JP6295170B2 - Method for producing magnesium hydride - Google Patents
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- JP6295170B2 JP6295170B2 JP2014181282A JP2014181282A JP6295170B2 JP 6295170 B2 JP6295170 B2 JP 6295170B2 JP 2014181282 A JP2014181282 A JP 2014181282A JP 2014181282 A JP2014181282 A JP 2014181282A JP 6295170 B2 JP6295170 B2 JP 6295170B2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229910012375 magnesium hydride Inorganic materials 0.000 title claims description 15
- 239000000843 powder Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 4
- 239000005453 ketone based solvent Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 20
- 239000011777 magnesium Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 alicyclic hydrocarbon Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
本発明は、水素貯蔵材料として有用な水素化マグネシウムの製造法に関する。 The present invention relates to a method for producing magnesium hydride useful as a hydrogen storage material.
水素化マグネシウム（MgH2）は大気中で安定に存在し、以下の反応により多量の水素を放出することから、有望な水素貯蔵材料として期待されている。 Magnesium hydride (MgH 2 ) is stably present in the atmosphere and releases a large amount of hydrogen by the following reaction, and thus is expected as a promising hydrogen storage material.
MgH2 → Mg ＋ H2
MgH2 ＋ H2O → Mg(OH)2 ＋ 2H2
MgH 2 → Mg + H 2
MgH 2 + H 2 O → Mg (OH) 2 + 2H 2
また、水素化マグネシウムはマグネシウムを主成分とした高性能な水素吸蔵材料の原料としても用いられている。すなわち、水素化マグネシウムと五酸化ニオブをミリング処理した後に脱水素化を行うこと常温で４wt％もの水素吸蔵を可能にするマグネシウムと酸化ニオブからなる水素吸蔵材料の製造方法が報告されている（特許文献１）。 Magnesium hydride is also used as a raw material for high-performance hydrogen storage materials mainly composed of magnesium. That is, a method for producing a hydrogen storage material composed of magnesium and niobium oxide that enables hydrogen storage of 4 wt% at room temperature by performing dehydrogenation after milling magnesium hydride and niobium pentoxide has been reported (patent) Reference 1).
水素化マグネシウムの製造法としては、金属マグネシウムと五酸化ニオブを水素ガス雰囲気下でメカニカルミリング処理を行うことで水素化マグネシウムを製造する方法が報告されている（特許文献２）。また、金属マグネシウムに耐圧容器中で加圧水素を反応させる方法、加圧水素反応の加圧加熱を２段階で行う方法等が報告されている（非特許文献１、特許文献４〜６）。 As a method for producing magnesium hydride, there has been reported a method for producing magnesium hydride by subjecting metallic magnesium and niobium pentoxide to mechanical milling in a hydrogen gas atmosphere (Patent Document 2). In addition, a method of reacting metal magnesium with pressurized hydrogen in a pressure vessel, a method of performing pressurized heating of the pressurized hydrogen reaction in two stages, and the like have been reported (Non-Patent Document 1, Patent Documents 4 to 6).
しかしながら、特許文献２及び３に記載の方法では、高圧に耐えられる特殊仕様の粉砕容器が必要であるといった問題がある。特に大量に製造する場合には、水素化反応の進行に伴う発熱温度の制御が難しくなり、粉砕装置や粉砕容器（特にシール部分）へかかる負荷が大きくなるという問題がある。また、特許文献４及び５記載の方法では、２段階以上の加熱処理工程が必要であることや５００℃以上の高温が必要である。さらに、特許文献６記載の方法では、高活性の触媒Mg粉末を得るために不安定な有機マグネシウムを経た反応が必要であるという問題があった。 However, the methods described in Patent Documents 2 and 3 have a problem that a specially pulverized container that can withstand high pressure is required. In particular, when manufacturing in large quantities, it becomes difficult to control the heat generation temperature accompanying the progress of the hydrogenation reaction, and there is a problem that the load on the pulverizer and the pulverization container (especially the seal portion) becomes large. Moreover, in the method of patent document 4 and 5, the heat processing process of two steps or more is required, and the high temperature of 500 degreeC or more is required. Furthermore, the method described in Patent Document 6 has a problem that a reaction via unstable organomagnesium is required to obtain highly active catalyst Mg powder.
従って、本発明の課題は、高圧高温の条件を必要とせず、制御不能となるような発熱を伴なうことなく、高純度の水素化マグネシウムを安定して製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for stably producing high-purity magnesium hydride without requiring high-pressure and high-temperature conditions and without generating heat that cannot be controlled. .
そこで本発明者は、水素化反応の条件を緩和な条件であっても反応が進行する手段について検討した結果、金属マグネシウムと触媒量の五酸化ニオブとの混合物を不活性有機溶媒中で粉砕した後に、水素化反応を行えば、水素化反応が５００℃以下の条件で速やかに進行し、制御不能な発熱も生じることなく、高純度の水素化マグネシウムが製造できることを見出し、本発明を完成した。 Thus, as a result of studying means for allowing the reaction to proceed even under mild conditions for the hydrogenation reaction, the present inventors pulverized a mixture of metallic magnesium and a catalytic amount of niobium pentoxide in an inert organic solvent. Later, if a hydrogenation reaction was performed, the hydrogenation reaction proceeded rapidly under conditions of 500 ° C. or less, and it was found that high-purity magnesium hydride could be produced without causing uncontrollable heat generation, thereby completing the present invention. .
すなわち、本発明は、以下の発明〔１〕〜〔６〕を提供するものである。 That is, the present invention provides the following inventions [1] to [6].
〔１〕金属マグネシウム粉末及び触媒量の五酸化ニオブ粉末を不活性有機溶媒中で粉砕する工程と、該粉砕物を水素ガス雰囲気下２００〜４５０℃に加熱する工程とを有することを特徴とする水素化マグネシウムの製造法。
〔２〕五酸化ニオブ粉末の使用量が、金属マグネシウム粉末１モルに対して０．００５〜０．０２モルである〔１〕記載の製造法。
〔３〕金属マグネシウム粉末の平均粒子径が２００〜５００μｍであり、五酸化ニオブ粉末の平均粒子径が１〜１０μｍであり、粉砕物の平均粒子径が１０〜１００μｍである〔１〕又は〔２〕記載の製造法。
〔４〕不活性有機溶媒が、炭化水素系溶媒、エーテル系溶媒、ケトン系溶媒及びアミド系溶媒から選ばれる１種又は２種以上である〔１〕〜〔３〕のいずれか１項記載の製造法。
〔５〕加熱工程が、水素圧１〜１０MPa下、２００〜４５０℃に１０〜２４時間加熱する工程である〔１〕〜〔４〕のいずれか１項記載の製造法。
〔６〕不活性有機溶媒の使用量が、金属マグネシウム粉末１質量部に対して１〜５質量部である〔１〕〜〔５〕のいずれか１項記載の製造法。
[1] It comprises a step of pulverizing metallic magnesium powder and a catalytic amount of niobium pentoxide powder in an inert organic solvent, and a step of heating the pulverized product to 200 to 450 ° C. in a hydrogen gas atmosphere. Manufacturing method of magnesium hydride.
[2] The production method according to [1], wherein the amount of niobium pentoxide powder used is 0.005 to 0.02 mol with respect to 1 mol of metal magnesium powder.
[3] The average particle size of the metal magnesium powder is 200 to 500 μm, the average particle size of the niobium pentoxide powder is 1 to 10 μm, and the average particle size of the pulverized product is 10 to 100 μm [1] or [2 ] The manufacturing method of description.
[4] The method according to any one of [1] to [3], wherein the inert organic solvent is one or more selected from hydrocarbon solvents, ether solvents, ketone solvents, and amide solvents. Manufacturing method.
[5] The production method according to any one of [1] to [4], wherein the heating step is a step of heating at 200 to 450 ° C. for 10 to 24 hours under a hydrogen pressure of 1 to 10 MPa.
[6] The production method according to any one of [1] to [5], wherein the amount of the inert organic solvent used is 1 to 5 parts by mass with respect to 1 part by mass of the metal magnesium powder.
本発明方法によれば、５００℃未満の水素化反応で速やかに水素化が進行し、制御不能な発熱も生じることなく、安全に高純度の水素化マグネシウムを大量に製造することができる。 According to the method of the present invention, hydrogenation proceeds rapidly in a hydrogenation reaction at less than 500 ° C., and a large amount of high-purity magnesium hydride can be produced safely without causing uncontrollable heat generation.
本発明の水素化マグネシウムの製造法は、
（１）金属マグネシウム粉末及び触媒量の五酸化ニオブ粉末を不活性有機溶媒中で粉砕する工程（工程（１））と、
（２）該粉砕物を水素ガス雰囲気下２００〜４５０℃に加熱する工程（工程（２））とを有する。
The method for producing magnesium hydride of the present invention includes
(1) a step of pulverizing metallic magnesium powder and a catalytic amount of niobium pentoxide powder in an inert organic solvent (step (1));
(2) A step of heating the pulverized product to 200 to 450 ° C. in a hydrogen gas atmosphere (step (2)).
工程（１）に用いられる金属マグネシウム粉末の粒子径は通常入手できるものであればよく、例えば平均粒子径２００〜５００μｍの粉末が好ましく、２００〜４００μｍの粉末がより好ましく、２００〜３００μｍの粉末がさらに好ましい。
平均粒子径は、粉末を走査型電子顕微鏡で観察し、その粉末の最大長を粒子径とし、５０個の粉末の最大長を平均したものである。
The particle diameter of the metal magnesium powder used in the step (1) is not particularly limited as long as it is usually available. For example, a powder having an average particle diameter of 200 to 500 μm is preferable, a powder of 200 to 400 μm is more preferable, Further preferred.
The average particle diameter is obtained by observing the powder with a scanning electron microscope, setting the maximum length of the powder as the particle diameter, and averaging the maximum length of 50 powders.
五酸化ニオブ粉末の粒子径は、通常入手できるものであればよく、例えば平均粒子径１〜１０μｍの粉末が好ましく、１〜８μｍの粉末がより好ましく、１〜６μｍの粉末がさらに好ましい。 The particle diameter of the niobium pentoxide powder is not particularly limited as long as it is usually available. For example, a powder having an average particle diameter of 1 to 10 μm is preferable, a powder of 1 to 8 μm is more preferable, and a powder of 1 to 6 μm is more preferable.
五酸化ニオブの使用量は、触媒量であればよいが、具体的には金属マグネシウム粉末１モルに対して０．００５〜０．０２モルが好ましく、０．００５〜０．０１５モルがより好ましく、０．００７〜０．０１２モルがさらに好ましい。 The amount of niobium pentoxide used may be a catalytic amount, but specifically 0.005-0.02 mol is preferable with respect to 1 mol of metal magnesium powder, and 0.005-0.015 mol is more preferable. 0.007 to 0.012 mol is more preferable.
本発明方法においては、金属マグネシウム粉末と五酸化ニオブ粉末の粉砕を、不活性有機溶媒中で行うことが重要である。不活性有機溶媒を使用しないで粉砕を行った場合、粉砕の容器やボールへの金属の付着、金属同士の固着が生じ、粉砕が進行しない。また、次の工程の水素化反応において、水素化反応はほとんど進行しない。
不活性有機溶媒としては、カルボキシル基や水酸基等の官能性基を有しない溶媒であればよく、例えば炭化水素系溶媒、エーテル系溶媒、ケトン系溶媒及びアミド系溶媒から選ばれる１種又は２種以上の溶媒が好ましい。このうち、炭化水素系溶媒が特に好ましい。
In the method of the present invention, it is important to grind the magnesium metal powder and the niobium pentoxide powder in an inert organic solvent. When pulverization is performed without using an inert organic solvent, the metal adheres to the pulverization container or ball and the metals adhere to each other, and the pulverization does not proceed. In the hydrogenation reaction in the next step, the hydrogenation reaction hardly proceeds.
The inert organic solvent may be any solvent that does not have a functional group such as a carboxyl group or a hydroxyl group. For example, one or two types selected from hydrocarbon solvents, ether solvents, ketone solvents, and amide solvents. The above solvents are preferred. Of these, hydrocarbon solvents are particularly preferred.
このうち、炭化水素系溶媒としては、炭素数４〜５０の飽和又は不飽和炭化水素が好ましく、炭素数４〜５０の脂肪族炭化水素、炭素数４〜５０の脂環式炭化水素、炭素数５〜５０の芳香族炭化水素が好ましい。より具体的には、ｎ−ヘキサン、シクロヘキサン、ベンゼン、トルエン、キシレン、オクタン、デカン等が挙げられる。 Among these, the hydrocarbon solvent is preferably a saturated or unsaturated hydrocarbon having 4 to 50 carbon atoms, an aliphatic hydrocarbon having 4 to 50 carbon atoms, an alicyclic hydrocarbon having 4 to 50 carbon atoms, or a carbon number. 5-50 aromatic hydrocarbons are preferred. More specifically, n-hexane, cyclohexane, benzene, toluene, xylene, octane, decane and the like can be mentioned.
エーテル系溶媒としては、ジエチルエーテル、イソプロピルエーテル、ジブチルエーテル等のジアルキルエーテル、テトラヒドロフラン、ジオキサン等の環状エーテル等が挙げられる。 Examples of ether solvents include dialkyl ethers such as diethyl ether, isopropyl ether and dibutyl ether, and cyclic ethers such as tetrahydrofuran and dioxane.
ケトン系溶媒としては、アセトン、メチルエチルケトン、ジイソブチルケトン、シクロヘキサノン等が挙げられる。 Examples of the ketone solvent include acetone, methyl ethyl ketone, diisobutyl ketone, and cyclohexanone.
アミド系溶媒としては、ジメチルホルムアミド、ジメチルアセトアミド等が挙げられる。 Examples of amide solvents include dimethylformamide and dimethylacetamide.
不活性有機溶媒の使用量は、粉砕を効率よく進行させる点、粉砕容器への固着を抑制させる点から、金属マグネシウム粉末１質量部に対して１〜５質量部以上が好ましく、１〜４質量部がより好ましく、１〜３質量部がさらに好ましい。 The amount of the inert organic solvent used is preferably 1 to 5 parts by mass or more and 1 to 4 parts by mass with respect to 1 part by mass of the metal magnesium powder from the viewpoint of efficiently proceeding the pulverization and suppressing the fixation to the pulverization container. Part is more preferable, and 1 to 3 parts by mass is further preferable.
粉砕装置としては、振動型ミリング装置、遊星型ボールミル装置、ローラーミル、内外筒回転型ミル、アトライターミル、インナーピース型ミル等が用いられる。粉砕装置に用いるボールとしては、クローム鋼、ＳＵＳ、ジルコニウム、メノー、タングステンカーバイド等が挙げられる。 As the grinding device, a vibration milling device, a planetary ball mill device, a roller mill, an inner / outer cylinder rotating mill, an attritor mill, an inner piece mill, and the like are used. Examples of the balls used in the pulverizer include chrome steel, SUS, zirconium, meno, tungsten carbide, and the like.
粉砕条件は、特に限定されず、室温条件下、大気圧条件で行うことができる。 The pulverization conditions are not particularly limited, and can be performed under room temperature conditions and atmospheric pressure conditions.
粉砕処理により得られる粉砕物の平均粒子径は、原料金属マグネシウム粉末の粒子径より小さくなっているのが好ましく、例えば１０〜１００μｍであるのが好ましく、２０〜８０μｍであるのがより好ましく、３０〜７０μｍであるのがさらに好ましい。 The average particle size of the pulverized product obtained by the pulverization treatment is preferably smaller than the particle size of the raw metal magnesium powder, for example, preferably 10 to 100 μm, more preferably 20 to 80 μm, 30 More preferably, it is -70 micrometers.
次に、粉砕物を水素ガス雰囲気下２００〜４５０℃に加熱する（工程（２））。工程（２）は、耐圧容器中で行なわれる。
工程（２）の水素圧は、水素化反応をスムーズに進行させる点から、ゲージ圧で１〜１０MPaが好ましく、２〜８MPaがより好ましく、３〜７MPaがさらに好ましい。
Next, the pulverized product is heated to 200 to 450 ° C. in a hydrogen gas atmosphere (step (2)). Step (2) is performed in a pressure vessel.
The hydrogen pressure in the step (2) is preferably 1 to 10 MPa, more preferably 2 to 8 MPa, and further preferably 3 to 7 MPa in terms of gauge pressure from the viewpoint of smoothly proceeding the hydrogenation reaction.
工程（２）の加熱温度は、５００℃未満で十分であり、２００〜４５０℃が好ましく、３００〜４５０℃がより好ましく、３５０〜４５０℃がさらに好ましい。 The heating temperature in the step (2) is sufficient to be less than 500 ° C, preferably 200 to 450 ° C, more preferably 300 to 450 ° C, and further preferably 350 to 450 ° C.
加熱時間は、１０〜２４時間が好ましく、１０〜２０時間がより好ましく、１２〜１８時間がさらに好ましい。 The heating time is preferably 10 to 24 hours, more preferably 10 to 20 hours, and further preferably 12 to 18 hours.
工程（２）により、金属マグネシウムが効率良く水素化され、高純度（９５％以上）の水素化マグネシウムが得られる。なお、得られた水素化マグネシウム中には、触媒量の五酸化ニオブが含まれているが、水素吸着材料として使用するに際しては何ら問題がない。 By the step (2), magnesium metal is efficiently hydrogenated, and high purity (95% or more) magnesium hydride is obtained. The obtained magnesium hydride contains a catalytic amount of niobium pentoxide, but there is no problem when used as a hydrogen adsorbing material.
次に実施例を挙げて本発明を更に詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
実施例１
（１）原料として高純度化学社製マグネシウム粉末（Mg；平均粒子径約２００μｍ、図１参照）、添川理化学社製五酸化ニオブ粉末（Nb2O5；平均粒子径約５μｍ）を用いた。原料を総重量１０．０ｇ、Nb2O5 １mol％となるように秤量し、鋼鉄製のミル容器（２５０cc）内に１００個の鋼鉄製のボール（φ１０mm）とヘキサンを２５mLを封入した。封入後、遊星ボールミル装置Ｐ−５（フリッチュ・ジャパン製）を用い、回転数２５０rpm、１０時間公転させることで、マグネシウム中にサブミクロンサイズ以下の酸化ニオブが分散した、平均粒子径が約５０μｍ以下の混合粉末を作製した（図２参照）。
Example 1
(1) Magnesium powder (Mg; average particle size of about 200 μm, see FIG. 1) and Niobium pentoxide powder (Nb 2 O 5 ; average particle size of about 5 μm) manufactured by Soekawa Rikagaku Co., Ltd. were used as raw materials. The raw materials were weighed to a total weight of 10.0 g and Nb 2 O 5 1 mol%, and 100 steel balls (φ10 mm) and 25 mL of hexane were sealed in a steel mill container (250 cc). After sealing, using a planetary ball mill device P-5 (manufactured by Fritsch Japan) and revolving at 250 rpm for 10 hours, niobium oxide of submicron size or less is dispersed in magnesium, and the average particle size is about 50 μm or less (See FIG. 2).
（２）混合粉末を耐圧容器に封入し、水素圧力（ケージ圧）４MPa、４００℃の温度で１２時間保持することで、水素化処理を行った。水素化処理後に熱伝導度法により試料中の水素濃度を求めることによって水素化率（MgH2／Mg＋MgH2＊１００）を算出したところ、水素化率は９５％に達した。 (2) The mixed powder was sealed in a pressure-resistant vessel, and hydrogenation was performed by maintaining the hydrogen pressure (cage pressure) at 4 MPa and a temperature of 400 ° C. for 12 hours. When the hydrogenation rate (MgH 2 / Mg + MgH 2 * 100) was calculated by obtaining the hydrogen concentration in the sample by the thermal conductivity method after the hydrogenation treatment, the hydrogenation rate reached 95%.
比較例１
実施例１において、ヘキサンを添加せずに粉砕処理を行ったところ、容器及びボールに金属マグネシウムが付着し、また金属マグネシウム同士が固着してしまい粉砕することができなかった。
Comparative Example 1
In Example 1, when pulverization was performed without adding hexane, metal magnesium adhered to the container and the balls, and metal magnesium adhered to each other, and could not be pulverized.
比較例２
原料として高純度化学社製マグネシウム粉末（Mg；平均粒子径約２００μｍ）のみを用いた。粉末を粉砕せずに、耐圧容器に封入し、水素圧力７MPa、４００℃の温度で１２時間保持することで、水素化処理を行った。水素化処理後に熱伝導度法により試料中の水素濃度を求めることによって水素化率（MgH2／Mg＋MgH2＊１００）を算出した。
測定の結果、７ＭＰａの高い圧力条件においても水素化率は８９％であった。
Comparative Example 2
Only magnesium powder (Mg; average particle size of about 200 μm) manufactured by Kojundo Chemical Co., Ltd. was used as a raw material. Without pulverizing the powder, the powder was enclosed in a pressure vessel and kept at a hydrogen pressure of 7 MPa and a temperature of 400 ° C. for 12 hours to perform a hydrogenation treatment. The hydrogenation rate (MgH 2 / Mg + MgH 2 * 100) was calculated by determining the hydrogen concentration in the sample by the thermal conductivity method after the hydrogenation treatment.
As a result of the measurement, the hydrogenation rate was 89% even under a high pressure condition of 7 MPa.
比較例３
（１）原料として高純度化学社製マグネシウム粉末（Mg）のみを用いた。原料を総重量１０．０ｇとなるように秤量し、鋼鉄製のミル容器（２５０cc）内に１００個の鋼鉄製のボール（φ１０mm）とヘキサンを２５mlを封入した。封入後、遊星ボールミル装置Ｐ−５（フリッチュ・ジャパン製）を用い、回転数２５０rpm、１０時間公転させることで平均粒子径が５０μｍ以下の粒子になるよう粉砕処理を行った（図３参照）。
Comparative Example 3
(1) Only magnesium powder (Mg) manufactured by Koyo Chemical Co., Ltd. was used as a raw material. The raw materials were weighed to a total weight of 10.0 g, and 100 steel balls (φ10 mm) and 25 ml of hexane were sealed in a steel mill container (250 cc). After encapsulating, a planetary ball mill device P-5 (manufactured by Fritsch Japan) was used to perform revolving treatment at a rotational speed of 250 rpm for 10 hours to obtain particles having an average particle diameter of 50 μm or less (see FIG. 3).
（２）処理後の粉末を耐圧容器に封入し、水素圧力（ケージ圧）４MPa、４００℃の温度で１２時間保持を行った。水素化処理後に熱伝導度法により試料中の水素濃度を求めることによって水素化率（MgH2／Mg＋MgH2＊１００）を算出したところ、水素化率は７６％であった。 (2) The treated powder was sealed in a pressure vessel and held at a hydrogen pressure (cage pressure) of 4 MPa and a temperature of 400 ° C. for 12 hours. When the hydrogenation rate (MgH 2 / Mg + MgH 2 * 100) was calculated by obtaining the hydrogen concentration in the sample by the thermal conductivity method after the hydrogenation treatment, the hydrogenation rate was 76%.
Claims (6)
The production method according to any one of claims 1 to 5, wherein the amount of the inert organic solvent used is 1 to 5 parts by mass with respect to 1 part by mass of the metal magnesium powder.
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