JP2001192701A - Spherical catalytic powder composed of nickel-aluminum alloy, sponge nickel catalyst composed thereof, and their manufacturing method - Google Patents
Spherical catalytic powder composed of nickel-aluminum alloy, sponge nickel catalyst composed thereof, and their manufacturing methodInfo
- Publication number
- JP2001192701A JP2001192701A JP2000003002A JP2000003002A JP2001192701A JP 2001192701 A JP2001192701 A JP 2001192701A JP 2000003002 A JP2000003002 A JP 2000003002A JP 2000003002 A JP2000003002 A JP 2000003002A JP 2001192701 A JP2001192701 A JP 2001192701A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- aluminum
- catalyst
- area ratio
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000843 powder Substances 0.000 title claims abstract description 87
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 229910000838 Al alloy Inorganic materials 0.000 title description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 82
- 239000000956 alloy Substances 0.000 claims abstract description 82
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000007712 rapid solidification Methods 0.000 claims abstract description 13
- 229910000943 NiAl Inorganic materials 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000000265 homogenisation Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910003310 Ni-Al Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011214 refractory ceramic Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 102220253765 rs141230910 Human genes 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 101100000419 Autographa californica nuclear polyhedrosis virus AC41 gene Proteins 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、触媒用ニッケル−
アルミニウム合金の球状粉末及びそれからなる球状スポ
ンジニッケル触媒、並びにそれらの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention
The present invention relates to a spherical powder of an aluminum alloy, a spherical nickel sponge catalyst comprising the same, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来からスポンジニッケル触媒は接触水
素化反応等の還元反応用触媒として広く使用されている
が、一般にNi-Al 合金のインゴットの粉砕又はアトマイ
ズにより得た合金粉末をアルカリ水溶液で展開すること
により調製されている。しかし、粉砕法により得られる
合金粉末は粒径分布が広く、微粉末を多量に含有してい
る。微粉末は活性化工程において厄介な存在であり、さ
らに流動床においては逸流してロスとなるため、著しく
不利である。そのため、所望の粒度範囲の合金粉末を得
るためには、粉砕後に篩分けをしなければならず、製品
歩留りが悪い。2. Description of the Related Art Conventionally, sponge nickel catalysts have been widely used as catalysts for reduction reactions such as catalytic hydrogenation reactions. However, in general, alloy powders obtained by crushing or atomizing Ni-Al alloy ingots are developed with an aqueous alkaline solution. It has been prepared by However, the alloy powder obtained by the pulverization method has a wide particle size distribution and contains a large amount of fine powder. Fine powders are a significant disadvantage because they are a nuisance in the activation process and, in a fluidized bed, can escape and become lossy. Therefore, in order to obtain an alloy powder having a desired particle size range, the powder must be sieved after pulverization, and the product yield is poor.
【０００３】一方、アトマイズ法により得られた合金粉
末は比較的球状になりやすく、また粉砕法による合金粉
末よりも粒径分布が狭くなる傾向がある。そのため、ア
トマイズ法により触媒用合金粉末を製造する方法につい
て、種々の提案がなされている。例えば特開平5-23597
号は、触媒活性金属にアルミニウム又はシリコンを含有
させてなる合金の溶湯を不活性ガス雰囲気中で高速回転
する円盤上に滴下し、遠心力により飛散させて、微細液
滴を冷却凝固させることにより、粒径がコントロールさ
れた触媒用合金を製造する方法を提案している。この方
法により得られる合金粉末は球状であり、流動床反応に
使用するのに好適である。On the other hand, alloy powders obtained by the atomization method tend to be relatively spherical, and the particle size distribution tends to be narrower than alloy powders obtained by the pulverization method. Therefore, various proposals have been made for a method for producing an alloy powder for a catalyst by an atomizing method. For example, JP-A-5-23597
No. is a method in which a molten metal of an alloy containing aluminum or silicon in a catalytically active metal is dropped on a disk rotating at high speed in an inert gas atmosphere, and scattered by centrifugal force to cool and solidify fine droplets. A method for producing a catalyst alloy having a controlled particle size is proposed. The alloy powder obtained by this method is spherical and is suitable for use in a fluidized bed reaction.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、アトマ
イズ法により得た球状Ni-Al 合金をそのままアルカリ水
溶液により展開するとアルミニウムの溶出が不十分であ
るという問題があることが分かった。これは、アトマイ
ズ法によりニッケル−アルミニウム合金の溶湯が急冷凝
固すると、アルカリ水溶液中でアルミニウムが溶出し易
い化合物相の割合が低下し、比較的溶出性が低い化合物
相が多量に生成されるためであると考えられる。However, it has been found that when the spherical Ni-Al alloy obtained by the atomization method is developed as it is with an aqueous alkali solution, there is a problem that the elution of aluminum is insufficient. This is because when the molten metal of the nickel-aluminum alloy is rapidly solidified by the atomizing method, the proportion of the compound phase in which aluminum is easily eluted in the alkaline aqueous solution is reduced, and a large amount of the relatively low-eluting compound phase is generated. It is believed that there is.
【０００５】従って、本発明の目的は、球状で均一な粒
径分布を有するとともに優れた触媒活性を有するスポン
ジニッケル触媒、かかるスポンジニッケル触媒を生成す
ることができるニッケル−アルミニウム合金の球状粉
末、及びそれらの製造方法を提供することである。Accordingly, it is an object of the present invention to provide a sponge nickel catalyst having a spherical and uniform particle size distribution and excellent catalytic activity, a nickel-aluminum alloy spherical powder capable of producing such a sponge nickel catalyst, and The purpose is to provide a method for producing them.
【０００６】[0006]
【課題を解決するための手段】上記目的に鑑み鋭意研究
の結果、ガスアトマイズ法等の急冷凝固法により作製し
たニッケル−アルミニウム合金の球状粉末に均質化処理
を施した後、アルカリ水溶液で展開すると、良好な触媒
活性を有する還元反応用触媒が得られることを発見し、
本発明に想到した。Means for Solving the Problems As a result of intensive studies in view of the above-mentioned object, after homogenizing a spherical powder of a nickel-aluminum alloy produced by a rapid solidification method such as a gas atomizing method, and then developing with an aqueous alkaline solution, Discovered that a catalyst for reduction reaction having good catalytic activity can be obtained,
The present invention has been made.
【０００７】すなわち、本発明の触媒用合金粉末は、ニ
ッケルとアルミニウムとを主成分とする合金からなり、
実質的に球状であって、アルカリ水溶液中でアルミニウ
ムが溶出し易い化合物相の相対面積率（粉末断面におい
て平衡状態における化合物相の面積率を100 ％としたと
きの面積率）が70％以上であることを特徴とする。That is, the alloy powder for a catalyst of the present invention comprises an alloy containing nickel and aluminum as main components,
When the relative area ratio of the compound phase which is substantially spherical and aluminum is easily eluted in an alkaline aqueous solution (the area ratio of the compound phase in the cross section of the powder when the area ratio of the compound phase in the equilibrium state is 100%) is 70% or more. There is a feature.
【０００８】また本発明の触媒用合金粉末の製造方法
は、(a) ニッケルとアルミニウムとを主成分とする合金
の溶湯から急冷凝固法により実質的に球状の合金粉末を
作製し、次いで(b) 前記合金粉末を300 ℃〜800 ℃の温
度に保持することにより均質化処理を行うことを特徴と
する。The method for producing an alloy powder for a catalyst according to the present invention comprises the steps of: (a) producing a substantially spherical alloy powder from a molten alloy of nickel and aluminum as a main component by a rapid solidification method, and then (b) ) The homogenization treatment is performed by maintaining the alloy powder at a temperature of 300 ° C to 800 ° C.
【０００９】さらに本発明のスポンジニッケル触媒は、
(a) ニッケルとアルミニウムとを主成分とする合金の溶
湯から急冷凝固法により実質的に球状の合金粉末を作製
し、(b) 前記合金粉末を300 ℃〜800 ℃の温度に保持す
ることにより均質化処理を行い、次いで(c) 合金粉末を
アルカリ水溶液に投入することにより、大部分のアルミ
ニウムを溶出してなることを特徴とする。The sponge nickel catalyst of the present invention further comprises
(a) preparing a substantially spherical alloy powder from a molten metal of an alloy containing nickel and aluminum as main components by a rapid solidification method, and (b) maintaining the alloy powder at a temperature of 300 ° C to 800 ° C. It is characterized in that most of the aluminum is eluted by homogenizing and then (c) pouring the alloy powder into an aqueous alkaline solution.
【００１０】さらに本発明のスポンジニッケル触媒の製
造方法は、(a) ニッケルとアルミニウムとを主成分とす
る合金の溶湯から急冷凝固法により実質的に球状の合金
粉末を作製し、(b) 前記合金粉末を300 ℃〜800 ℃の温
度に保持することにより均質化処理を行い、次いで(c)
合金粉末をアルカリ水溶液に投入することにより大部分
のアルミニウムを溶出することを特徴とする。Further, the method for producing a sponge nickel catalyst of the present invention comprises the steps of (a) preparing a substantially spherical alloy powder from a molten alloy of nickel and aluminum as a main component by a rapid solidification method; A homogenization treatment is performed by maintaining the alloy powder at a temperature of 300 ° C to 800 ° C, and then (c)
Most aluminum is eluted by pouring the alloy powder into an alkaline aqueous solution.
【００１１】アルカリ水溶液中でアルミニウムが溶出し
易い化合物相は実質的にNiAl3 相である。また触媒用合
金粉末は30〜55重量％のニッケルを含有するのが好まし
い。前記合金はさらにCo、Fe、Cr、Mo、W 及びSnからな
る群から選ばれた少なくとも一種の元素を含有しても良
い。スポンジニッケル触媒を製造する均質化処理工程に
より、アルカリ水溶液中でアルミニウムが溶出し易い化
合物相の相対面積率（粉末断面において平衡状態におけ
る化合物相の面積率を100 ％としたときの面積率）は70
％以上となる。The compound phase from which aluminum is easily eluted in an alkaline aqueous solution is substantially a NiAl 3 phase. The alloy powder for a catalyst preferably contains 30 to 55% by weight of nickel. The alloy may further contain at least one element selected from the group consisting of Co, Fe, Cr, Mo, W and Sn. The relative area ratio of the compound phase from which aluminum is easily eluted in an aqueous alkaline solution by the homogenization treatment process for producing a sponge nickel catalyst (the area ratio when the area ratio of the compound phase in the equilibrium state is 100% in the powder cross section) is as follows: 70
% Or more.
【００１２】[0012]
【発明の実施の形態】[1] 合金粉末 (A) 組成 本発明を適用し得る合金は、ニッケルとアルミニウムと
を主成分とするもので、その他に助触媒として、Co、F
e、Cr、Mo、W 及びSnからなる群から選ばれた少なくと
も一種の元素を含有しても良い。BEST MODE FOR CARRYING OUT THE INVENTION [1] Alloy powder (A) Composition The alloy to which the present invention can be applied is mainly composed of nickel and aluminum.
It may contain at least one element selected from the group consisting of e, Cr, Mo, W and Sn.
【００１３】ニッケルの含有量は30〜55重量％であるの
が好ましい。ニッケルの含有量が30重量％未満であると
展開により形成されるスポンジニッケル触媒の強度が不
足し、また55重量％超であると展開によるアルミニウム
の溶出性が不足する。ニッケルのより好ましい含有量は
35〜55重量％である。また助触媒用元素の含有量は10重
量％以下が好ましい。The nickel content is preferably between 30 and 55% by weight. If the nickel content is less than 30% by weight, the strength of the sponge nickel catalyst formed by the development is insufficient, and if it exceeds 55% by weight, the elution property of aluminum due to the development is insufficient. The more preferable content of nickel is
35-55% by weight. The content of the promoter element is preferably 10% by weight or less.
【００１４】(B) 粉末化 上記組成を有する合金溶湯をアトマイズ法等の急冷凝固
法により微粉末とする。アトマイズ法の場合、アルゴン
ガス等の不活性ガス中で行なうのが好ましい。アトマイ
ズ法としては、例えば特開平5-23597 号に記載の方法を
使用しても良い。アトマイズ法により得られる合金粉末
の粒径は５〜200 μｍの範囲内にあるのが好ましく、ま
たその粒径分布はできるだけ狭いのが好ましい。(B) Powderization The molten alloy having the above composition is made into a fine powder by a rapid solidification method such as an atomizing method. In the case of the atomizing method, it is preferable to carry out in an inert gas such as argon gas. As the atomizing method, for example, a method described in JP-A-5-23597 may be used. The particle size of the alloy powder obtained by the atomization method is preferably in the range of 5 to 200 μm, and the particle size distribution is preferably as narrow as possible.
【００１５】(C) 均質化処理 ニッケル−アルミニウム合金の凝固による化合物相の生
成について検討する。例えばNiが42重量％以下の場合、
ニッケル−アルミニウム合金が凝固する過程で、下記
式： Ｌ→Ｌ＋Ni2Al3→Ｌ＋NiAl3 → NiAl3＋〔Al〕 により表される通り、まずNi2Al3相が生成され、次いで
NiAl3相が生成される。ただしＬは液相を示す。また先
に析出するNi2Al3相はアルカリ水溶液により溶出しにく
い相であり、後で析出する NiAl3相はアルカリ水溶液中
でアルミニウムが溶出し易い化合物相である。(C) Homogenization The formation of a compound phase by solidification of a nickel-aluminum alloy will be examined. For example, when Ni is 42% by weight or less,
During the process of solidification of the nickel-aluminum alloy, a Ni 2 Al 3 phase is first formed, as represented by the following equation: L → L + Ni 2 Al 3 → L + NiAl 3 → NiAl 3 + [Al]
NiAl three phases are formed. Here, L indicates a liquid phase. The Ni 2 Al 3 phase which precipitates first is a phase which is hardly eluted by an alkaline aqueous solution, and the NiAl 3 phase which precipitates later is a compound phase in which aluminum is easily eluted in an alkaline aqueous solution.
【００１６】急冷凝固する場合には、Ni2Al3相の晶出時
に過冷が進むことにより、Ni2Al3相の晶出が進み、Ｌが
減少するが、残存Ｌの組成が変化し、溶出性が良いNiAl
3 相が減少する方向へと進むと考えられる。また急冷凝
固では、Niが過飽和となるとともに、Ni2Al3相及び
液相の拡散により、NiAl3 の晶出量がさらに少なくなる
傾向を示す。In the case of rapid solidification, the supercooling proceeds during the crystallization of the Ni 2 Al 3 phase, so that the crystallization of the Ni 2 Al 3 phase proceeds and L decreases, but the composition of the remaining L changes. NiAl with good dissolution
It is thought that the three phases will decrease. In the rapid solidification, Ni becomes supersaturated, and the crystallization amount of NiAl 3 tends to further decrease due to diffusion of the Ni 2 Al 3 phase and the liquid phase.
【００１７】そこでアトマイズ法により急冷凝固したニ
ッケル−アルミニウム合金粉末に均質化処理を行うと、
合金粉末は平衡状態に近い状態となり、NiAl3 相が状態
図に近い状態となる。そのため NiAl3相の割合が多くな
り、爾後のアルカリ水溶液による展開によりアルミニウ
ムの溶出が多くなる。その結果、複雑な活性表面を有
し、良好な触媒活性を有するスポンジ状の触媒粉末が得
られると考えられる。Therefore, when the nickel-aluminum alloy powder rapidly solidified by the atomizing method is subjected to a homogenization treatment,
The alloy powder is in a state close to the equilibrium state, and the NiAl 3 phase is in a state close to the state diagram. Therefore, the proportion of the NiAl 3 phase increases, and the subsequent elution with an alkaline aqueous solution increases the elution of aluminum. As a result, it is considered that a sponge-like catalyst powder having a complex active surface and good catalytic activity is obtained.
【００１８】上記作用を有する均質化処理は、合金粉末
を300 ℃〜800 ℃の温度に保持することにより行なう。
保持温度が300 ℃未満であると、合金中の元素の拡散が
不十分であり、Ni2Al3→NiAl3 の変化が十分に起こらな
い。また800 ℃超であると合金粉末が焼結又は溶融して
一体化し、脱Al性が低下する。そのため800 ℃以下と比
較的低い温度で均質化処理を行う必要がある。より好ま
しい保持温度はNiが42重量％以下では400 〜600 ℃であ
り、またNiが42〜55重量％では600 〜800 ℃である。保
持時間は温度によるが、一般に１〜３時間程度で良い。
なお均質化処理中に合金粉末が酸化するのを防止するた
めに、アルゴンガス等の不活性ガス雰囲気中又は真空中
で行なうのが好ましい。The homogenizing treatment having the above action is performed by maintaining the alloy powder at a temperature of 300 ° C. to 800 ° C.
If the holding temperature is less than 300 ° C., the diffusion of elements in the alloy is insufficient, and the change from Ni 2 Al 3 → NiAl 3 does not sufficiently occur. On the other hand, when the temperature exceeds 800 ° C., the alloy powder is sintered or melted and integrated, and the Al removal property is reduced. Therefore, it is necessary to perform the homogenization treatment at a relatively low temperature of 800 ° C. or less. More preferably, the holding temperature is 400 to 600 ° C. when the Ni content is 42% by weight or less, and 600 to 800 ° C. when the Ni content is 42 to 55% by weight. The holding time depends on the temperature, but generally may be about 1 to 3 hours.
In order to prevent the alloy powder from being oxidized during the homogenization treatment, it is preferable to carry out the treatment in an atmosphere of an inert gas such as argon gas or in a vacuum.
【００１９】(D) 形状 本発明の触媒用合金粉末は、アトマイズ法により得られ
た場合実質的に球状である。そのため流動床法等の反応
に使用するのに好適である。(D) Shape The alloy powder for a catalyst of the present invention is substantially spherical when obtained by an atomizing method. Therefore, it is suitable for use in reactions such as a fluidized bed method.
【００２０】(E) 組織 本発明の触媒用合金粉末の組織では、アルカリ水溶液中
でアルミニウムが溶出し易い化合物相（NiAl3 相）が大
部分を占めている。この化合物相以外は実質的にアルミ
ニウム相及び／又はNi2Al3相である。(E) Structure In the structure of the alloy powder for a catalyst of the present invention, a compound phase (NiAl 3 phase) in which aluminum is easily eluted in an alkaline aqueous solution is mostly occupied. Other than this compound phase, it is substantially an aluminum phase and / or a Ni 2 Al 3 phase.
【００２１】この化合物相の相対面積率は70％以上であ
る。ここで化合物相の相対面積率とは、粉末断面におい
て平衡状態における化合物相の面積率を100 ％としたと
きの面積率であると定義できる。なお平衡状態図から読
み取れる化合物相の割合は体積率であって面積率ではな
いが、断面を厚さ方向に重ねると体積となるので、面積
率と体積率を同様のものとして扱うことができる。従っ
て、一断面についての面積率が100 ％の場合、平衡状態
における体積率が100 ％であるのと同じである。ここで
具体例を示すと、Niが41重量％でAlが59重量％の場合、
NiAl3 相の面積率が90％とすると、Ni-Al 状態図ではNi
Al3 相が97.6％であるので、NiAl3 相の相対面積率は90
／97.6≒92.2％となる。The relative area ratio of the compound phase is 70% or more. Here, the relative area ratio of the compound phase can be defined as an area ratio when the area ratio of the compound phase in the equilibrium state is 100% in the cross section of the powder. Note that the ratio of the compound phase read from the equilibrium diagram is a volume ratio and not an area ratio. However, since the volume is obtained by overlapping the cross sections in the thickness direction, the area ratio and the volume ratio can be treated as the same. Therefore, when the area ratio of one section is 100%, the volume ratio in the equilibrium state is the same as that of 100%. Here, as a specific example, when Ni is 41% by weight and Al is 59% by weight,
Assuming that the area ratio of the NiAl 3 phase is 90%, the Ni-Al phase diagram shows Ni
Since the Al 3 phase is 97.6%, the relative area ratio of the NiAl 3 phase is 90%.
/97.6≒92.2%.
【００２２】[2] スポンジニッケル触媒及びその製造方
法 (A) 展開 上記合金粉末をアルカリ水溶液に投入して展開すること
により、合金粉末中の大部分のアルミニウムを溶出させ
る。アルカリ水溶液としては、カセイソーダ水溶液を使
用するのが普通であるが、これに限定されず、アルカリ
金属の水溶液であれば良い。アルカリ水溶液の温度は50
〜110 ℃であるのが好ましい。またアルカリ水溶液の濃
度は10〜30重量％程度で良い。展開時間は温度にもよる
が、一般に30〜300 分間程度で良い。[2] Nickel sponge catalyst and method for producing the same (A) Development Most of the aluminum in the alloy powder is eluted by putting the above alloy powder into an aqueous alkaline solution and developing it. As the alkaline aqueous solution, a caustic soda aqueous solution is generally used, but the present invention is not limited to this, and an aqueous solution of an alkali metal may be used. The temperature of the alkaline aqueous solution is 50
Preferably it is ~ 110 ° C. The concentration of the aqueous alkali solution may be about 10 to 30% by weight. The development time depends on the temperature, but is generally about 30 to 300 minutes.
【００２３】(B) スポンジニッケル触媒 展開により大部分のアルミニウムが溶出しているのが好
ましい。このようにして得られるスポンジニッケル触媒
は、球状で均一な粒径分布を有するので、反応系からの
分離が容易であるのみならず、優れた活性を有する。そ
のためアセトン、ニトロベンゼン、フェノール、ブチロ
ニトリル等の各種の有機化合物の接触水素化反応に好適
である。(B) Most of the aluminum is preferably eluted by the sponge nickel catalyst development. Since the sponge nickel catalyst thus obtained has a spherical and uniform particle size distribution, it is not only easily separated from the reaction system, but also has excellent activity. Therefore, it is suitable for the catalytic hydrogenation of various organic compounds such as acetone, nitrobenzene, phenol, and butyronitrile.
【００２４】[0024]
【実施例】本発明を以下の実施例によりさらに詳細に説
明するが、本発明はそれらに限定されるものではない。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００２５】実施例１ 下記組成： サンプル１ 50wt重量％Ni−50wt重量％ Al 、及び サンプル２ 41wt重量％Ni−59wt重量％Al を有するNi-Al 合金の溶湯を耐火セラミック製ロート中
に流し込み、ロート下端より直径約５mmの溶湯流を落下
させた。その溶湯流に高圧アルゴンガスを吹き付けるこ
とにより噴霧化し、約５〜200 μm の粒径を有する球状
ニッケル−アルミニウム合金粉末を得た。次いで各合金
粉末にアルゴンガス中で700 ℃（サンプル１）又は500
℃（サンプル２）で１時間の均質化処理を行なった。 Example 1 A molten metal of a Ni-Al alloy having the following composition: Sample 1 50 wt% Ni-50 wt% Al and Sample 2 41 wt% Ni-59 wt% Al was poured into a refractory ceramic funnel. A molten metal stream having a diameter of about 5 mm was dropped from the lower end of the funnel. The molten metal stream was atomized by blowing high-pressure argon gas to obtain a spherical nickel-aluminum alloy powder having a particle size of about 5 to 200 μm. Next, each alloy powder was heated to 700 ° C (sample 1) or 500 ° C in argon gas.
A homogenization treatment was performed at 1 ° C. (sample 2) for 1 hour.
【００２６】各合金粉末について、均質化処理の前後で
それぞれ走査型電子顕微鏡（SEM ）写真を撮った。サン
プル１及び２のSEM 写真を図１及び２にそれぞれ示す。
またSEM 像の画像解析によりNiAl3 相の面積率を求め
た。結果を表１に示す。Scanning electron microscope (SEM) photographs were taken of each alloy powder before and after the homogenization treatment. SEM photographs of Samples 1 and 2 are shown in FIGS. 1 and 2, respectively.
The area ratio of the NiAl 3 phase was determined by image analysis of the SEM image. Table 1 shows the results.
【００２７】 注：＊（NiAl3 相の面積率／状態図でのNiAl3 相の比
率）×100 。[0027] Note: * (a ratio of NiAl 3 phase at an area ratio / state diagram of NiAl 3 phase) × 100.
【００２８】表１から明らかなように、急冷凝固したま
まの合金粉末では、いずれの組成でも、NiAl3 相の面積
率が低く、その相対面積率は70％未満であるが、均質化
処理を行なうとNiAl3 相の面積率が著しく向上し、その
相対面積率は70％以上になる。これは、急冷凝固したま
まの状態ではNi2Al3相が多く存在するが、均質化処理に
よりNi2Al3相がNiAl3 相に転化するためであると考えら
れる。As is evident from Table 1, in the alloy powder as it is rapidly solidified, the area ratio of the NiAl 3 phase is low and the relative area ratio is less than 70% in any composition. When this is performed, the area ratio of the NiAl 3 phase is remarkably improved, and the relative area ratio becomes 70% or more. This is considered to be because a large amount of Ni 2 Al 3 phase is present in the state of rapid solidification, but the Ni 2 Al 3 phase is converted to the NiAl 3 phase by the homogenization treatment.
【００２９】各合金粉末を濃度25重量％で95℃のカセイ
ソーダ水溶液に投入してアルミニウムを溶出させる展開
処理を行い、大部分のアルミニウムが溶出した球状スポ
ンジニッケル触媒を作製した。各触媒について、比表面
積及びフェノール活性を測定した。なおフェノール活性
は、50℃及び常圧のH2雰囲気下でフェノールを接触水素
化したときの初期活性である。測定結果を表２に示す。
表２から明らかなように、急冷凝固した合金粉末に均質
化処理を行なうことにより、比表面積が大きく、触媒活
性が向上した触媒が得られることが分かる。Each of the alloy powders was put into an aqueous solution of caustic soda at a concentration of 25% by weight at 95 ° C., and a developing process for eluting aluminum was performed to prepare a spherical sponge nickel catalyst from which most of the aluminum was eluted. The specific surface area and phenol activity were measured for each catalyst. The phenol activity is the initial activity when phenol is catalytically hydrogenated under an atmosphere of H 2 at 50 ° C. and normal pressure. Table 2 shows the measurement results.
As is clear from Table 2, it can be seen that by performing homogenization treatment on the rapidly solidified alloy powder, a catalyst having a large specific surface area and an improved catalytic activity can be obtained.
【００３０】 注＊単位：H2ml/g-Ni/hr。[0030] * Unit: H 2 ml / g-Ni / hr.
【００３１】実施例２ ニッケル5.0kg 及びアルミニウム5.0kg を高周波溶解炉
により1500℃で溶解し、得られた溶湯を耐火セラミック
製ロート中に流し込み、ロート下端より直径約５mmの溶
湯流を落下させた。その溶湯流に高圧アルゴンガスを吹
き付けることにより噴霧化し、約５〜200 μm の粒径を
有する球状ニッケル−アルミニウム合金粉末9.5kg を得
た。 Example 2 5.0 kg of nickel and 5.0 kg of aluminum were melted in a high-frequency melting furnace at 1500 ° C., and the obtained molten metal was poured into a refractory ceramic funnel, and a molten metal stream having a diameter of about 5 mm was dropped from the lower end of the funnel. . The molten metal stream was atomized by blowing a high-pressure argon gas to obtain 9.5 kg of a spherical nickel-aluminum alloy powder having a particle size of about 5 to 200 μm.
【００３２】得られた球状粉末をアルゴンガス中で700
℃×１時間の均質化処理を行った後、濃度25重量％で95
℃のカセイソーダ水溶液に投入してアルミニウムを溶出
させる展開処理を行い、大部分のアルミニウムが溶出し
た球状スポンジニッケル触媒を作製した。The obtained spherical powder was placed in an argon gas for 700 hours.
After the homogenization treatment at 1 ° C x 1 hour, 95%
The solution was poured into an aqueous solution of caustic soda at 0 ° C. and subjected to a developing process of eluting aluminum, thereby producing a spherical sponge nickel catalyst from which most of the aluminum was eluted.
【００３３】球状スポンジニッケルを700 ℃で１時間加
熱した後で、SEM 写真を撮り、SEM像の画像解析によりN
iAl3 相の面積率を求めた。その結果、NiAl3 相は37％
であることが分かった。Ni-Al 状態図より、Niが50％で
はNiAl3 相は45.7％であり、Ni2Al3相は54.3％であるの
で、NiAl3 相の相対面積率は81.0％であることが分かっ
た。After the spherical nickel sponge was heated at 700 ° C. for 1 hour, a SEM photograph was taken, and N was obtained by image analysis of the SEM image.
The area ratio of the iAl 3 phase was determined. As a result, 37% of NiAl 3 phase
It turned out to be. From the Ni-Al phase diagram, it was found that when the Ni content was 50%, the NiAl 3 phase was 45.7% and the Ni 2 Al 3 phase was 54.3%, so that the relative area ratio of the NiAl 3 phase was 81.0%.
【００３４】実施例３ ニッケル4.8kg 、アルミニウム5.0kg 、鉄0.1 kg及びク
ロム0.1kg を高周波溶解炉により溶解した。得られた溶
湯を溶解炉下部の孔より落下させ、約30000rpmの高速で
回転するボロンナイトライド円盤に当てることにより噴
霧化し、約40〜200 μm の粒径を有する球状ニッケル−
アルミニウム−鉄合金粉末9.4 kgを得た。 Example 3 4.8 kg of nickel, 5.0 kg of aluminum, 0.1 kg of iron and 0.1 kg of chromium were melted in a high frequency melting furnace. The obtained molten metal is dropped from a hole in the lower part of the melting furnace, and is atomized by being applied to a boron nitride disk rotating at a high speed of about 30,000 rpm to obtain a spherical nickel having a particle size of about 40 to 200 μm.
9.4 kg of aluminum-iron alloy powder was obtained.
【００３５】得られた球状合金粉末に対して、アルゴン
ガス中で700 ℃×１時間の均質化処理を行った後、濃度
25重量％で95℃のカセイソーダ水溶液中で展開を行い、
大部分のAlを溶出させてスポンジニッケル触媒を作製し
た。700 ℃で１時間加熱した後で撮影したSEM 像の画像
解析により、NiAl3 相の面積率を求めた。その結果、本
実施例の球状合金粉末は35％のNiAl3 相を有しているこ
とが確認された。Ni-Al 状態図より、Niが50重量％では
NiAl3 相は45.7％であり、Ni2Al3相は54.3％である。従
って、本実施例の球状合金粉末のNiAl3 相の相対面積率
は77.3％であった。The obtained spherical alloy powder was homogenized at 700 ° C. for 1 hour in an argon gas, and then subjected to a concentration
It is developed in a 25% by weight aqueous solution of caustic soda at 95 ° C.
Most of Al was eluted to produce a sponge nickel catalyst. The area ratio of the NiAl 3 phase was determined by image analysis of an SEM image taken after heating at 700 ° C. for 1 hour. As a result, it was confirmed that the spherical alloy powder of this example had a NiAl 3 phase of 35%. From the Ni-Al phase diagram, it can be seen that Ni
The NiAl 3 phase is 45.7% and the Ni 2 Al 3 phase is 54.3%. Therefore, the relative area ratio of the NiAl 3 phase in the spherical alloy powder of this example was 77.3%.
【００３６】実施例４ ニッケル５kg、アルミニウム4.5 kg及びモリブデン0.5
kgを高周波溶解炉により1450℃で溶解し、得られた溶湯
を耐火セラミック製ロート中に流し込み、ロート下端よ
り直径約５mmの溶湯流を落下させた。その溶湯流に高圧
アルゴンガスを吹き付けることにより噴霧化し、約５〜
200 μm の粒径を有する球状ニッケル−アルミニウム合
金粉末9.5 kgを得た。 Example 4 5 kg of nickel, 4.5 kg of aluminum and 0.5 of molybdenum
kg was melted in a high-frequency melting furnace at 1450 ° C., and the obtained molten metal was poured into a refractory ceramic funnel, and a molten metal stream having a diameter of about 5 mm was dropped from the lower end of the funnel. The molten metal stream is atomized by blowing high-pressure argon gas, and is
9.5 kg of spherical nickel-aluminum alloy powder having a particle size of 200 μm were obtained.
【００３７】得られた球状合金粉末に対してアルゴンガ
ス中で700 ℃×１時間の均質化処理を行った後で、濃度
25重量％で95℃のカセイソーダ水溶液中で展開を行うこ
とにより大部分のAlを溶出させて、ニッケル−モリブデ
ン系スポンジニッケル触媒を作製した。700 ℃で１時間
加熱した後実施例１と同様にして、NiAl3 相の面積率を
求めた。その結果、NiAl3 相を32.4％有していることが
確認できた。Ni-Al 状態図より、Niが50重量％ではNiAl
3 相は45.7％であり、Ni2AI3相は54.3％であるので、本
実施例の合金粉末のNiAl3 相の相対面積率は70.9％であ
った。The obtained spherical alloy powder was subjected to a homogenization treatment at 700 ° C. × 1 hour in an argon gas, and then the concentration was reduced.
Most of Al was eluted by developing in a 25% by weight aqueous solution of caustic soda at 95 ° C to prepare a nickel-molybdenum sponge nickel catalyst. After heating at 700 ° C. for 1 hour, the area ratio of the NiAl 3 phase was determined in the same manner as in Example 1. As a result, it was confirmed that the NiAl 3 phase had 32.4%. According to the Ni-Al phase diagram, NiAl
Since the three phases were 45.7% and the Ni 2 AI 3 phase was 54.3%, the relative area ratio of the NiAl 3 phase in the alloy powder of this example was 70.9%.
【００３８】比較例１〜３ 実施例２〜４において均質化処理を施す前の合金粉末を
それぞれ比較例１〜３の前駆合金粉末とする。それらの
前駆合金粉末の組成及びNiAl3 相の相対面積率は下記表
３に示す通りである。これらの合金粉末を濃度25重量％
で95℃のカセイソーダ水溶液中で展開を行うことにより
大部分のAlを溶出させて、スポンジニッケル触媒を作製
した。 Comparative Examples 1 to 3 In Examples 2 to 4, the alloy powders before being subjected to the homogenization treatment are referred to as precursor alloy powders of Comparative Examples 1 to 3, respectively. The composition of the precursor alloy powder and the relative area ratio of the NiAl 3 phase are as shown in Table 3 below. 25% by weight of these alloy powders
Most of the Al was eluted by developing in a caustic soda aqueous solution at 95 ° C to produce a sponge nickel catalyst.
【００３９】実施例５ 実施例２〜４及び比較例１で調製した触媒を使用し、50
0 ｍｌの電磁攪拌式オートクレーブにより、ニトロベン
ゼン、アジポニトリル、及びグルコースの接触水素化反
応を行い、反応生成物をＧＣ分析又はＨＰＬＣ分析し、
原料の転化率を求めた。結果を表４に示す。 Example 5 Using the catalysts prepared in Examples 2 to 4 and Comparative Example 1, 50
A catalytic hydrogenation reaction of nitrobenzene, adiponitrile, and glucose was performed in a 0 ml electromagnetic stirring type autoclave, and the reaction product was analyzed by GC or HPLC.
The conversion of the raw material was determined. Table 4 shows the results.
【００４０】表４ Table 4
【００４１】[0041]
【発明の効果】以上詳述した通り、本発明によればアト
マイズ法により作製したニッケル−アルミニウム合金の
球状粉末に対して、均質化処理を行なった後でアルカリ
水溶液により展開を行なうので、アルミニウムの溶出を
十分に行なうことができる。そのため、得られるスポン
ジニッケル触媒は比表面積が大きく、触媒活性に優れて
いる。本発明のスポンジニッケル触媒は各種の有機化合
物の接触還元反応に広く使用することができる。As described above in detail, according to the present invention, the spherical powder of the nickel-aluminum alloy produced by the atomization method is subjected to homogenization treatment and then developed with an aqueous alkali solution, so that the aluminum powder is developed. Elution can be sufficiently performed. Therefore, the obtained sponge nickel catalyst has a large specific surface area and is excellent in catalytic activity. The sponge nickel catalyst of the present invention can be widely used for a catalytic reduction reaction of various organic compounds.
【図１】 サンプル１のニッケル−アルミニウム合金の
組織を表す走査型電子顕微鏡写真（4000倍）であり、
(a) はガスアトマイズ法により急冷凝固したままの状態
を示し、(b) は均質化処理後の状態を示す。FIG. 1 is a scanning electron micrograph (× 4000) showing the structure of a nickel-aluminum alloy of Sample 1.
(a) shows the state after rapid solidification by gas atomization, and (b) shows the state after homogenization.
【図２】 サンプル２のニッケル−アルミニウム合金の
組織を表す走査型電子顕微鏡写真（4000倍）であり、
(a) はガスアトマイズ法により急冷凝固したままの状態
を示し、(b) は均質化処理後の状態を示す。FIG. 2 is a scanning electron micrograph (× 4000) showing the structure of a nickel-aluminum alloy of Sample 2.
(a) shows the state after rapid solidification by gas atomization, and (b) shows the state after homogenization.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２２Ｆ 9/08 Ｂ２２Ｆ 9/08 Ａ Ｃ０７Ｃ 29/156 Ｃ０７Ｃ 29/156 29/19 29/19 31/26 31/26 35/08 35/08 209/36 209/36 209/48 209/48 209/72 209/72 211/12 211/12 211/35 211/35 Ｃ２２Ｃ 1/04 Ｃ２２Ｃ 1/04 Ｂ 19/03 19/03 Ｚ 21/00 21/00 Ｎ 30/02 30/02 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Ｃ２２Ｆ 1/00 ６２１ Ｃ２２Ｆ 1/00 ６２１ ６４１ ６４１Ａ ６８２ ６８２ ６８７ ６８７ ６９１ ６９１Ｂ (72)発明者 中村 秀樹 島根県安来市安来町2107番地２ 日立金属 株式会社冶金研究所内 (72)発明者 平山 秀二 群馬県邑楽郡明和町大佐貫22 日興リカ株 式会社群馬工場内 (72)発明者 坂村 秀樹 群馬県邑楽郡明和町大佐貫22 日興リカ株 式会社群馬工場内 (72)発明者 関本 学 群馬県邑楽郡明和町大佐貫22 日興リカ株 式会社群馬工場内 Ｆターム(参考） 4G069 AA02 AA08 BA17 BB03A BB03B BB05B BC02B BC16A BC16B BC59B BC66B BC68A BC68B CB02 DA05 EA01X EA01Y FA01 FA08 FB04 FC02 FC04 FC08 4H006 AA05 AC11 AC41 AC52 BA14 BA21 BA61 BB61 BC10 BC11 BC19 BN20 FG60 4H039 CA60 CA71 CB10 CB20 CB30 CB40 4K017 AA04 BA01 BA03 BB01 BB04 BB06 CA01 DA09 EB00 FA03 4K018 BA04 BA08 BA09 BA13 BA20 BB04 BB06 BC01 BD10 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) B22F 9/08 B22F 9/08 A C07C 29/156 C07C 29/156 29/19 29/19 31/26 31 / 26 35/08 35/08 209/36 209/36 209/48 209/48 209/72 209/72 211/12 211/12 211/35 211/35 C22C 1/04 C22C 1/04 B 19/03 19/03 Z 21/00 21/00 N 30/02 30/02 // C07B 61/00 300 C07B 61/00 300 C22F 1/00 621 C22F 1/00 621 641 641A 682 682 687 687 691 691B (72) Inventor Hideki Nakamura 2107-2 Yasugi-cho, Yasugi City, Shimane Pref.Hitachi Metals Co., Ltd. Hideki Sakamura Akira Oraku-gun, Gunma Prefecture 22 Osanuki-machi, Nikko Rika Co., Ltd. Gunma Plant (72) Inventor Manabu Sekimoto, 22 Meiwa-cho, Euraku-gun, Gunma Prefecture, Nikko Rika Co., Ltd. Gunma Plant F-term (reference) 4G069 AA02 AA08 BA17 BB03A BB03B BB05B BC02B BC16A BC16B BC59B BC66B BC68A BC68B CB02 DA05 EA01X EA01Y FA01 FA08 FB04 FC02 FC04 FC08 4H006 AA05 AC11 AC41 AC52 BA14 BA21 BA61 BB61 BC10 BC11 BC19 BN20 FG60 4H039 CA60 CA71 CB10 CB20 CB30 BA04 BA03 BA04 BA03 BA04 BA03 BA04 BA03 BA04 BA03 BA09 BA13 BA20 BB04 BB06 BC01 BD10
Claims (13)
る合金からなる実質的に球状の触媒用合金粉末であっ
て、アルカリ水溶液中でアルミニウムが溶出し易い化合
物相の相対面積率（粉末断面において平衡状態における
化合物相の面積率を100 ％としたときの面積率）が70％
以上であることを特徴とする触媒用合金粉末。1. A substantially spherical catalyst alloy powder comprising an alloy containing nickel and aluminum as main components, and a relative area ratio of a compound phase in which aluminum is easily eluted in an alkaline aqueous solution (equilibrium in the powder cross section). Area ratio when the area ratio of the compound phase in the state is 100%) is 70%
An alloy powder for a catalyst characterized by the above.
て、前記化合物相が実質的にNiAl3 相であることを特徴
とする触媒用合金粉末。2. The catalyst alloy powder according to claim 1, wherein the compound phase is substantially a NiAl 3 phase.
において、30〜55重量％のニッケルを含有することを特
徴とする触媒用合金粉末。3. The alloy powder for a catalyst according to claim 1, wherein the alloy powder contains 30 to 55% by weight of nickel.
合金粉末において、前記合金がさらにCo、Fe、Cr、Mo、
W 及びSnからなる群から選ばれた少なくとも一種の元素
を含有することを特徴とする触媒用合金粉末。4. The catalyst alloy powder according to claim 1, wherein the alloy further comprises Co, Fe, Cr, Mo,
An alloy powder for a catalyst, comprising at least one element selected from the group consisting of W and Sn.
合金粉末において、粒径が実質的に200 μｍ以下である
ことを特徴とする触媒用合金粉末。5. The catalyst alloy powder according to claim 1, wherein the particle size is substantially 200 μm or less.
合金粉末の製造方法において、(a) ニッケルとアルミニ
ウムとを主成分とする合金の溶湯から急冷凝固法により
実質的に球状の合金粉末を作製し、次いで(b) 前記合金
粉末を300 ℃〜800 ℃の温度に保持することにより均質
化処理を行うことを特徴とする方法。6. The method for producing an alloy powder for a catalyst according to any one of claims 1 to 5, wherein (a) a substantially spherical metal is formed from a molten metal of an alloy mainly containing nickel and aluminum by a rapid solidification method. (B) a method comprising: preparing an alloy powder; and (b) performing a homogenization treatment by maintaining the alloy powder at a temperature of 300 ° C to 800 ° C.
質化処理により、アルカリ水溶液中でアルミニウムが溶
出し易い化合物相の相対面積率を70％以上とすることを
特徴とする方法。7. The method according to claim 6, wherein the homogenization treatment sets the relative area ratio of the compound phase in which aluminum is easily eluted in an aqueous alkaline solution to 70% or more.
合金粉末からなるスポンジニッケル触媒であって、(a)
ニッケルとアルミニウムとを主成分とする合金の溶湯か
ら急冷凝固法により実質的に球状の合金粉末を作製し、
(b) 前記合金粉末を300 ℃〜800 ℃の温度に保持するこ
とにより均質化処理を行い、次いで(c) 合金粉末をアル
カリ水溶液に投入することにより、大部分のアルミニウ
ムを溶出してなることを特徴とするスポンジニッケル触
媒。8. A sponge nickel catalyst comprising the alloy powder for a catalyst according to any one of claims 1 to 5, wherein (a)
Producing a substantially spherical alloy powder from a melt of an alloy containing nickel and aluminum as main components by a rapid solidification method,
(b) A homogenization treatment is performed by maintaining the alloy powder at a temperature of 300 ° C to 800 ° C, and then (c) most of the aluminum is eluted by pouring the alloy powder into an alkaline aqueous solution. A sponge nickel catalyst comprising:
において、前記均質化処理により、アルカリ水溶液中で
アルミニウムが溶出し易い化合物相の相対面積率（粉末
断面において平衡状態における化合物相の面積率を100
％としたときの面積率）が70％以上であることを特徴と
するスポンジニッケル触媒。9. The sponge nickel catalyst according to claim 8, wherein the homogenization treatment causes a relative area ratio of a compound phase in which aluminum is easily eluted in an alkaline aqueous solution (an area ratio of a compound phase in an equilibrium state in a cross section of the powder). 100
% Sponge nickel catalyst having an area ratio of 70% or more.
において、アルカリ水溶液中でアルミニウムが溶出し易
い化合物相が実質的にNiAl3 相であることを特徴とする
スポンジニッケル触媒。10. The sponge nickel catalyst according to claim 9, wherein the compound phase from which aluminum is easily eluted in an aqueous alkaline solution is substantially a NiAl 3 phase.
ジニッケル触媒において、前記合金粉末が30〜55重量％
のニッケルを含有することを特徴とするスポンジニッケ
ル触媒。11. The sponge nickel catalyst according to claim 8, wherein the alloy powder is 30 to 55% by weight.
A sponge nickel catalyst comprising: nickel.
ジニッケル触媒を製造する方法であって、(a) ニッケル
とアルミニウムとを主成分とする合金の溶湯から急冷凝
固法により実質的に球状の合金粉末を作製し、(b) 前記
合金粉末を300 ℃〜800 ℃の温度に保持することにより
均質化処理を行い、次いで(c) 合金粉末をアルカリ水溶
液に投入することにより、大部分のアルミニウムを溶出
し、スポンジ状とすることを特徴とする方法。12. A method for producing a sponge nickel catalyst according to any one of claims 8 to 11, comprising: (a) substantially quenching and solidifying a molten metal of an alloy containing nickel and aluminum as main components. A spherical alloy powder is prepared, (b) the alloy powder is homogenized by maintaining the alloy powder at a temperature of 300 ° C. to 800 ° C., and (c) most of the alloy powder is poured into an alkaline aqueous solution. Eluting aluminum into a sponge.
の製造方法において、前記均質化処理により、アルカリ
水溶液中でアルミニウムが溶出し易い化合物相の相対面
積率（粉末断面において平衡状態における化合物相の面
積率を100 ％としたときの面積率）を70％以上とするこ
とを特徴とする方法。13. The method for producing a sponge nickel catalyst according to claim 12, wherein, by the homogenization treatment, a relative area ratio of a compound phase in which aluminum is easily eluted in an alkaline aqueous solution (a ratio of the compound phase in an equilibrium state in a cross section of the powder). A method characterized in that the area ratio (when the area ratio is 100%) is 70% or more.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7084302B2 (en) | 2003-07-04 | 2006-08-01 | Sinorgchem Shandong Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US7176333B2 (en) | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
| CN101613817B (en) * | 2008-06-27 | 2010-08-11 | 中国科学院金属研究所 | Application of nickel aluminum-based composite material as high temperature self-lubricating abrasion-proof material |
| US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
-
2000
- 2000-01-11 JP JP2000003002A patent/JP2001192701A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7084302B2 (en) | 2003-07-04 | 2006-08-01 | Sinorgchem Shandong Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US7176333B2 (en) | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
| US7235694B2 (en) | 2003-07-04 | 2007-06-26 | Sinorgchem Co., Shandong | Process for preparing 4-aminodiphenylamine |
| US7989662B2 (en) | 2003-07-04 | 2011-08-02 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US8293673B2 (en) | 2003-07-04 | 2012-10-23 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US9029603B2 (en) | 2003-07-04 | 2015-05-12 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing alkylated p-phenylenediamines |
| CN101613817B (en) * | 2008-06-27 | 2010-08-11 | 中国科学院金属研究所 | Application of nickel aluminum-based composite material as high temperature self-lubricating abrasion-proof material |
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