱部３は、触媒１を４４０〜７００℃に加熱することができる。
メタノール供給部５は、触媒１に対してガス状のメタノールを供給できるものであればその構成は特に限定されないが、一例では、液体状のメタノールを収容するメタノール収容部７と、メタノール収容部７から液体状のメタノールを送り出すポンプ９と、液体状のメタノールを蒸発させてガス状のメタノールにする蒸発器１１を備える。蒸発器１１には、ガス化されたメタノールを触媒１に向けて搬送するキャリアガスを供給するキャリアガス供給部１３が接続されていてもよい。
さらに、触媒１よりも下流側には水素透過フィルター１５が配置されていてもよい。この場合、メタノールが分解されて生成される混合ガスにこのフィルターを通過させることによって水素を分離することができる。
Although the structure of the heating part 3 is not specifically limited, For example, an aluminum block furnace can be used for the heating part 3. The heating unit 3 can heat the catalyst 1 to 440 to 700 ° C.
The configuration of the methanol supply unit 5 is not particularly limited as long as gaseous methanol can be supplied to the catalyst 1, but in one example, a methanol storage unit 7 that stores liquid methanol and a methanol storage unit 7 are provided. A pump 9 for feeding liquid methanol from the gas generator, and an evaporator 11 for evaporating the liquid methanol into gaseous methanol. The evaporator 11 may be connected to a carrier gas supply unit 13 that supplies a carrier gas that transports the gasified methanol toward the catalyst 1.
Further, a hydrogen permeation filter 15 may be disposed downstream of the catalyst 1. In this case, hydrogen can be separated by passing this filter through a mixed gas produced by decomposition of methanol.
４．効果実証実験
本発明の水素製造用触媒を用いてメタノールを分解して水素を製造することによって本発明の水素製造用触媒が優れた触媒性能を有していることを実証した。
4). Effect Verification Experiment It was demonstrated that the hydrogen production catalyst of the present invention has excellent catalytic performance by decomposing methanol using the hydrogen production catalyst of the present invention to produce hydrogen.
４−１．Ｎｉ3（Ｓｉ，Ｔｉ）箔からなる水素製造用触媒の作製
以下の方法で，Ｎｉ3（Ｓｉ，Ｔｉ）箔からなる水素製造用触媒を作製した。
4-1. In Ni 3 (Si, Ti) Preparation following method of the hydrogen production catalyst consisting of a foil, to prepare a Ni 3 (Si, Ti) made of foil for hydrogen production catalyst.
４−１−１．鋳塊作製工程
まず，表２に示す組成になるようにＮｉ，Ｓｉ，Ｔｉの地金（それぞれ純度９９．９重量％）とＢを秤量したものをアーク溶解炉で溶解，鋳造した厚さ１０ｍｍの鋳塊からなる試料を作製した。アーク溶解炉の雰囲気は，まず，溶解室内を真空排気し，その後不活性ガス（アルゴンガス）に置換した。電極は，非消耗タングステン電極を用い，鋳型には水冷式銅ハースを使用した。
4-1-1. Ingot preparation process First, Ni, Si, Ti ingots (purity 99.9% by weight) and B were weighed and melted in an arc melting furnace to have the composition shown in Table 2 and cast to a thickness of 10 mm. A sample made of an ingot was prepared. The arc melting furnace was first evacuated and then replaced with an inert gas (argon gas). The electrode was a non-consumable tungsten electrode and the mold was a water-cooled copper hearth.
４−１−２．均質化熱処理工程
次に，鋳造偏析を解消し，上記試料を均質化するために，１０５０℃で４８時間保持の真空熱処理（炉冷）を行った。
4-1-2. Homogenization heat treatment step Next, vacuum heat treatment (furnace cooling) was performed at 1050 ° C. for 48 hours in order to eliminate casting segregation and homogenize the sample.
４−１−３．温間圧延及び焼鈍工程
次に，上記工程で得られた試料に対して，温間圧延と焼鈍を５度繰り返すことにより厚さ２ｍｍの薄板を作製した。
4-1-3. Warm rolling and annealing process Next, a thin plate having a thickness of 2 mm was prepared by repeating the warm rolling and annealing for the sample obtained in the above process 5 times.
温間圧延では，試料を大気中で３００℃に加熱し，２段圧延機を用いて，１パスの圧下量を約０．１ｍｍとして，１０〜２０パスの圧延を行った。試料は，１パス毎に加熱した。焼鈍は，真空中で１０００℃，５時間（炉冷）の条件で行った。 In the warm rolling, the sample was heated to 300 ° C. in the atmosphere, and rolling was performed for 10 to 20 passes using a two-high rolling mill with a reduction amount of one pass being about 0.1 mm. The sample was heated every pass. Annealing was performed in a vacuum at 1000 ° C. for 5 hours (furnace cooling).
４−１−４．冷間圧延及び焼鈍工程
次に，上記工程で得られた薄板に対して，室温で冷間圧延を行った。冷間圧延は，途中で焼鈍を行わずに圧延率が９０％となるように行った。冷間圧延は，加工が進むにつれて，大径２段圧延機→小径２段圧延機の順に圧延機を変えて行った。冷間圧延後の試料の厚さは，０．２ｍｍであった。
4-1-4. Cold Rolling and Annealing Step Next, the thin plate obtained in the above step was cold rolled at room temperature. Cold rolling was performed so that the rolling rate would be 90% without annealing. Cold rolling was performed by changing the rolling mill in the order of large diameter two-high rolling mill → small diameter two-high rolling mill as the processing progressed. The thickness of the sample after cold rolling was 0.2 mm.
次に、冷間圧延後の試料に対して焼鈍を行った。焼鈍は、真空中で１０００℃，１時間（炉冷）の条件で行った。 Next, the sample after cold rolling was annealed. The annealing was performed in a vacuum at 1000 ° C. for 1 hour (furnace cooling).
次に、焼鈍後の試料に対して室温で冷間圧延を行い、厚さ４０μｍの箔を得た。この箔をそのまま水素製造用触媒として用いた。冷間圧延は，途中で焼鈍を行わずに圧延率が８０％となるように行った。冷間圧延は，小径２段圧延機を用いて行った。 Next, the sample after annealing was cold-rolled at room temperature to obtain a foil having a thickness of 40 μm. This foil was used as a hydrogen production catalyst. Cold rolling was performed so that the rolling rate would be 80% without annealing. Cold rolling was performed using a small diameter two-high rolling mill.
４−２．メタノール分解実験
次に、作製したＮｉ3（Ｓｉ，Ｔｉ）箔を水素製造用触媒として用いてメタノールを分解させて水素を製造する実験を行った。この実験は、図２に示す固定床流通式触媒反応装置を用いて行った。
4-2. Methanol decomposition experiment Next, an experiment was performed in which hydrogen was produced by decomposing methanol using the produced Ni 3 (Si, Ti) foil as a catalyst for hydrogen production. This experiment was conducted using the fixed bed flow type catalytic reaction apparatus shown in FIG.
４−２−１．温度依存性試験
以下の方法で温度依存性試験を行った。
まず、２枚の６ｍｍ×６３．５ｍｍ×４０μｍのＮｉ3（Ｓｉ，Ｔｉ）箔をそれぞれ図３に示すように渦巻状に変形させ、その後、これらの箔を石英チューブ内に配置して５００℃に加熱し、その状態で水素のみを流量３０ｍｌ／分で１時間流して、Ｎｉ3（Ｓｉ，Ｔｉ）箔の表面の還元処理を行った。
4-2-1. Temperature dependency test A temperature dependency test was performed by the following method.
First, two 6 mm × 63.5 mm × 40 μm Ni 3 (Si, Ti) foils were each deformed into a spiral shape as shown in FIG. 3, and then these foils were placed in a quartz tube and placed at 500 ° C. In this state, hydrogen alone was allowed to flow at a flow rate of 30 ml / min for 1 hour to reduce the surface of the Ni 3 (Si, Ti) foil.
次に、水素の供給を停止させ、Ｎｉ3（Ｓｉ，Ｔｉ）箔の温度を２４０℃に下げ、その後、窒素のみを流量３０ｍｌ／分で３０分流して、反応装置内部の水素を窒素で置換した。 Next, the supply of hydrogen is stopped, the temperature of the Ni 3 (Si, Ti) foil is lowered to 240 ° C., and then only nitrogen is flowed at a flow rate of 30 ml / min for 30 minutes to replace the hydrogen inside the reactor with nitrogen. did.
次に、ポンプの作用によりＬＨＳＶが０．００４１２ｍ3ｈ-1ｍ-2となるように液体状のメタノールをメタノール収容部から蒸発器に供給し、蒸発器で蒸発させてガス化し、ガス状のメタノールを窒素（キャリアガスとして機能する。）と共に石英チューブ内に導入し、ガス状のメタノールとＮｉ3（Ｓｉ，Ｔｉ）箔と接触させ、石英チューブからの排出ガスの成分をガスクロマトグラフで測定し、排出ガスの全流量をソープバブルメーターで測定した。Ｎｉ3（Ｓｉ，Ｔｉ）箔の温度は、３０分ごとに４０℃ずつ上昇させた。 Next, liquid methanol is supplied from the methanol container to the evaporator so that LHSV is 0.00412 m 3 h −1 m −2 by the action of the pump, and is evaporated and gasified by the evaporator. Methanol is introduced into the quartz tube together with nitrogen (which functions as a carrier gas), brought into contact with gaseous methanol and Ni 3 (Si, Ti) foil, and the components of the exhaust gas from the quartz tube are measured with a gas chromatograph. The total flow rate of the exhaust gas was measured with a soap bubble meter. The temperature of the Ni 3 (Si, Ti) foil was increased by 40 ° C. every 30 minutes.
この測定によって得られた結果を図４及び図５に示す。図４は、反応温度（Ｎｉ3（Ｓｉ，Ｔｉ）箔の温度）とメタノール転化率との関係を示すグラフであり、図５は、反応温度と、各種ガスの生成速度との関係を示すグラフである。 The results obtained by this measurement are shown in FIGS. FIG. 4 is a graph showing the relationship between the reaction temperature (temperature of the Ni 3 (Si, Ti) foil) and the methanol conversion rate, and FIG. 5 is a graph showing the relationship between the reaction temperature and the production rates of various gases. It is.
図４を参照すると、４８０℃以上ではメタノールの分解が起こり、温度が上がるにつれて転化率が高くなったことが分かる。また、図５を参照すると、全ての温度域でＨ2Ｏ，ＣＨ4，ＣＯ2は、ほとんど生成されず、４８０℃以上の温度では、Ｈ2とＣＯがほぼ２：１で生成したことが分かる。このことは、ＣＨ3ＯＨ→２Ｈ2＋ＣＯという反応によってメタノールが分解される割合が極めて高かったことを示している。 Referring to FIG. 4, it can be seen that the decomposition of methanol occurred at 480 ° C. or higher, and the conversion rate increased as the temperature increased. Referring to FIG. 5, almost no H 2 O, CH 4 , or CO 2 is generated in all temperature ranges, and H 2 and CO are generated at a ratio of about 2: 1 at a temperature of 480 ° C. or higher. I understand. This indicates that the rate at which methanol is decomposed by the reaction of CH 3 OH → 2H 2 + CO is extremely high.
４−２−２．時間依存性試験
以下の方法で時間依存性試験を行った。
まず、２枚の６ｍｍ×３１．８ｍｍ×４０μｍのＮｉ3（Ｓｉ，Ｔｉ）箔をそれぞれ図３に示すように渦巻状に変形させ、その後、これらの箔を石英チューブ内に配置して５００℃に加熱し、その状態で水素のみを流量３０ｍｌ／分で１時間流して、Ｎｉ3（Ｓｉ，Ｔｉ）箔の表面の還元処理を行った。
4-2-2. Time dependency test A time dependency test was performed by the following method.
First, two 6 mm × 31.8 mm × 40 μm Ni 3 (Si, Ti) foils were each deformed into a spiral shape as shown in FIG. 3, and then these foils were placed in a quartz tube and placed at 500 ° C. In this state, hydrogen alone was allowed to flow at a flow rate of 30 ml / min for 1 hour to reduce the surface of the Ni 3 (Si, Ti) foil.
次に、水素の供給を停止させ、Ｎｉ3（Ｓｉ，Ｔｉ）箔の温度を４４０℃、４８０℃、５２０℃の何れかに設定した。同時に、窒素のみを流量３０ｍｌ／分で流して、実験装置内部の水素を窒素で置換した。 Next, the supply of hydrogen was stopped, and the temperature of the Ni 3 (Si, Ti) foil was set to either 440 ° C., 480 ° C., or 520 ° C. At the same time, only nitrogen was flowed at a flow rate of 30 ml / min to replace the hydrogen inside the experimental apparatus with nitrogen.
次に、ポンプの作用によりＬＨＳＶが０．００４１２ｍ3ｈ-1ｍ-2となるように液体メタノールをメタノール収容部から蒸発器に供給し、蒸発器で蒸発させてガス化し、ガス状のメタノールを窒素と共に石英チューブ内に導入し、ガス状のメタノールとＮｉ3（Ｓｉ，Ｔｉ）箔と接触させ、石英チューブからの排出ガスの成分をガスクロマトグラフで測定し、排出ガスの全流量をソープバブルメーターで測定した。Ｎｉ3（Ｓｉ，Ｔｉ）箔の温度は、上記の設定温度で一定に保った。 Next, liquid methanol is supplied from the methanol container to the evaporator so that the LHSV is 0.00412 m 3 h −1 m −2 by the action of the pump, and vaporized by the evaporator to be gasified. It is introduced into the quartz tube together with nitrogen, brought into contact with gaseous methanol and Ni 3 (Si, Ti) foil, the components of the exhaust gas from the quartz tube are measured with a gas chromatograph, and the total flow rate of the exhaust gas is measured with a soap bubble meter. Measured with The temperature of the Ni 3 (Si, Ti) foil was kept constant at the above set temperature.
この測定によって得られた結果を図６及び図７（ａ）〜（ｃ）に示す。図６は、反応温度が４４０℃、４８０℃、５２０℃のそれぞれの場合についての反応時間とメタノール転化率との関係を示すグラフであり、図７（ａ）〜（ｃ）は、それぞれ、反応温度が４４０℃、４８０℃、５２０℃の場合についての、反応時間と各種ガスの生成速度との関係を示すグラフである。 The results obtained by this measurement are shown in FIGS. 6 and 7A to 7C. FIG. 6 is a graph showing the relationship between the reaction time and the methanol conversion for each case where the reaction temperature is 440 ° C., 480 ° C., and 520 ° C., and FIGS. It is a graph which shows the relationship between reaction time and the production rate of various gases about the case where temperature is 440 degreeC, 480 degreeC, and 520 degreeC.
図６を参照すると、何れの温度の場合でも時間が経過するに従ってメタノール転化率が上昇したことが分かる。このことは、Ｎｉ3（Ｓｉ，Ｔｉ）箔からなる触媒の性能が使用中に向上したことを意味している。また、図７（ａ）〜（ｃ）を参照すると、何れの温度の場合でも、長時間経過後もＣＨ4やＣＯ2の生成速度が極めて０に近いままであり、長時間が経過してもＣＨ3ＯＨ→２Ｈ2＋ＣＯという反応によってメタノールが分解される割合が極めて高かったことを示している。 Referring to FIG. 6, it can be seen that the methanol conversion increased as time passed at any temperature. This means that the performance of the catalyst made of Ni 3 (Si, Ti) foil was improved during use. Further, referring to FIGS. 7A to 7C, at any temperature, the generation rate of CH 4 or CO 2 remains very close to 0 even after a long time has passed, and a long time has passed. This also shows that the rate of decomposition of methanol by the reaction of CH 3 OH → 2H 2 + CO was extremely high.
Claims (6)
加熱された触媒に対してガス状のメタノールを接触させることによって前記メタノールを分解して水素を生成する工程を備える水素製造方法。 Heating the catalyst according to any one of claims 1 to 3 to a temperature of 400 to 700 ° C;
A method for producing hydrogen, comprising a step of decomposing the methanol to produce hydrogen by bringing gaseous methanol into contact with the heated catalyst.
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| JP5900894B2 (en) * | 2011-03-14 | 2016-04-06 | 公立大学法人大阪府立大学 | Hydrogen production catalyst containing Ni3Si intermetallic compound, method for activating the catalyst, hydrogen production method and apparatus using the catalyst |
| JP5798425B2 (en) * | 2011-09-26 | 2015-10-21 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2918405A1 (en) * | 1979-05-08 | 1980-11-20 | Metallgesellschaft Ag | METHOD FOR PRODUCING CARBON MONOXIDE AND HYDROGEN FROM METHANOL |
| JPS58125603A (en) * | 1982-01-20 | 1983-07-26 | Toyo Eng Corp | Preparation of gaseous mixture containing hydrogen and carbon monoxide by decomposition of methanol |
| JPS62176545A (en) * | 1986-01-31 | 1987-08-03 | Idemitsu Kosan Co Ltd | Catalyst for reforming methanol |
| JPH03267325A (en) * | 1990-03-16 | 1991-11-28 | Nippon Stainless Steel Co Ltd | Production of ni3 (si, ti) intermetallic compound-based material by melting |
| JP3822022B2 (en) * | 2000-05-17 | 2006-09-13 | 株式会社日本製鋼所 | Hydrocarbon decomposition material and hydrocarbon decomposition apparatus |
| JP4701455B2 (en) * | 2005-09-16 | 2011-06-15 | 独立行政法人物質・材料研究機構 | Catalyst for hydrogen production, method for producing the same, and method for producing hydrogen |
| JP4756974B2 (en) * | 2005-09-26 | 2011-08-24 | 公立大学法人大阪府立大学 | Ni3 (Si, Ti) -based foil and method for producing the same |
| JP4973301B2 (en) * | 2007-04-24 | 2012-07-11 | 公立大学法人大阪府立大学 | Ni3 (Si, Ti) intermetallic compound excellent in oxidation resistance and corrosion resistance, the intermetallic compound rolled foil, and a method for producing the intermetallic compound rolled foil |
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