JPH0371171B2 - - Google Patents
Info
- Publication number
- JPH0371171B2 JPH0371171B2 JP61117530A JP11753086A JPH0371171B2 JP H0371171 B2 JPH0371171 B2 JP H0371171B2 JP 61117530 A JP61117530 A JP 61117530A JP 11753086 A JP11753086 A JP 11753086A JP H0371171 B2 JPH0371171 B2 JP H0371171B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- zeolite
- oxygen
- weight
- oxygen scavenger
- 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.)
- Expired - Lifetime
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- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Drying Of Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は除湿能を有する脱酸素剤に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen scavenger having dehumidifying ability.
脱酸素剤としては還元鉄、又は第１鉄塩に酸化
促進剤を配合した鉄系酸素吸収剤があり、鉄と酸
素の反応性を向上するために酸化促進剤の配合法
に種々の提案がなされている。
Oxygen scavengers include reduced iron or iron-based oxygen absorbers made by blending oxidation promoters with ferrous salts, and various proposals have been made for blending oxidation promoters in order to improve the reactivity between iron and oxygen. being done.
例えば特公昭61−8741号公報では、表面活性化
した還元鉄粉と、NaCl等の電解質を含む水溶液
をゼオライト等の多孔質充填剤に担持させた酸化
促進成分から成る脱酸素剤組成物が開示されてい
る。 For example, Japanese Patent Publication No. 61-8741 discloses an oxygen scavenger composition consisting of surface-activated reduced iron powder and an oxidation promoting component in which an aqueous solution containing an electrolyte such as NaCl is supported on a porous filler such as zeolite. has been done.
又、除湿剤としては塩化カルシウム、シリカゲ
ル、ゼオライトなどがある。しかしながら除湿能
をも有する脱酸素剤は知られていない。 Further, examples of dehumidifying agents include calcium chloride, silica gel, and zeolite. However, no oxygen scavenger is known that also has dehumidifying ability.
精密機器、電子部品等、或いはある種の食品の
保存に際しては、酸素と同時に水分も除去するこ
とが重要である。従来の鉄系酸素吸収剤は鉄の酸
化、いわゆる錆びを生成する反応を利用したもの
であつて、水分とハロゲン化物等の促進成分の共
存下でないと反応が遅く、乾燥雰囲気下では使用
することができず、腐食性物質を含むといつた問
題点がある。
When preserving precision instruments, electronic parts, etc., or certain types of food, it is important to remove moisture as well as oxygen. Conventional iron-based oxygen absorbers utilize the oxidation of iron, a reaction that produces so-called rust, and the reaction is slow unless moisture and promoting components such as halides coexist, so they cannot be used in a dry atmosphere. There are problems in that it cannot be used as a fuel and contains corrosive substances.
本発明者等は微細なニツケル金属を還元し、活
性化すると乾燥雰囲気下でも酸素吸収能力が高い
ことを見出し、本発明に到達した。すなわち、本
発明は除湿能をも伴せ有する新規な脱酸素剤を提
供するものである。更には腐食性物質を含有しな
い脱酸素剤を提供するものである。 The present inventors have discovered that when fine nickel metal is reduced and activated, it has a high oxygen absorption ability even in a dry atmosphere, and has thus arrived at the present invention. That is, the present invention provides a novel oxygen scavenger that also has dehumidifying ability. Furthermore, the present invention provides an oxygen scavenger that does not contain corrosive substances.
本発明の目的は、活性な担持型ニツケル金属10
〜70重量％とゼオライトを主成分とし、腐食性物
質を含まないことを特徴とする脱酸素剤により達
成される。
The object of the present invention is to provide active supported nickel metal 10
This is achieved by using an oxygen scavenger that is characterized by containing ~70% by weight and zeolite as a main component and does not contain corrosive substances.
本発明における活性なニツケル金属としては、
例えば還元性、又は分解性ニツケル化合物があ
る。 The active nickel metal in the present invention includes:
For example, there are reducible or degradable nickel compounds.
還元性ニツケル化合物としてはニツケルの硫酸
塩、炭素塩、硝酸塩、塩化物が好ましく、又分解
性ニツケル化合物としてはギ酸ニツケル、シユウ
酸ニツケルが好ましく用いられる。 As the reducible nickel compound, nickel sulfate, carbonate, nitrate, and chloride are preferable, and as the degradable nickel compound, nickel formate and nickel oxalate are preferably used.
本発明においては、かかる活性なニツケル金属
は担持されていることが必要であり、活性な担持
型ニツケル金属として用いられることが重要であ
る。ここでニツケル化合物はゼオライト上に直接
担持せしめても良く、或いはシリカ、アルミナ、
ケイソウ土等の担体に担持せしめた後、ゼオライ
トと混合することもできる。 In the present invention, such active nickel metal must be supported, and it is important that it be used as an active supported nickel metal. Here, the nickel compound may be directly supported on zeolite, or silica, alumina,
It can also be supported on a carrier such as diatomaceous earth and then mixed with zeolite.
本発明におけるゼオライトは合成ゼオライト又
は天然ゼオライトの何れもが使用可能であるが、
本邦で大量に産出する天然モルデナイト、天然ク
リノプチロライトが好ましい。 The zeolite in the present invention can be either a synthetic zeolite or a natural zeolite, but
Natural mordenite and natural clinoptilolite, which are produced in large quantities in Japan, are preferred.
脱酸素剤中のニツケル金属量とゼオライト量
は、ニツケル金属として10〜70重量％、ゼオライ
ト成分として（天然ゼオライトの場合は共存成分
を含む見掛けの量）30〜90重量％であることが必
要である。 The amount of nickel metal and zeolite in the oxygen scavenger must be 10 to 70% by weight as nickel metal and 30 to 90% by weight as the zeolite component (in the case of natural zeolite, the apparent amount including coexisting components). be.
本発明の脱酸素剤は活性なニツケルとゼオライ
トを含むことを必須とするが、例えばニツケル金
属とゼオライトを混合し、適当な形状に成形後、
還元雰囲気下で加熱処理し、ニツケル及びゼオラ
イトの活性化を行つて製造することができる。 The oxygen scavenger of the present invention must contain active nickel and zeolite. For example, after mixing nickel metal and zeolite and molding it into an appropriate shape,
It can be produced by heating nickel and zeolite in a reducing atmosphere to activate them.
これら両成分の混合法には従来から知られてい
る種々の方法が用いられる。既に述べた様に、ゼ
オライトの粉末にニツケル化合物を含浸法、沈澱
法で担持せしめても良く、担体粉末にニツケル化
合物を担持せしめた後、ゼオライト粉末と混合し
ても良い。 Various conventionally known methods can be used to mix these two components. As already mentioned, the nickel compound may be supported on the zeolite powder by an impregnation method or a precipitation method, or the nickel compound may be supported on the carrier powder and then mixed with the zeolite powder.
本発明の脱酸素剤は腐食性物質を含まないこと
を必須とする。 It is essential that the oxygen scavenger of the present invention does not contain corrosive substances.
本発明において腐食性物質とは、特公昭61−
8741号公報でいう電解質であり、NaCl、KCl、
NaBr、KBrなどのアルカリ金属ハロゲン化物、
MgCl2、CaCl2、CaBr2、MgBr2、BaBr2などの
アルカリ土類金属ハロゲン化物の他、AgCl2、
ZnCl2、AlCl3、SnCl2、MnCl2、FeCl2、FeCl3、
CoCl2、NiCl2、CuCl、ZnBr2、SnBr2、FeBr2、
CuBrなどの各種ハロゲン化物、さらにNa2SO4、
K2SO4、CaSO4、MgSO4、Al2（SO4）3、NiSO4、
FeSO4などの各種硫酸塩、NH4Cl、NH4Br
（NH4）2SO4などの各種アンモニウム塩が挙げら
れる。 In the present invention, corrosive substances refer to
It is an electrolyte as referred to in Publication No. 8741, and includes NaCl, KCl,
Alkali metal halides such as NaBr, KBr,
In addition to alkaline earth metal halides such as MgCl 2 , CaCl 2 , CaBr 2 , MgBr 2 , BaBr 2 , AgCl 2 ,
ZnCl2 , AlCl3 , SnCl2 , MnCl2 , FeCl2 , FeCl3 ,
CoCl2 , NiCl2 , CuCl, ZnBr2 , SnBr2 , FeBr2 ,
Various halides such as CuBr, as well as Na 2 SO 4 ,
K 2 SO 4 , CaSO 4 , MgSO 4 , Al 2 (SO 4 ) 3 , NiSO 4 ,
Various sulfates such as FeSO4 , NH4Cl , NH4Br
Examples include various ammonium salts such as (NH 4 ) 2 SO 4 .
ニツケルとゼオライトを含む粉末混合物は圧縮
成形、押出し成形などの通常の方法で適当な形状
に成形される。成形に際して必要ならばセメン
ト、粘土、シリカゾル、アルミナゾル等のバイン
ダーを用いることもできる。次でこの成形体を水
素又は窒素、アルゴン等のイナートガス中で200
〜500℃で10分〜10時間、更に好ましくは250〜
350℃で30分〜５時間熱処理し、ニツケル成分と
ゼオライト成分を活性化し、脱酸素剤を調製す
る。得られた脱酸素剤は、ガス−バリヤー性袋、
又は容器内に収納し、その都度取出して使用すれ
ば良い。 The powder mixture containing nickel and zeolite is molded into a suitable shape by a conventional method such as compression molding or extrusion molding. If necessary during molding, a binder such as cement, clay, silica sol, alumina sol, etc. can be used. Next, this molded body is heated for 200 minutes in an inert gas such as hydrogen, nitrogen, or argon.
〜500℃ for 10 minutes to 10 hours, more preferably 250℃〜
Heat treatment is performed at 350°C for 30 minutes to 5 hours to activate the nickel component and zeolite component, and prepare an oxygen scavenger. The obtained oxygen scavenger is a gas-barrier bag,
Alternatively, it may be stored in a container and taken out and used each time.
以下、本発明を実施例をもつて説明する。 Hereinafter, the present invention will be explained using examples.
実施例 １
硫酸ニツケル90ｇを水350c.c.に加熱溶解し、こ
れに粉砕した本邦宮城県仙台産天然モルデナイト
20ｇを加えて撹拌しながら50〜60℃に保つ。これ
に無水炭酸ナトリウム70ｇを300c.c.の水に溶解し
た液を滴下し、しばらく同温度で撹拌を続け、天
然モルデナイト上に塩基性炭酸ニツケルを沈着せ
しめる。次いでこの沈澱生成物を濾過、水洗し、
100〜120℃で乾燥する。この様にして得られたニ
ツケル−天然モルデナイトの乾燥ケーキに7.2ｇ
のセメントと約40ｇの水を加え、良く混練し５cm
×５cm×５mm厚の大きさに成形する。この成形体
を空気中400℃で熱処理し、酸化ニツケルとした
後、次に雰囲気を水素に変え300℃で酸化ニツケ
ルを金属ニツケルに還元し、脱酸素剤とする。Example 1 Natural mordenite from Sendai, Miyagi Prefecture, Japan, which was prepared by heating and dissolving 90 g of nickel sulfate in 350 c.c. of water and pulverizing it.
Add 20g and keep at 50-60℃ while stirring. A solution prepared by dissolving 70 g of anhydrous sodium carbonate in 300 c.c. of water was added dropwise to this, and stirring was continued for a while at the same temperature to deposit basic nickel carbonate on the natural mordenite. The precipitated product was then filtered and washed with water.
Dry at 100-120℃. The thus obtained nickel-natural mordenite dry cake contains 7.2 g.
Add cement and about 40g of water, mix well and make a 5cm
Form into a size of x5cm x 5mm thick. After this molded body is heat-treated in air at 400°C to form nickel oxide, the atmosphere is changed to hydrogen and the nickel oxide is reduced to metallic nickel at 300°C to form an oxygen scavenger.
以上の様にして得られた脱酸素剤は、ニツケル
37重量％、天然ゼオライト46重量％を含有してい
る。 The oxygen scavenger obtained in the above manner is
37% by weight and 46% by weight of natural zeolite.
５cm×５cm×５mm厚（重さ20ｇ）の脱酸素剤１個
を相対湿度50％の空気を含む0.5の容器に入れ
密封する。１時間後の容器内の相当湿度は１％以
下、酸素濃度は0.2％（除去率99％）であつた。Place one oxygen absorber with a thickness of 5 cm x 5 cm x 5 mm (weight 20 g) in a 0.5 container containing air at a relative humidity of 50% and seal it. After 1 hour, the equivalent humidity in the container was 1% or less, and the oxygen concentration was 0.2% (removal rate 99%).
実施例 ２
硝酸ニツケル90ｇを水350c.c.に加熱溶解し、こ
れにケイソウ土粉末15ｇを加えて撹拌しながら50
〜60℃に保つ。これに無水炭酸ナトリウム70ｇを
水300c.c.に溶解した液を滴下し、しばらく同温度
で撹拌を続け、ケイソウ土上に塩基性炭酸ニツケ
ルを沈着せしめる。次いでこの沈澱生成物を濾
過、水洗し100〜120℃で乾燥する。この様にして
得られた乾燥ケーキ、仙台産天然モルデナイト粉
末、セメント及び水を当量比で１：１：0.1：１
の割合で混合し、以後実施例１と同様の方法で成
形、還元処理し脱酸素剤とする。Example 2 90 g of nickel nitrate was heated and dissolved in 350 c.c. of water, 15 g of diatomaceous earth powder was added thereto, and the mixture was heated for 50 g with stirring.
Keep at ~60°C. A solution prepared by dissolving 70 g of anhydrous sodium carbonate in 300 c.c. of water was added dropwise to this, and stirring was continued for a while at the same temperature to deposit basic nickel carbonate on the diatomaceous earth. The precipitated product is then filtered, washed with water and dried at 100-120°C. The dry cake thus obtained, natural mordenite powder from Sendai, cement and water were mixed in an equivalent ratio of 1:1:0.1:1.
The mixture was mixed in the same proportion as in Example 1, and then molded and reduced in the same manner as in Example 1 to obtain an oxygen absorber.
以上の様にして得られた脱酸素剤はニツケル22
重量％、ケイソウ土25重量％、天然ゼオライト48
重量％を含有している。この脱酸素剤を実施例１
と同じ条件で除湿、脱酸素能力を評価したとこ
ろ、相対湿度は１％以下、酸素濃度は0.4％（除
去率98％）であつた。 The oxygen absorber obtained in the above manner is Nickel 22
Weight%, diatomaceous earth 25% by weight, natural zeolite 48
% by weight. This oxygen absorber was used in Example 1.
When the dehumidification and oxygen removal abilities were evaluated under the same conditions as above, the relative humidity was less than 1% and the oxygen concentration was 0.4% (removal rate 98%).
比較例 １
還元鉄粉末30重量部、亜塩素酸ナトリウム0.5
重量部、宮城県仙台産天然モルデナイト粉60重量
部、セメント10重量部と水50重量部を加えて良く
混合し、実施例１と同様の成形体を調製する。こ
の成形体をそのまま実施例１の方法で除湿、脱酸
素テストを行つたところ、酸素濃度は0.4％（除
去率98％）であつたが、湿度は低下しなかつた。
なお、この成形体を水素気流中300℃で２時間の
処理を行い、同様の除湿、脱酸素テストを行つた
ところ、相対湿度は２％に低下したが酸素濃度は
19.1％（除去率９％）であつた。Comparative example 1 30 parts by weight of reduced iron powder, 0.5 parts by weight of sodium chlorite
60 parts by weight of natural mordenite powder from Sendai, Miyagi Prefecture, 10 parts by weight of cement, and 50 parts by weight of water were added and mixed well to prepare a molded article similar to Example 1. When this molded article was directly subjected to a dehumidification and deoxidation test using the method of Example 1, the oxygen concentration was 0.4% (removal rate 98%), but the humidity did not decrease.
When this molded body was treated for 2 hours at 300°C in a hydrogen stream and subjected to similar dehumidification and deoxidation tests, the relative humidity decreased to 2%, but the oxygen concentration did not.
It was 19.1% (removal rate 9%).
比較例 ２
実施例１において、硫酸ニツケルを硫酸第一鉄
に代えた他は全て同じ方法で成形体の調製、活性
化を行い除湿脱酸素テストを行つたところ、１時
間後の容器内の相対湿度は１％以下に下がつた
が、酸素濃度は18.4％（除去率12％）であつた。Comparative Example 2 A molded product was prepared and activated in the same manner as in Example 1 except that ferrous sulfate was used instead of nickel sulfate, and a dehumidification and deoxidation test was performed. Although the humidity dropped to below 1%, the oxygen concentration remained at 18.4% (removal rate 12%).
又、この活性化成形体を相対湿度90％の窒素ガ
スと接触させ、十分吸湿処理を行つたものは、酸
素濃度0.6％（除去率97％）と脱酸素能を示した
が、相対湿度は変わらず除湿能は示さなかつた。 In addition, when this activated molded body was brought into contact with nitrogen gas at a relative humidity of 90% and subjected to sufficient moisture absorption treatment, it showed oxygen removal ability with an oxygen concentration of 0.6% (removal rate of 97%), but the relative humidity did not change. No dehumidification ability was shown.
従来から知られている鉄系の酸素吸収剤は、乾
燥条件下では酸化能力が低下するので、乾燥剤と
組合せて使用することができない。しかるに、本
発明の活性化された担持されたニツケル金属とゼ
オライトを含む脱酸素剤は腐食性物質を含まない
上、更に簡単な取扱いで吸湿と脱酸素を同時に行
うことができる。
Conventionally known iron-based oxygen absorbers cannot be used in combination with a desiccant because their oxidizing ability decreases under dry conditions. However, the oxygen scavenger containing the activated supported nickel metal and zeolite of the present invention does not contain corrosive substances and can perform moisture absorption and oxygen removal simultaneously with easier handling.
Claims (1)
オライトを主成分とし、腐食性物質を含まないこ
とを特徴とする脱酸素剤。1. An oxygen scavenger characterized by containing 10 to 70% by weight of active supported nickel metal and zeolite as its main components, and containing no corrosive substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11753086A JPS62277148A (en) | 1986-05-23 | 1986-05-23 | Deoxidizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11753086A JPS62277148A (en) | 1986-05-23 | 1986-05-23 | Deoxidizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62277148A JPS62277148A (en) | 1987-12-02 |
| JPH0371171B2 true JPH0371171B2 (en) | 1991-11-12 |
Family
ID=14714069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11753086A Granted JPS62277148A (en) | 1986-05-23 | 1986-05-23 | Deoxidizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62277148A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4330081A1 (en) * | 1993-09-06 | 1995-03-09 | Messer Griesheim Gmbh | Process for removing moisture from gases |
| WO2012105457A1 (en) | 2011-01-31 | 2012-08-09 | 三菱瓦斯化学株式会社 | Oxygen absorber and method for storing same |
| WO2013073590A1 (en) | 2011-11-15 | 2013-05-23 | 三菱瓦斯化学株式会社 | Oxygen-absorbing resin composition, oxygen-absorbing multilayer laminate, and oxygen-absorbing hollow container |
| WO2014014083A1 (en) | 2012-07-20 | 2014-01-23 | 三菱瓦斯化学株式会社 | Method for producing resin composition containing active particles |
| KR20150038277A (en) | 2012-08-02 | 2015-04-08 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for producing oxygen absorber |
| EP2883607A4 (en) | 2012-08-08 | 2016-03-30 | Mitsubishi Gas Chemical Co | OXYGEN ABSORBENT |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54471A (en) * | 1977-06-02 | 1979-01-05 | Hitachi Ltd | Drum type fully automatic washer |
-
1986
- 1986-05-23 JP JP11753086A patent/JPS62277148A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62277148A (en) | 1987-12-02 |
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