JP2018053359A - Porous sponge copper, manufacturing method of porous sponge copper, porous sponge copper catalyst and manufacturing method of porous sponge copper catalyst - Google Patents
Porous sponge copper, manufacturing method of porous sponge copper, porous sponge copper catalyst and manufacturing method of porous sponge copper catalyst Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 105
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- ZITOPJKFJBLAMM-UHFFFAOYSA-N 1-(2-oxopropanoyl)pyrrolidine-2-carboxylic acid Chemical compound CC(=O)C(=O)N1CCCC1C(O)=O ZITOPJKFJBLAMM-UHFFFAOYSA-N 0.000 title claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 241000446313 Lamella Species 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 230000007423 decrease Effects 0.000 claims description 11
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000006011 modification reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 238000002386 leaching Methods 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 210000003041 ligament Anatomy 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
本発明は新規な多孔質スポンジ銅、多孔質スポンジ銅の製造方法並びにその触媒用途に関するものである。 The present invention relates to a novel porous sponge copper, a method for producing porous sponge copper, and its catalytic use.
スポンジ金属とは多孔質の金属または合金のことを言い、一般に、２種以上の金属の合金から、合金を構成する金属の少なくとも一種が溶解しないで残る条件で、一部の金属を溶解除去することにより製造される。金属の溶解除去にあたっては、酸やアルカリを使用して除去対象である金属を溶解することが知られている。このようなスポンジ金属はラネー（登録商標）合金として知られており、触媒として使用されるものはラネー触媒と言われている。 Sponge metal refers to a porous metal or alloy. In general, a part of metal is dissolved and removed from an alloy of two or more metals under the condition that at least one of the metals constituting the alloy remains undissolved. It is manufactured by. In dissolving and removing a metal, it is known to dissolve the metal to be removed using an acid or an alkali. Such a sponge metal is known as a Raney (registered trademark) alloy, and what is used as a catalyst is called a Raney catalyst.
スポンジ金属としては、ニッケルやクロムをスポンジ化したものが古くから知られているが、使用する金属の種類やその組合せによって多様な展開があり、ニッケルやクロムの他、金属として金（Ａｕ）を使用したスポンジ金属についても報告され、その触媒としての用途も期待されている（特許文献１）。 Sponge metal nickel or chromium has been known for a long time, but there are various developments depending on the type of metal used and its combination. In addition to nickel and chromium, gold (Au) is used as the metal. The sponge metal used was also reported, and its use as a catalyst is also expected (Patent Document 1).
触媒に使用される金属としては、上記のニッケル、クロム、金の他、白金などの貴金属が有名であるが、銅も触媒としての用途が期待される金属である。銅はそのものを触媒として用いる他、貴金属やゼオライトに添加して活性の向上などを図るための助触媒としての用途も知られている。銅系触媒はメタノール水蒸気改質、メタノール合成、水性ガスシフト反応（ｗａｔｅｒ−ｇａｓ ｓｈｉｆｔ ｒｅａｃｔｉｏｎ） ならびに有機化合物の水素化や水素化分解反応などに対し広範に用いられている。 As the metal used for the catalyst, noble metals such as platinum are famous in addition to the above nickel, chromium and gold, but copper is also a metal expected to be used as a catalyst. In addition to using copper itself as a catalyst, copper is also known to be used as a co-catalyst for adding to noble metals and zeolites to improve activity. Copper catalysts are widely used for methanol steam reforming, methanol synthesis, water-gas shift reaction, and hydrogenation and hydrocracking reactions of organic compounds.
スポンジ金属の製法として、２種以上の金属を溶融混合した金属に対し、アルカリ溶液や酸溶液をもって溶融混合物から一部の金属を溶解除去（リーチング）することで多孔質化する方法が知られている。ここで溶解除去される金属としてはアルミニウムが選択されることが多く、アルミニウムと残留させるべき金属とが溶融混合される。このようにアルミニウムを使用する場合は、酸性環境下で不動態を形成して溶解が困難になる場合があることから、リーチング処理には水酸化ナトリウム等のアルカリ溶液を用いることが一般的である。 As a method for producing sponge metal, a method is known in which a metal obtained by melting and mixing two or more metals is made porous by dissolving and removing (leaching) a part of the metal from the molten mixture with an alkali solution or an acid solution. Yes. Here, aluminum is often selected as the metal to be dissolved and removed, and aluminum and the metal to be left are melted and mixed. When aluminum is used in this way, it may be difficult to dissolve by forming a passivity in an acidic environment, and therefore it is common to use an alkali solution such as sodium hydroxide for the leaching treatment. .
このように従来から知られているスポンジ金属であるが、産業の発展に伴い従来にない新規な構成のスポンジ金属が求められている。 As described above, the sponge metal is conventionally known, but with the development of the industry, there is a demand for a sponge metal having a novel structure which has not been conventionally used.
本発明者らは鋭意検討を重ねた結果、銅とアルミニウムの溶融混合物に対して塩酸（ＨＣｌ）水溶液によるリーチングをもってアルミニウムを溶解除去することで、従来に無い新規な多孔質スポンジ銅が得られることを見いだし、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that a novel porous sponge copper can be obtained by dissolving and removing aluminum by leaching with a hydrochloric acid (HCl) aqueous solution to a molten mixture of copper and aluminum. As a result, the present invention has been completed.
本発明の多孔質スポンジ銅は、高温で熱処理を施したり、加熱を伴う反応において触媒として使用しても比表面積の減少が少なく熱安定性に優れ、触媒として繰り返しの使用や熱的に過酷な条件での使用においても高い触媒活性を維持することができ、耐久性に優れるものである。 The porous sponge copper of the present invention is heat-treated at a high temperature, and even when used as a catalyst in a reaction involving heating, the specific surface area does not decrease and is excellent in thermal stability. High catalytic activity can be maintained even when used under conditions, and the durability is excellent.
本発明の多孔質スポンジ銅は、例えば、アルミニウムと銅の溶融混合を経て得られた粒子から、塩酸水溶液を使用してアルミニウムを溶解除去（リーチング処理）することによって得られるものである。具体的には、例えば、アルミニウム及び銅を所定の組成となるように秤量し、アーク溶解炉にて溶融混合した後、冷却することにより、アルミニウム及び銅からなる金属間化合物のインゴットを得る。このインゴットを必要に応じアニール処理した後、粉砕してアルミニウム及び銅の金属間化合物粒子を得る。アルミニウム合金中の銅の原子％組成比は、１０〜４０原子％が好ましく、１５〜３３原子％がより好ましい。また、アルミニウム及び銅の溶融混合物を、ガスアトマイズ法、水アトマイズ法、回転円板遠心噴霧法などの方法によって粒子化してもよい。金属間化合物粒子の粒子径は特に限定されないが、篩分け法等により、１０〜１２０μｍの範囲に調整することが好ましく、１０〜２５μｍがより好ましい。 The porous sponge copper of the present invention is obtained, for example, by dissolving and removing aluminum (leaching treatment) from particles obtained through melt mixing of aluminum and copper using an aqueous hydrochloric acid solution. Specifically, for example, aluminum and copper are weighed to have a predetermined composition, melted and mixed in an arc melting furnace, and then cooled to obtain an ingot of an intermetallic compound composed of aluminum and copper. The ingot is annealed as necessary and then pulverized to obtain aluminum and copper intermetallic compound particles. The atomic percent composition ratio of copper in the aluminum alloy is preferably 10 to 40 atomic percent, and more preferably 15 to 33 atomic percent. Moreover, you may granulate the molten mixture of aluminum and copper by methods, such as a gas atomizing method, a water atomizing method, and a rotating disc centrifugal spraying method. The particle size of the intermetallic compound particles is not particularly limited, but is preferably adjusted to a range of 10 to 120 μm, more preferably 10 to 25 μm by a sieving method or the like.
この金属間化合物粒子を塩酸（ＨＣｌ）水溶液でリーチング処理し、アルミニウムを選択的に溶出させる。塩酸水溶液の濃度は特に限定されないが、５〜３７質量％が好ましく、１０〜２０質量％がより好ましい。この塩酸水溶液の金属間化合物粒子に対する処理量は特に制限されないが、例えば、５ｇの金属間化合物粒子に対し１０質量％塩酸水溶液２５０ｇ程度で処理すればよい。リーチング処理条件も特に限定されるものではなく、例えば室温で２４時間程度行えばよい。リーチング処理による金属間化合物からのアルミニウム溶出量は、金属間化合物中のアルミニウム全量に対して９５％以上が好ましく、９８％以上がより好ましい。リーチング処理後、水溶液中から残留物を取り出し、必要に応じ、水洗、乾燥、Ｈ２還元処理等を行うことにより、本発明の多孔質スポンジ銅が得られる。 The intermetallic compound particles are leached with an aqueous hydrochloric acid (HCl) solution to selectively elute aluminum. Although the density | concentration of hydrochloric acid aqueous solution is not specifically limited, 5-37 mass% is preferable and 10-20 mass% is more preferable. The amount of treatment of the aqueous hydrochloric acid solution with respect to the intermetallic compound particles is not particularly limited. For example, the treatment may be performed with about 250 g of 10 mass% aqueous hydrochloric acid solution with respect to 5 g of intermetallic compound particles. The leaching process conditions are not particularly limited, and may be performed, for example, at room temperature for about 24 hours. The amount of aluminum eluted from the intermetallic compound by the leaching treatment is preferably 95% or more, and more preferably 98% or more with respect to the total amount of aluminum in the intermetallic compound. After the leaching treatment, the residue is taken out from the aqueous solution and, if necessary, washed with water, dried, H 2 reduction treatment, etc., to obtain the porous sponge copper of the present invention.
かくして得られる本発明の多孔質スポンジ銅は、高密度の双晶構造を有しており、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ；ＴＥＭ）により観察される双晶の境界線の数が、５０ｎｍあたり１０以上、好ましくは１５以上である双晶組織を含む。また双晶組織における双晶ラメラ距離（双晶境界面の距離）は１〜５ｎｍであることが好ましく、より好ましくは１．５〜２．５ｎｍである。双晶ラメラ距離は、ＴＥＭ像によって求められる値である。多孔質スポンジ銅を構成する双晶粒子（リガメント）は、平行な境界面を持って構成される。双晶粒子の大きさ（リガメント径）は２０〜２００nmが好ましく、６０〜２００nmがより好ましい。本明細書において、双晶の境界線の数、双晶ラメラ距離、リガメント径は、ＦＥＩ社製透過型電子顕微鏡、型番：Ｔｉｔａｎ Ｇ２ ６０−３００による加速電圧３００ｋＶで測定される値である。 The porous sponge copper of the present invention thus obtained has a high density twin structure, and the number of twin boundaries observed by a transmission electron microscope (TEM) is about 50 nm. It contains a twin structure that is 10 or more, preferably 15 or more. Moreover, it is preferable that the twin lamella distance (distance of a twin interface) in a twin structure is 1-5 nm, More preferably, it is 1.5-2.5 nm. The twin lamella distance is a value obtained from a TEM image. The twin particles (ligaments) constituting the porous sponge copper are configured to have parallel boundary surfaces. The size (ligament diameter) of twin particles is preferably 20 to 200 nm, more preferably 60 to 200 nm. In the present specification, the number of twin boundaries, twin lamella distance, and ligament diameter are values measured at an acceleration voltage of 300 kV using a transmission electron microscope manufactured by FEI, model number: Titan G2 60-300.
本発明の多孔質スポンジ銅の比表面積は、好ましくは０．５〜５０ｍ２／ｇ、より好ましくは１．０〜５０ｍ２／ｇ、さらに好ましくは１．０〜５．０ｍ２／ｇ、特に好ましくは１．０〜４．０ｍ２／ｇである。本明細書において、比表面積はＢＥＴ法により求められる値である。本発明の多孔質スポンジ銅は、このような多孔質構造に基づき優れた触媒活性を有し、加熱を伴う反応において触媒として使用しても比表面積の減少がほとんどない。例えば、反応温度２４０〜３６０℃でのメタノール水蒸気改質反応（Ｓｔｅａｍ Ｒｅｆｏｒｍｉｎｇ ｏｆ Ｍｅｔｈａｎｏｌｅ；ＳＲＭ）においても、比表面積の減少はほとんどなく、例えば、比表面積の減少率が好ましくは１０％以下、より好ましくは５％以下である。また、より高温で熱処理（アニール処理）しても比表面積の減少はほとんどなく、例えば、６００℃熱処理後の比表面積の減少率が、好ましくは２０％以下、より好ましくは１０％以下である。比表面積の減少率は、下記式によって求められる。
比表面積の減少率（％）＝（Ｓ０−Ｓ１）×１００／Ｓ０
Ｓ０：ＳＲＭ反応前または熱処理前の比表面積
Ｓ１：ＳＲＭ反応後または熱処理後の比表面積
The specific surface area of the porous sponge copper of the present invention is preferably 0.5 to 50 m 2 / g, more preferably 1.0 to 50 m 2 / g, still more preferably 1.0 to 5.0 m 2 / g, particularly Preferably it is 1.0-4.0m < 2 > / g. In the present specification, the specific surface area is a value determined by the BET method. The porous sponge copper of the present invention has excellent catalytic activity based on such a porous structure, and even when used as a catalyst in a reaction involving heating, there is almost no decrease in specific surface area. For example, even in a methanol reforming reaction (SRM) at a reaction temperature of 240 to 360 ° C., there is almost no decrease in the specific surface area. For example, the reduction rate of the specific surface area is preferably 10% or less, more preferably. Is 5% or less. Further, even when heat treatment (annealing) is performed at a higher temperature, the specific surface area hardly decreases. For example, the reduction rate of the specific surface area after heat treatment at 600 ° C. is preferably 20% or less, more preferably 10% or less. The reduction rate of the specific surface area is obtained by the following formula.
Reduction rate of specific surface area (%) = (S 0 −S 1 ) × 100 / S 0
S 0 : Specific surface area before SRM reaction or before heat treatment S 1 : Specific surface area after SRM reaction or after heat treatment
このように、高温でも比表面積の減少が少ないことに基づき、本発明の多孔質スポンジ銅は高温条件でも高い触媒活性を発揮する。例えば、反応温度２４０〜３６０℃でのメタノール水蒸気改質反応において、３２０℃での水素生成速度よりも３６０℃での水素生成速度の方が高いことが好ましく、より好ましくは１．２倍以上高く、さらに１．５倍以上高いことが好ましい。また昇温時の３２０℃における水素生成速度に対する降温時の３２０℃における水素生成速度の減少率が、好ましくは４０％以下、より好ましくは３０％以下である。水素生成速度の減少率は、下記式によって求められる。
水素生成速度の減少率（％）＝（Ｖ０−Ｖ１）×１００／Ｖ０
Ｖ０：昇温時の３２０℃における水素生成速度
Ｖ１：降温時の３２０℃における水素生成速度
As described above, the porous sponge copper of the present invention exhibits high catalytic activity even under high temperature conditions, based on the fact that the decrease in specific surface area is small even at high temperatures. For example, in the methanol steam reforming reaction at a reaction temperature of 240 to 360 ° C., the hydrogen production rate at 360 ° C. is preferably higher than the hydrogen production rate at 320 ° C., more preferably 1.2 times higher. Further, it is preferably 1.5 times higher. Further, the rate of decrease in the hydrogen production rate at 320 ° C. when the temperature is lowered is preferably 40% or less, more preferably 30% or less, relative to the hydrogen production rate at 320 ° C. when the temperature is raised. The reduction rate of the hydrogen production rate is obtained by the following equation.
Reduction rate of hydrogen production rate (%) = (V 0 −V 1 ) × 100 / V 0
V 0 : Hydrogen production rate at 320 ° C. during temperature increase V 1 : Hydrogen production rate at 320 ° C. during temperature decrease
本発明の多孔質スポンジ銅を粒子のまま本発明の触媒として用いてもよく、押出成形や打錠成形によって成形体としたり、固定床触媒等として使用することもできる。 The porous sponge copper of the present invention may be used as the catalyst of the present invention in the form of particles, or may be formed into a molded body by extrusion molding or tableting, or may be used as a fixed bed catalyst or the like.
以上のように、本発明の多孔質スポンジ銅は、高温で熱処理を施したり、加熱を伴う反応において触媒として使用しても比表面積の減少が少なく熱安定性に優れ、触媒として繰り返しの使用や熱的に過酷な条件での使用において高い触媒活性を維持することができ、耐久性に優れるものである。本発明の触媒は、種々の反応に使用することができ、例えば、メタノール水蒸気改質反応、ＮＯ−ＣＯ反応等が例示される。また他の触媒を担持させることもできる。 As described above, the porous sponge copper of the present invention is excellent in thermal stability with little reduction in specific surface area even when subjected to heat treatment at a high temperature or used as a catalyst in a reaction involving heating. High catalytic activity can be maintained in use under thermally severe conditions, and the durability is excellent. The catalyst of the present invention can be used for various reactions, and examples thereof include methanol steam reforming reaction and NO-CO reaction. Other catalysts can also be supported.
以下、図面を引用しながら本発明の具体的な実施形態を説明するが、本発明は以下の実施例に限定されるものではなく、その趣旨を逸脱しない限り広く展開可能であることは言うまでもない。 Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples, and it is needless to say that the present invention can be widely deployed without departing from the gist thereof. .
（実施例１）
［多孔質スポンジ銅の製造］：塩酸処理
＜金属間化合物の合成工程＞
先ず、Ｃｕ（純度：９９．９質量％）とＡｌ（純度：９９．９質量％）とを各２．７０ｇ（Ｃｕ）、２．３０ｇ（Ａｌ）秤量し、これらをアーク溶解炉装置（株式会社ＧＥＳ製、「ＧＭＡＣ−１１００」）の溶解用チャンバー内に導入して、溶解用チャンバー内のＡｒ圧：５００Ｔｏｒｒ、アーク電極電流：１２０Ａの条件で溶解した後、自然放冷して固体化させ、ＣｕとＡｌとを含有する金属間化合物のインゴットを製造した。
次に、前記インゴットを石英反応菅に真空封入（１×１０−５Ｔｏｒｒ）し、前記インゴットに対してアニール処理（５５０℃、２４時間）を行った。次いで、アニール処理後の金属間化合物のインゴットを粉砕し微粉末化させ、最終的に篩を用いて２５μｍ以下に整粒し、微粉末状の金属間化合物（組成：Ａｌ２Ｃｕ）を得た。なお、このようにして得られた金属間化合物をＸＲＤにより測定したところ、金属間化合物はＣｕとＡｌとが原子レベルで混合したＡｌでもＣｕでもない別の合金状態となっていることが確認された。
Example 1
[Production of Porous Sponge Copper]: Hydrochloric Acid Treatment <Intermetallic Compound Synthesis Process>
First, 2.70 g (Cu) and 2.30 g (Al) of Cu (purity: 99.9% by mass) and Al (purity: 99.9% by mass) were weighed, and these were weighed into an arc melting furnace apparatus (stock) (GMAC-1100, manufactured by GES, Inc.) and dissolved in the melting chamber under the conditions of Ar pressure: 500 Torr and arc electrode current: 120 A, and then naturally cooled to solidify. An ingot of an intermetallic compound containing Cu and Al was produced.
Next, the ingot was vacuum sealed (1 × 10 −5 Torr) in a quartz reaction vessel, and the ingot was annealed (550 ° C., 24 hours). Next, the ingot of the intermetallic compound after the annealing treatment was pulverized to be finely powdered, and finally sized to 25 μm or less using a sieve to obtain a finely powdered intermetallic compound (composition: Al 2 Cu). . In addition, when the intermetallic compound obtained in this way was measured by XRD, it was confirmed that the intermetallic compound was in another alloy state in which Cu and Al were mixed at the atomic level and neither Al nor Cu. It was.
＜Ａｌの選択的溶出（ｌｅａｃｈｉｎｇ）工程＞
先ず、上述のようにして得られた微粉末状の金属間化合物５ｇを１０質量％ＨＣｌ水溶液２５０ｇに投入し（室温、２４時間）、金属間化合物からＡｌを溶出させた。次いで、前記水溶液中から前記金属間化合物の残留物を取り出し、水洗、乾燥（１００℃、１時間）、Ｈ２還元処理してＣｕを含有する多孔性金属を製造した。なお、Ａｌの溶出量は、前記金属間化合物中のＡｌの全量に対して９９％であった。得られた粒子の比表面積は１．０８ｍ２／ｇであった。以下これを［実施例スポンジ銅］という。得られた［実施例スポンジ銅］について、ＴＥＭにより組織観察を行った（図１〜４）。［実施例スポンジ銅］は、全体に高密度の双晶が導入され、双晶界面が極めて緻密であることが確認された。ＴＥＭ画像に基づき求めた双晶間の距離は平均２．３ｎｍであり（図５）、５０ｎｍあたり双晶の境界線の数は２１.７本であった。またリガメント径は６０〜２００ｎｍであった。細孔表面には、ファセットによる凹凸構造を有しており、表面に酸化物（Ｃｕ２Ｏ）が付着していることが認められた（図１、４）。双晶粒子（リガメント）は平行な境界面をもって構成され、他の平行な境界面をもって構成される双晶粒子と９０度の角度で交接していた（図２）。
<Al selective leaching step>
First, 5 g of finely powdered intermetallic compound obtained as described above was added to 250 g of a 10% by mass HCl aqueous solution (room temperature, 24 hours), and Al was eluted from the intermetallic compound. Subsequently, the residue of the intermetallic compound was taken out from the aqueous solution, washed with water, dried (100 ° C., 1 hour), and subjected to H 2 reduction treatment to produce a porous metal containing Cu. The elution amount of Al was 99% with respect to the total amount of Al in the intermetallic compound. The specific surface area of the obtained particles was 1.08 m 2 / g. Hereinafter, this is referred to as [Example Sponge Copper]. About the obtained [Example sponge copper], structure | tissue observation was performed by TEM (FIGS. 1-4). [Example Sponge Copper] was confirmed that a high-density twin was introduced to the whole and the twin interface was extremely dense. The distance between twins obtained based on the TEM image was 2.3 nm on average (FIG. 5), and the number of twin boundaries per 50 nm was 21.7. The ligament diameter was 60 to 200 nm. The surface of the pores had a concavo-convex structure due to facets, and it was recognized that oxides (Cu 2 O) were attached to the surface (FIGS. 1 and 4). Twin grains (ligaments) were composed of parallel boundary surfaces, and were in contact with twin grains composed of other parallel boundary surfaces at an angle of 90 degrees (FIG. 2).
（比較例１）
［スポンジ銅の製造］：水酸化ナトリウム処理
水酸化ナトリウムを使用してアルミニウムのリーチング処理を施した例を以下に示す。
(Comparative Example 1)
[Production of Sponge Copper]: Sodium Hydroxide Treatment An example of aluminum leaching treatment using sodium hydroxide is shown below.
＜Ａｌの選択的溶出（ｌｅａｃｈｉｎｇ）工程＞
Ａｌの選択的溶出工程において、１０質量％ＨＣｌ水溶液の代わりに１０質量％ＮａＯＨ水溶液を用いた以外は実施例１と同様にして、Ｃｕを含有する多孔性金属を得た。なお、Ａｌの溶出量は、金属間化合物中のＡｌの全量に対して９６％であった。得られた粒子の比表面積は５．１２ｍ２／ｇであった。以下これを［比較例スポンジ銅］という。
<Al selective leaching step>
In the selective elution step of Al, a porous metal containing Cu was obtained in the same manner as in Example 1 except that a 10% by mass NaOH aqueous solution was used instead of the 10% by mass HCl aqueous solution. The elution amount of Al was 96% with respect to the total amount of Al in the intermetallic compound. The specific surface area of the obtained particles was 5.12 m 2 / g. Hereinafter, this is referred to as [Comparative Sponge Copper].
＜触媒活性試験＞ ：メタノール水蒸気改質反応
上記の方法で得られた多孔性金属０．６ｇを秤量し、固定床流通式反応装置で常圧、反応温度２４０〜３６０℃（昇温速度１０［℃／ｍｉｎ］）に設定し、水／ メタノールのモル比１．５の混合液を流通させた。ガスの流通条件は、ＬＨＳＶ＝６０ｈ−１とした。発生ガスをガスクロマトグラフィーにより分析し、水素生成速度により触媒の活性を評価した。この評価においては、［実施例スポンジ銅］と［比較例スポンジ銅］に加え、市販の銅粉末 （和光純薬工業株式会社、粒径７５μｍ未満、製品名：０３０−１８３５２）についても評価を行った。結果を図６に示す。また反応前後の［実施例スポンジ銅］及び［比較例スポンジ銅］について、ＢＥＴ比表面積測定（表１）、粉末Ｘ線回折（図７）、ＴＥＭおよびＳＥＭによる組織観察（図８〜１５、表１）を行った。なお、［実施例スポンジ銅］及び［比較例スポンジ銅］を熱処理（６００℃、６時間；ａｆｔｅｒ ａｎｎｅａｌｌｉｎｇ）したものについても比表面積の測定及びリガメント径の測定を行った。
<Catalyst activity test>: Methanol steam reforming reaction 0.6 g of the porous metal obtained by the above method was weighed and measured at normal pressure and reaction temperature of 240 to 360 ° C. (temperature increase rate of 10 [ [° C./min]), and a water / methanol mixture having a molar ratio of 1.5 was circulated. The gas flow conditions were LHSV = 60 h −1 . The generated gas was analyzed by gas chromatography, and the activity of the catalyst was evaluated by the hydrogen production rate. In this evaluation, in addition to [Example Sponge Copper] and [Comparative Sponge Copper], a commercially available copper powder (Wako Pure Chemical Industries, Ltd., particle size of less than 75 μm, product name: 030-18352) was also evaluated. It was. The results are shown in FIG. Further, for [Example Sponge Copper] and [Comparative Sponge Copper] before and after the reaction, BET specific surface area measurement (Table 1), powder X-ray diffraction (FIG. 7), structure observation by TEM and SEM (FIGS. 8 to 15, Table) 1) was performed. In addition, the specific surface area and the ligament diameter were also measured for [Example Sponge Copper] and [Comparative Example Sponge Copper] heat treated (600 ° C., 6 hours; after annealing).
図６に示すとおり、［比較例スポンジ銅］（ＮａＯＨ）は、３２０℃から３６０℃に昇温すると触媒活性が低下し、水素生成速度が減少したが、［実施例スポンジ銅］（ＨＣｌ）は、３６０℃まで昇温に伴って水素生成速度が増大し続け、高い耐熱性を有していることが実証された。また、［比較例スポンジ銅］は、反応温度を下げていった際の水素生成速度が昇温時の同温度での水素生成速度と比較して著しく低下していたのに対し、［実施例スポンジ銅］は、降温時と昇温時の同温度での触媒活性がほとんど変わらず、３２０℃での減少率はほぼ２０％と僅かなものであった。なお、市販の銅粉末（Ｐｏｗｄｅｒ）は、ほとんど触媒活性を示さなかった。 As shown in FIG. 6, [Comparative Example Sponge Copper] (NaOH) decreased in catalytic activity and reduced hydrogen production rate when heated from 320 ° C. to 360 ° C., but [Example Sponge Copper] (HCl) It was proved that the hydrogen generation rate continued to increase as the temperature rose to 360 ° C., and it had high heat resistance. [Comparative Example Sponge Copper] showed that the hydrogen production rate when the reaction temperature was lowered was significantly lower than the hydrogen production rate at the same temperature when the temperature was raised, whereas [Examples] Sponge copper] showed almost no change in the catalytic activity at the same temperature when the temperature was lowered and when the temperature was raised, and the decrease rate at 320 ° C. was as little as 20%. The commercially available copper powder (Powder) showed almost no catalytic activity.
＜ＢＥＴ比表面積＞
表１より、［比較例スポンジ銅］では触媒反応の前後における比表面積の減少がみられるのに対し、［実施例スポンジ銅］では比表面積の変化はなかった。さらに６００℃熱処理によって、［比較例スポンジ銅］では著しく比表面積が減少するのに対し、［実施例スポンジ銅］はほとんど減少が認められなかった。このことから、本発明の多孔質スポンジ銅は、高い熱的安定性を有し、触媒としての繰り返し使用や熱的に過酷な条件での使用において触媒活性を維持でき、耐久性に優れることが示された。なお、［実施例スポンジ銅］ではリーチング処理後の比表面積値が１．０８（ｍ２／ｇ）と［比較例スポンジ銅］の５．１２（ｍ２／ｇ）と比べて低いにも関わらず高い触媒活性を発揮している。
<BET specific surface area>
From Table 1, the specific surface area decreased before and after the catalytic reaction in [Comparative Sponge Copper], whereas the specific surface area did not change in [Example Sponge Copper]. Furthermore, the specific surface area of [Comparative Sponge Copper] is significantly reduced by heat treatment at 600 ° C., whereas [Example Sponge Copper] hardly shows any decrease. From this, the porous sponge copper of the present invention has high thermal stability, can maintain catalytic activity in repeated use as a catalyst and use under severe heat conditions, and is excellent in durability. Indicated. In [Example Sponge Copper], although the specific surface area value after leaching was 1.08 (m 2 / g), it was lower than 5.12 (m 2 / g) of [Comparative Example Sponge Copper]. It exhibits high catalytic activity.
＜ＸＲＤ＞
図７に示すとおり、［実施例スポンジ銅］及び［比較例スポンジ銅］はいずれも、ＳＲＭ反応前後の粉末Ｘ線回折パターンにおいて、銅あるいは酸化銅によるピーク変化がほとんど認められなかった。６００℃熱処理後も同様に変化はなかった。
<XRD>
As shown in FIG. 7, in [Example Sponge Copper] and [Comparative Sponge Copper], almost no peak change due to copper or copper oxide was observed in the powder X-ray diffraction patterns before and after the SRM reaction. There was no change after heat treatment at 600 ° C.
＜組織観察＞
［比較例スポンジ銅］では、触媒反応前は、双晶ラメラ距離３．５ｎｍの双晶組織を有し、粒子径（リガメント径）５０ｎｍ程度の均一なポーラス構造を有していたが、触媒反応後、部分的な凝集・粒成長が生じ、粒子径の増大が認められた（図８〜１１）。これに対し、［実施例スポンジ銅］では触媒反応後における粒子径の増大は認められず、多孔質としての状態も維持され、双晶組織も密な状態を保っていることが分かった（図１２〜１５）。６００℃熱処理後も、密な双晶構造は消滅するが、なおポーラス構造は維持される（図１４（ｃ））。
<Tissue observation>
[Comparative Sponge Copper] had a twin structure with a twin lamella distance of 3.5 nm and a uniform porous structure with a particle diameter (ligament diameter) of about 50 nm before the catalytic reaction. Later, partial agglomeration and grain growth occurred, and an increase in particle diameter was observed (FIGS. 8 to 11). On the other hand, in [Example Sponge Copper], it was found that the particle diameter did not increase after the catalytic reaction, the porous state was maintained, and the twin structure was kept in a dense state (see FIG. 12-15). Even after heat treatment at 600 ° C., the dense twin structure disappears, but the porous structure is maintained (FIG. 14C).
本発明の多孔質スポンジ銅は、高温で熱処理を施したり、加熱を伴う反応において触媒として使用しても比表面積の減少が少なく、触媒として繰り返しの使用や熱的に過酷な条件での使用において高い触媒活性を維持することができ、耐久性に優れるものである。そのため、メタノール水蒸気改質反応やＮＯ−ＣＯ反応など種々の反応における触媒として利用可能である。
The porous sponge copper of the present invention undergoes heat treatment at a high temperature or has a small decrease in specific surface area even when used as a catalyst in a reaction involving heating, and can be used repeatedly and as a catalyst under severe conditions. High catalytic activity can be maintained, and durability is excellent. Therefore, it can be used as a catalyst in various reactions such as methanol steam reforming reaction and NO-CO reaction.
Claims (12)
The method for producing a porous sponge copper catalyst according to claim 11, wherein the particles obtained by melt mixing of aluminum and copper are particles obtained by pulverizing an intermetallic compound composed of aluminum and copper.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109133001A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of metal powder and souring activity charcoal composite hydrogen manufacturing material |
| JP2020122181A (en) * | 2019-01-30 | 2020-08-13 | 星和電機株式会社 | Porous copper and method for producing the same |
| CN112091207A (en) * | 2020-09-10 | 2020-12-18 | 安徽德诠新材料科技有限公司 | Composite porous copper powder and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109133001A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of metal powder and souring activity charcoal composite hydrogen manufacturing material |
| JP2020122181A (en) * | 2019-01-30 | 2020-08-13 | 星和電機株式会社 | Porous copper and method for producing the same |
| CN112091207A (en) * | 2020-09-10 | 2020-12-18 | 安徽德诠新材料科技有限公司 | Composite porous copper powder and preparation method and application thereof |
| CN112091207B (en) * | 2020-09-10 | 2024-04-26 | 安徽德诠新材料科技有限公司 | Composite porous copper powder and preparation method and application thereof |
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