JPS61119606A - Production of amorphous metallic powder - Google Patents
Production of amorphous metallic powderInfo
- Publication number
- JPS61119606A JPS61119606A JP24206684A JP24206684A JPS61119606A JP S61119606 A JPS61119606 A JP S61119606A JP 24206684 A JP24206684 A JP 24206684A JP 24206684 A JP24206684 A JP 24206684A JP S61119606 A JPS61119606 A JP S61119606A
- Authority
- JP
- Japan
- Prior art keywords
- sulfate
- powder
- nickel
- amorphous
- reaction
- 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
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
(産業上の利用分野)
本発明は、−酸化炭素(Co)、−酸化窒素(No)の
水素反応に使用する触媒の製法に関するものであり、反
応速度が早く、表面積の大きいニッケル(N i )
−R(P)−アモルファス触媒として使用されるもので
ある。[Detailed description of the invention] [Object of the invention] (Industrial application field) The present invention relates to a method for producing a catalyst used in the hydrogen reaction of -carbon oxide (Co) and -nitrogen oxide (No), Nickel (N i ) has a fast reaction rate and a large surface area.
-R(P)- It is used as an amorphous catalyst.
(従来の技術)
従来のN1−Pアモルファス触媒を製造する方法として
は、液体急冷法があり、化学工学雑誌(VOL 47.
P41.1983) ニN 1soPzoノ組成で
厚さ18μmのリボンを急冷法により製造し、比表面積
(BET、Nz)が0.2rrr/gである旨開示され
ており、更にアモルファス粉末の製造法として゛ スプ
レー法、アトマイズ法、キャビテーション法により気体
中で液滴を粒径にする製法がある。(Prior Art) As a conventional method for producing N1-P amorphous catalyst, there is a liquid quenching method, which is described in the Journal of Chemical Engineering (VOL 47.
P41.1983) It is disclosed that a ribbon with a thickness of 18 μm having a composition of 2N1soPzo is manufactured by a rapid cooling method, and the specific surface area (BET, Nz) is 0.2rrr/g, and furthermore, a method for manufacturing an amorphous powder is described. There are manufacturing methods that reduce the size of droplets in a gas using the spray method, atomization method, and cavitation method.
(発明が解決しようとする問題点)
しかしながら、前記リボン急冷法は、リボンに連続性を
持たせるために、おのずと厚さに限界があって飛躍的に
表面積を大きくすることは困難でまた前記他の製法にお
いても、微粉末の製法は困難であり、例えば超音波アト
マイズ法では12.5〜6.5μmの粒径が製造でき、
これより小さい粒径は困難である。(Problems to be Solved by the Invention) However, in the ribbon quenching method, in order to provide continuity to the ribbon, there is a natural limit to the thickness, and it is difficult to dramatically increase the surface area. Even in the manufacturing method, it is difficult to manufacture fine powder. For example, the ultrasonic atomization method can produce particles with a particle size of 12.5 to 6.5 μm.
Particle sizes smaller than this are difficult.
そこで、本発明は、アモルファス粉末の粒径を極力小さ
くして重量当りの表面積を大きくすることを、技術的課
題とするものである。Therefore, the technical object of the present invention is to increase the surface area per weight by reducing the particle size of amorphous powder as much as possible.
(問題点を解決するための手段)
上記技術的課題を解決するために講じた手段は、水溶液
中での金属イオンを化学的に還元して、極小粒子を製造
するもので、塩化ニッケル、硫酸ニッケルなどのニッケ
ル塩、還元剤として次亜リン酸塩、錯化剤1反応開始剤
として亜リン酸塩。(Means for solving the problem) The method taken to solve the above technical problem was to chemically reduce metal ions in an aqueous solution to produce ultrasmall particles. Nickel salt such as nickel, hypophosphite as a reducing agent, phosphite as a complexing agent 1 reaction initiator.
リン析出促進剤としてN−(2ヒドロキシエチル)・エ
チレンジアミン−N、N’ 、N’ −トリ酢酸トリ
アルカリ金属塩(以下C1゜H+5NiNa30、とい
う)と、硫酸アンモニウム、硫酸リチウム、硫酸カリウ
ム、硫酸ナトリウムの硫酸塩から選ばれる1種類または
、2種類以上の成分からなる水溶液を80〜100℃の
高温にしてニッケルーイオン還元反応を行い、アモルフ
ァスN1−P粉末を析出し製造するものである。As a phosphorus precipitation accelerator, N-(2hydroxyethyl)-ethylenediamine-N,N',N'-triacetic acid trial-alkali metal salt (hereinafter referred to as C1°H+5NiNa30) and ammonium sulfate, lithium sulfate, potassium sulfate, and sodium sulfate were used. An aqueous solution consisting of one or more components selected from sulfates is heated to a high temperature of 80 to 100°C to perform a nickel ion reduction reaction to precipitate and produce amorphous N1-P powder.
また、Co、Noの水素化反応に高活性を示すN1ao
Proという高リン含有率については前記化学工学にも
記載されており、アモルファス粉末を析出させる反応液
にC3゜H15Nt N a 307及び前記硫酸塩を
添加して15〜20at%のP含有率を確保したもので
ある。In addition, N1ao exhibits high activity in hydrogenation reactions of Co and No.
The high phosphorus content called Pro is also described in the above chemical engineering, and a P content of 15 to 20 at% is secured by adding C3°H15Nt Na 307 and the above sulfate to the reaction solution from which amorphous powder is precipitated. This is what I did.
(作用)
前記技術的手段は次のようである。すなわち、水溶液を
A液とB液とし、A液にはCIo H+ s N zN
a、0.と前記硫酸塩を添加したものである。(Operation) The technical means is as follows. That is, the aqueous solutions are A liquid and B liquid, and A liquid contains CIo H+ s N zN
a, 0. and the above-mentioned sulfate were added.
A液 N i Cj’ z →30 g /
II拘儲酸N a −50g / ILi、
SO4→25 g/I
CIoHrsNz Na3− 07 /1サッカリンN
a −1g/j2
B tM N i Cl z −30g
/ 1拘儲酸N a −50g / 1サツカ
リンNa → 1g/l
第、表は、試料、1〜.砿つい−coアエ7い、
”アス粉末の析出状況を示す。漱1〜隘3について
最小粒径も小さくPat+m%も16.0以上を示し、
総合評価として多少の測定誤差もあるが、良好と判断さ
れる。A liquid N i Cj' z →30 g /
II binding acid Na -50g/ILi,
SO4 → 25 g/I CIoHrsNz Na3- 07 /1 Saccharin N
a -1g/j2 B tM N i Cl z -30g
/ 1 acidic acid Na -50g / 1 saccharin Na → 1g/l The table shows samples 1 to 1. Kokitsui-co Ae7i,
” Shows the precipitation status of asbestos powder. For Sho 1 to Sho 3, the minimum particle size is small and Pat+m% is 16.0 or more.
Although there are some measurement errors, the overall evaluation is judged to be good.
尚、前記化学工学の文献より、N1aop2oに示すP
#20の場合において最も活性化を示すものであると記
載されており、第2表の総合判定の評価として、■写真
による粒度の細かさ及び■Pの成分が20に近い16.
5atm%ものについての評価を行った。Furthermore, from the chemical engineering literature mentioned above, P shown in N1aop2o
It is stated that #20 shows the most activation, and as an overall evaluation in Table 2, ■ fineness of particle size as seen in the photograph and ■ P component close to 20 is 16.
An evaluation was performed on a 5 atm% product.
(実施例) 以下、本発明に係る具体的な実施例について説明する。(Example) Hereinafter, specific examples according to the present invention will be described.
実施例−1塩化ニッケル 30 g / IA
浴種 次亜リン酸ナトリウム 30g/β試料患3 亜
リン酸ナトリウム 40g/βC10H15Nz N
az o? 3 g/l硫酸リチウム 2
5g/n
サッカリンナトリウム l g/l
拘儲酸ナトリウム 50g/7!
からなる水溶液を、PH−7に調整し、浴温を90℃以
上に高め、反応させ、アモルファスN1−P粉末を得た
。Example-1 Nickel chloride 30 g/IA
Bath type Sodium hypophosphite 30g/β sample patient 3 Sodium phosphite 40g/βC10H15Nz N
az o? 3 g/l lithium sulfate 2
5g/n Sodium saccharin l g/l Sodium saccharin 50g/7! The aqueous solution consisting of was adjusted to pH-7, the bath temperature was raised to 90°C or higher, and the reaction was carried out to obtain amorphous N1-P powder.
前記粉末のN1−P組成及び粒径をEPMA及び顕微鏡
で測定した結果、P含有率9粒径は、P原子% 17
.2at%
平均粒径 1μm
であった。As a result of measuring the N1-P composition and particle size of the powder using EPMA and a microscope, the P content 9 particle size was P atomic % 17
.. The average particle size was 2 at% and 1 μm.
次に、前記第1表のNQ1〜7のアモルファス粒度の1
000倍の顕微鏡写真の状況を第1図に示す。Next, 1 of the amorphous particle size of NQ1-7 in Table 1 above.
Fig. 1 shows the situation in a micrograph taken at a magnification of 1,000 times.
本発明は次の特有の効果を有する。すなわち、従来の液
体急冷法で製造した触媒を、比表面積を大きくするため
に、ロール法によって製造したリボンや、アトマイズ法
によって製造した粉末を微細に粉砕することも考えられ
るが、硬度が高(、高強度のアモルファスを粉砕するに
は粉砕効果が悪く、多大なエネルギーと長時間を要し、
更に粒度を均一にすることが困難で、歩留りが悪い。然
し、本発明の製造法は、微粉末の反応液内の滞留時間を
一定にすることにより粒径を均一にすることができ、ま
た反応液内の滞留時間が長くても、粒子の析出形態がブ
ドウの房のように小粒子が寄り集まった群落の形で析出
し、増大してゆ(ので群落なる粉末をミルにかけ、軽く
粉砕すれば小粒子1つ1つが簡単に分離でき、粒度の小
粒子が製造することができる。The present invention has the following unique effects. In other words, in order to increase the specific surface area of the catalyst produced by the conventional liquid quenching method, it is possible to finely pulverize the ribbon produced by the roll method or the powder produced by the atomization method; , crushing high-strength amorphous materials has poor pulverizing effect and requires a large amount of energy and a long time.
Furthermore, it is difficult to make the particle size uniform, resulting in poor yield. However, in the production method of the present invention, the particle size can be made uniform by keeping the residence time of the fine powder in the reaction solution constant, and even if the residence time in the reaction solution is long, the precipitation form of the particles can be made uniform. The particles precipitate in the form of clusters of small particles gathered together like a bunch of grapes, and increase in size. Small particles can be produced.
次に、N1−PアモルファスのP含有率を上げる手段と
して、PHを下げる方法が・あるが、PHを下げると粉
末の析出スピードが低下するが、本発明は1);■記の
如くリン析出促進剤を添加することにより、反応スピー
ドを低下させずに高いP含有率を確保できるものである
。Next, there is a method of lowering the PH as a means of increasing the P content of N1-P amorphous, but lowering the PH lowers the precipitation speed of the powder, but the present invention does not allow phosphorus precipitation as described in 1); By adding a promoter, a high P content can be ensured without reducing the reaction speed.
図は1000倍の顕微鏡写真の図で、(1)〜(5)は
本実施例、(6)〜(7)は従来例によるものである。The figures are micrographs taken at a magnification of 1000 times, in which (1) to (5) are those of the present embodiment, and (6) to (7) are those of the conventional example.
Claims (1)
(2)還元剤としての次亜リン酸塩、(3)錯化剤、(
4)反応開始剤としての亜リン酸塩、(5)リン析出促
進剤としてのN−(2ヒドロキシエチル)・エチレンジ
アミン−N,N′,N′−トリ酢酸トリアルカリ金属塩
(C_1_0H_1_5N_2Na_3O_7)と硫酸
アンモニウム、硫酸リチウム、硫酸カリウム、硫酸ナト
リウムの硫酸塩から選ばれる1種類、または1種類以上
の成分からなる水溶液を70〜100℃の温度とし、ニ
ッケルイオン還元反応を進行させ、アモルファスNi−
P粉末を析出させる非晶質金属粉の製造方法。(1) Nickel salts such as nickel chloride and nickel sulfate,
(2) hypophosphite as a reducing agent, (3) a complexing agent, (
4) Phosphite as a reaction initiator, (5) N-(2hydroxyethyl)-ethylenediamine-N,N',N'-triacetic acid trial-alkali metal salt (C_1_0H_1_5N_2Na_3O_7) and ammonium sulfate as phosphorus precipitation accelerators , lithium sulfate, potassium sulfate, sodium sulfate, or one or more components selected from the group consisting of sulfates of lithium sulfate, potassium sulfate, and sodium sulfate.
A method for producing amorphous metal powder by precipitating P powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24206684A JPS61119606A (en) | 1984-11-15 | 1984-11-15 | Production of amorphous metallic powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24206684A JPS61119606A (en) | 1984-11-15 | 1984-11-15 | Production of amorphous metallic powder |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61119606A true JPS61119606A (en) | 1986-06-06 |
Family
ID=17083769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24206684A Pending JPS61119606A (en) | 1984-11-15 | 1984-11-15 | Production of amorphous metallic powder |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61119606A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009197317A (en) * | 2007-10-18 | 2009-09-03 | Hitachi Metals Ltd | REDUCTION PRECIPITATION TYPE SPHERICAL NiP PARTICLE AND PRODUCTION METHOD THEREOF |
CN113134623A (en) * | 2021-04-28 | 2021-07-20 | 西北工业大学 | Water-soluble amorphous noble metal nano particle and preparation method thereof |
-
1984
- 1984-11-15 JP JP24206684A patent/JPS61119606A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009197317A (en) * | 2007-10-18 | 2009-09-03 | Hitachi Metals Ltd | REDUCTION PRECIPITATION TYPE SPHERICAL NiP PARTICLE AND PRODUCTION METHOD THEREOF |
CN113134623A (en) * | 2021-04-28 | 2021-07-20 | 西北工业大学 | Water-soluble amorphous noble metal nano particle and preparation method thereof |
CN113134623B (en) * | 2021-04-28 | 2022-06-03 | 西北工业大学 | Water-soluble amorphous noble metal nano particle and preparation method thereof |
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