JP3991073B2 - Method for producing oxygen scavenger - Google Patents
Method for producing oxygen scavenger Download PDFInfo
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- JP3991073B2 JP3991073B2 JP09410499A JP9410499A JP3991073B2 JP 3991073 B2 JP3991073 B2 JP 3991073B2 JP 09410499 A JP09410499 A JP 09410499A JP 9410499 A JP9410499 A JP 9410499A JP 3991073 B2 JP3991073 B2 JP 3991073B2
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- iron powder
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- metal halide
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Description
【０００１】
【発明の属する技術分野】
本発明は食品の密封容器内の酸素を吸収して非酸化性雰囲気を保持するための脱酸素剤およびその製造方法に関するものである。
【０００２】
【従来の技術】
例えば保存食品等の酸素による変質を防止するための保存食品などと共に密封容器内に封入して該密封容器内の酸素を吸収させるべく鉄粉を処理した酸素吸収剤が実用化されている。ここで脱酸素剤とは酸素を吸収しやすくした鉄粉等直接酸素と反応する物質を表し、酸素吸収剤とは脱酸素剤を紙等に封入しあるいは樹脂に挿入するなど加工したものをいう。
このような鉄粉の処理は鉄粉にハロゲン化金属を被覆あるいは付着させる方法が採られている。
【０００３】
特開昭60-20986では鉄粉やハロゲン化金属の粒径などを事前に調整することによって、鉄粉表面にハロゲン化金属を付着させる方法が採られている。また、特開平60-129137，特開昭64-63039は鉄粉とハロゲン化金属を混合する際に圧縮や破砕という機械的外力を付加することによって付着させている。また、特開平4-290543，特開平5-293365では鉄粉とハロゲン化金属の粒径などを事前に制御したうえで、機械的摩擦力あるいは圧縮を加えて付着させている。
【０００４】
【発明が解決しようとする課題】
しかしながら、これら従来の技術は次のような課題があった。
単に金属やハロゲン化金属の粒径などを調整して混合しただけでは鉄粉表面への付着力が小さく、また機械的外力を加える場合には、粒子に外力が加わることで歪みが生じ酸素吸収力に悪影響を及ぼす。
したがって、従来の酸素吸収剤では酸素吸収速度が小さく、食品を密封包装後すみやかに、無酸素の状態にすることが困難であった。
また、樹脂に混練して使用する場合には混練中に、包装して使用する場合には保存中あるいは食品の包装内で水分を分解して水素が発生してしまうという問題があった。水素が発生すると発火、爆発の危険があり、また腐敗と誤認されるという問題がある。
【０００５】
【課題を解決するための手段】
本発明者らが種々検討した結果、以下の点が明らかとなってきた。
▲１▼酸素吸収速度を増加し、実質的な酸素吸収量を高めるためにはハロゲン化金属が鉄粉全体に均一に付着する必要があるが一般に使用される鉄粉は形状が複雑で混合等では十分に付着していない。
▲２▼酸素吸収量を増加させ、水素発生を抑制するためにはとくに表面付近で不純物としての酸素が少なく、金属鉄である必要があるが、一般に使用される鉄粉は表面が酸化されている。
▲３▼水素発生を抑制するためには残留応力が低いほど良いことがわかったが、解砕や粉砕などにおいて機械的な力を過度に加えることによって残留応力が発生する。
【０００６】
以上の知見にたって本発明者らは
▲１▼鉄粉にハロゲン化金属を付着させる工程では鉄粉を非水系溶媒にハロゲン化金属を溶かした溶液中浸漬させることによって、ハロゲン化金属を鉄粉粒子の隅々まで付着させる。とくに減圧下で浸漬させるとその効果は一層顕著となる。
▲２▼鉄粉を還元雰囲気中で熱処理を施すことによって、酸化鉄を還元して金属鉄にするとともに、残留応力を除去する。
以上の三点が酸素吸収速度が高く、酸素吸収量が多く、さらに水素発生量の少ない優れた脱酸素剤の製造にきわめて有効であることを見いだした。
【０００７】
これらの工程は各々単独でも効果があるが、複合させることによってさらにその効果は顕著となる。また、この工程は順番を問わない。
本発明者らは上記の方法によって得られる脱酸素剤を種々検討した結果、酸素吸収速度が最初の5時間で80mL/g以上あれば、食品を新鮮に保つのにきわめて有効であることを見いだした。
【０００８】
【発明の実施の形態】
原材料
鉄粉は一般的な鉄粉であれば使用でき、アトマイズ鉄粉や還元鉄粉等があるがコスト、純度を考慮すればいわゆるロータリー還元鉄粉が好ましい。
また、粒度は1μm以上100μm以下が好ましい。
ハロゲン化鉄はすべて使用できるが、有機溶媒に溶解させることやコスト、酸素吸収の性能を考慮すると、CaCl2やFeCl2が好ましい。
溶媒としては有機溶媒等が使用できるがメタノールが好ましい。
還元性ガスとしては還元性のガスであれば使用できるが、臭気、コスト等の点で水素が最も好ましい。
【０００９】
工程
鉄粉へのハロゲン化金属の浸漬は溶媒にハロゲン化金属を溶解し、この中に鉄粉を投入して、撹拌すればよい。有機溶媒を用いることによって潮解性、吸湿性が強い金属でも鉄粉に付着できる。減圧下で有機溶剤溶液に鉄粉を浸漬すると、ハロゲン化金属が鉄粉の内部まで深く浸透して、良好な脱酸素特性(酸素吸収特性）を示すことになる。
熱処理の温度範囲は200℃以下の低温ではその効果が小さく、また900℃以上の高温で行うと焼結が強くなって、焼結後の解砕を強く行わなければならず、解体によって歪が生じて、結果として水素ガス発生抑制効果が小さくなる。したがって、熱処理温度範囲としては200℃から900℃の間が好ましい。本発明のような還元熱処理を行うと、内部空孔が多く、比表面積（反応面積）が大きくなり、反応が促進される。
還元雰囲気中で熱処理を施すことによって、鉄粉の歪の低下をもたらし、FeOの減少などによって水素ガス発生が抑制される。また、金属鉄量の増加によって酸素吸収量が増加する。以上のことから良好な酸素吸収剤を得ることができる。
【００１０】
【実施例１】
（混合＋熱処理）
ロータリキルン還元鉄（平均粒径23μm）1000gとハロゲン化金属としてCaCl220ｇをV型混合機で30分間混合する。この粉末を静置式電気炉に入れ水素雰囲気中で600℃、2時間の還元熱処理を行う。こうして得られた鉄粉の酸素吸収量、水素ガス発生量を測定した。
【００１１】
酸素吸収量は以下の方法で行う。酸素吸収剤1gを通気性包装材(製品名 タイバック1073B, デュポン製)に入れ、水1mLをしみこませたろ紙と共にガスバリア性袋に封入し、袋内をポンプで一度排気する。次に空気1500mLを袋の中に入れ、20℃で保管する。所定の時間ごとに袋の中の酸素濃度を測定し、次式により酸素吸収量を算出する。
酸素吸収量(mL/g)={(20.9-酸素濃度)/(100-酸素濃度)}×1500
ただし、酸素濃度の単位は%
【００１２】
水素ガス発生量の測定は以下の通りに行う。酸素吸収剤25gと保水させた保水剤25gを混合し、通気性包材に入れ、ガスバリア性袋に封入する。袋内をポンプで脱気し、水中重量を測定する。これを50℃で保管し、1日後及び7日後の水中重量を測定し、増加分を水素ガス発生量とする。
また、ハロゲン化金属の浸透度は脱酸素剤10gを水100cc中に投入して洗浄後、残留したハロゲン量を分析して測定した。
【００１３】
【実施例２】
（熱処理＋混合）
ロータリーキルン還元鉄(平均23μm)を静置式電気炉に入れ水素雰囲気中で600℃、2時間の還元熱処理を行う。
この鉄粉1000gとハロゲン化金属としてCaCl220gをV型混合機で30分間混合する。こうして得られた鉄粉の酸素吸収量、水素ガス発生量を測定した。
【００１４】
【実施例３】
(浸漬)
CaCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均粒径45μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常圧に戻して、万能撹拌機に入れて窒素雰囲気中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００１５】
【実施例４】
(浸漬)
CaCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均粒径23μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常圧に戻して、万能撹拌機に入れて窒雰中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００１６】
【実施例５】
(浸漬)
FeCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均45μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００１７】
【実施例６】
(浸漬)
FeCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均23μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００１８】
【実施例７】
(浸漬＋熱処理)
FeCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均23μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。
この粉末を静置式電気炉に入れ水素雰囲気中で600℃、2時間の還元熱処理を行う。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量を測定した。
【００１９】
【実施例８】
(熱処理＋浸漬)
ロータリーキルン還元鉄(平均45μm)を静置式電気炉に入れ水素雰囲気中で600℃、2時間の還元熱処理を行う。
CaCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液に上記熱処理したロータリーキルン還元鉄(平均43μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量を測定した。
【００２０】
【実施例９】
(熱処理＋浸漬)
ロータリーキルン還元鉄(平均23μm)を静置式電気炉に入れ水素雰囲気中で600℃、2時間の還元熱処理を行う。
CaCl2を18gメタノール300g中に溶解させて金属塩有機溶剤とする。この溶液に上記熱処理したロータリーキルン還元鉄(平均23μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量を測定した。
【００２１】
【比較例１】
(混合)
ロータリーキルン還元鉄(平均45μm)1000gとハロゲン化金属としてCaCl2を20gをV型混合機で30分間混合する。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２２】
【比較例２】
(混合)
ロータリーキルン還元鉄(平均23μm)1000gとハロゲン化金属としてFeCl2を20gをV型混合機で30分間混合する。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２３】
【比較例３】
(混合)
ロータリーキルン還元鉄(平均45μm)1000gとハロゲン化金属としてFeCl2を20gをV型混合機で30分間混合する。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２４】
【比較例４】
(混合)
ロータリーキルン還元鉄(平均45μm)1000gとハロゲン化金属としてCaCl220gをV型混合機で30分間混合する。
こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２５】
【比較例５】
(浸漬)
CaCl2を18g水300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均45μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２６】
【比較例６】
(浸漬)
FeCl2を18g水300g中に溶解させて金属塩有機溶剤とする。この溶液にロータリーキルン還元鉄(平均45μm)1000gを浸漬させ、ロータリーポンプ減圧下で30分間保持する。これを常温に戻して、万能撹拌機に入れて窒素ガス雰囲気中で100℃で加熱乾燥させる。こうして得られた鉄粉の酸素吸収量、水素ガス発生量、ハロゲン量を測定した。
【００２７】
【発明の効果】
以上の結果をまとめて表１に示す。本発明による実施例では、不純物である酸素含有量が低く、歪みが緩和されて残留応力が無くなっているため水素発生量が低い。
また、本発明による実施例では比較例に示した混合法や水を使用した浸漬法に比べて、塩素化合物が粒子奥深くまで均一に付着しているので、酸素吸収量が高い。
このように本発明による脱酸素剤を空気透過性の樹脂に練混んだり、同様の包装材に包み込むことによって、安全でかつ酸素吸収能力の高い酸素吸収剤を製造することができる。
【００２８】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to an oxygen scavenger for absorbing oxygen in a sealed container for food and maintaining a non-oxidizing atmosphere, and a method for producing the same.
[0002]
[Prior art]
For example, an oxygen absorbent in which iron powder is treated so as to be enclosed in a sealed container together with a preserved food for preventing deterioration due to oxygen such as preserved food to absorb oxygen in the sealed container has been put into practical use. Here, the oxygen scavenger represents a substance that reacts directly with oxygen, such as iron powder that easily absorbs oxygen, and the oxygen absorber refers to a material processed by sealing the oxygen scavenger in paper or inserting it into a resin. .
Such a treatment of iron powder employs a method of coating or adhering a metal halide to the iron powder.
[0003]
Japanese Patent Laid-Open No. 60-20986 adopts a method of attaching metal halide to the surface of iron powder by adjusting the particle size of iron powder or metal halide in advance. JP-A-60-129137 and JP-A-64-63039 are adhered by applying mechanical external force such as compression or crushing when mixing iron powder and metal halide. In Japanese Patent Laid-Open Nos. 4-290543 and 5-933365, the particle sizes of iron powder and metal halide are controlled in advance and then adhered by applying mechanical frictional force or compression.
[0004]
[Problems to be solved by the invention]
However, these conventional techniques have the following problems.
Simply adjusting the particle size of the metal or metal halide and mixing them results in low adhesion to the iron powder surface, and when mechanical external force is applied, the external force is applied to the particles, causing distortion and oxygen absorption. Adversely affects force.
Therefore, conventional oxygen absorbents have a low oxygen absorption rate, and it has been difficult to make foods oxygen-free immediately after sealed packaging.
Further, there is a problem in that hydrogen is generated by decomposing moisture during kneading when used in a resin, and during storage when used in packaging or during food packaging. When hydrogen is generated, there is a risk of fire and explosion, and there is a problem that it is mistaken for corruption.
[0005]
[Means for Solving the Problems]
As a result of various studies by the present inventors, the following points have been clarified.
(1) In order to increase the oxygen absorption rate and increase the substantial oxygen absorption amount, it is necessary for the metal halide to uniformly adhere to the entire iron powder, but generally used iron powder is complicated in shape and mixed In, it does not adhere enough.
(2) In order to increase the amount of oxygen absorbed and suppress the generation of hydrogen, there is little oxygen as an impurity especially near the surface, and it is necessary to be metallic iron. Yes.
{Circle around (3)} It was found that the lower the residual stress, the better, in order to suppress the generation of hydrogen. However, the residual stress is generated by excessively applying mechanical force during crushing or grinding.
[0006]
Based on the above knowledge, the present inventors (1) in the step of attaching the metal halide to the iron powder, the metal powder is immersed in a solution in which the metal halide is dissolved in a non-aqueous solvent to thereby convert the metal halide into the iron powder. Adhere to every corner of the particle. In particular, the effect becomes more prominent when immersed under reduced pressure.
(2) The iron powder is heat-treated in a reducing atmosphere to reduce iron oxide to metallic iron and remove residual stress.
The above three points have been found to be extremely effective in producing an excellent oxygen scavenger with a high oxygen absorption rate, a large oxygen absorption amount, and a small hydrogen generation amount.
[0007]
Each of these steps is effective even when used alone, but the effect becomes more remarkable when combined. Moreover, this process does not ask | require an order.
As a result of various studies on the oxygen scavenger obtained by the above method, the present inventors have found that an oxygen absorption rate of 80 mL / g or more in the first 5 hours is extremely effective for keeping food fresh. It was.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The raw material iron powder can be used as long as it is general iron powder, and there are atomized iron powder and reduced iron powder, but so-called rotary reduced iron powder is preferable in consideration of cost and purity.
The particle size is preferably 1 μm or more and 100 μm or less.
Although all of the iron halides can be used, CaCl 2 and FeCl 2 are preferable in view of dissolution in an organic solvent, cost, and oxygen absorption performance.
As the solvent, an organic solvent or the like can be used, but methanol is preferable.
As the reducing gas, any reducing gas can be used, but hydrogen is most preferable in terms of odor and cost.
[0009]
The immersion of the metal halide in the process iron powder may be performed by dissolving the metal halide in a solvent, putting the iron powder into the solvent, and stirring. By using an organic solvent, even a metal with strong deliquescence and hygroscopicity can adhere to iron powder. When iron powder is immersed in an organic solvent solution under reduced pressure, the metal halide penetrates deeply into the iron powder and exhibits good deoxygenation characteristics (oxygen absorption characteristics).
The temperature range of the heat treatment is small at a low temperature of 200 ° C. or lower, and when it is performed at a high temperature of 900 ° C. or higher, the sintering becomes stronger and the pulverization after the sintering must be strongly performed. As a result, the effect of suppressing the generation of hydrogen gas is reduced. Therefore, the heat treatment temperature range is preferably between 200 ° C and 900 ° C. When the reduction heat treatment as in the present invention is performed, the number of internal vacancies increases, the specific surface area (reaction area) increases, and the reaction is promoted.
By performing the heat treatment in a reducing atmosphere, the distortion of the iron powder is reduced, and the generation of hydrogen gas is suppressed by the reduction of FeO. Moreover, the amount of oxygen absorption increases with the increase in the amount of metallic iron. From the above, a good oxygen absorbent can be obtained.
[0010]
[Example 1]
(Mixing + heat treatment)
1000 g of rotary kiln reduced iron (average particle size 23 μm) and 20 g of CaCl 2 as a metal halide are mixed in a V-type mixer for 30 minutes. This powder is placed in a static electric furnace and subjected to a reduction heat treatment at 600 ° C. for 2 hours in a hydrogen atmosphere. The oxygen absorption amount and hydrogen gas generation amount of the iron powder thus obtained were measured.
[0011]
The amount of oxygen absorbed is determined by the following method. Put 1 g of oxygen absorbent in a breathable packaging material (product name: Tyback 1073B, manufactured by DuPont), enclose it in a gas barrier bag with filter paper soaked with 1 mL of water, and exhaust the bag once with a pump. Next, put 1500mL of air in the bag and store at 20 ° C. The oxygen concentration in the bag is measured every predetermined time, and the oxygen absorption amount is calculated by the following equation.
Oxygen absorption (mL / g) = {(20.9-oxygen concentration) / (100-oxygen concentration)} × 1500
However, the unit of oxygen concentration is%
[0012]
The amount of hydrogen gas generated is measured as follows. Mix 25g of oxygen absorbent and 25g of water retaining agent, put it in a breathable packaging, and enclose it in a gas barrier bag. The inside of the bag is evacuated with a pump and the weight in water is measured. This is stored at 50 ° C., and the weight in water after 1 day and after 7 days is measured, and the increase is taken as the hydrogen gas generation amount.
Further, the permeability of the metal halide was measured by adding 10 g of oxygen scavenger into 100 cc of water and washing, and then analyzing the amount of remaining halogen.
[0013]
[Example 2]
(Heat treatment + mixing)
A rotary kiln reduced iron (average 23 μm) is placed in a static electric furnace and subjected to a reduction heat treatment at 600 ° C. for 2 hours in a hydrogen atmosphere.
1000 g of this iron powder and 20 g of CaCl 2 as a metal halide are mixed in a V-type mixer for 30 minutes. The oxygen absorption amount and hydrogen gas generation amount of the iron powder thus obtained were measured.
[0014]
[Example 3]
(Immersion)
CaCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of rotary kiln reduced iron (average particle size 45 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal pressure, put in a universal stirrer and dried by heating at 100 ° C. in a nitrogen atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0015]
[Example 4]
(Immersion)
CaCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of reduced kiln reduced iron (average particle size 23 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal pressure, put into a universal stirrer and dried by heating at 100 ° C. in a nitrogen atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0016]
[Example 5]
(Immersion)
FeCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of reduced iron kiln reduced iron (average 45 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal temperature, put into a universal stirrer, and dried by heating at 100 ° C. in a nitrogen gas atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0017]
[Example 6]
(Immersion)
FeCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of reduced kiln reduced iron (average 23 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal temperature, put into a universal stirrer, and dried by heating at 100 ° C. in a nitrogen gas atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0018]
[Example 7]
(Immersion + Heat treatment)
FeCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of reduced kiln reduced iron (average 23 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal temperature, put into a universal stirrer, and dried by heating at 100 ° C. in a nitrogen gas atmosphere.
This powder is placed in a static electric furnace and subjected to a reduction heat treatment at 600 ° C. for 2 hours in a hydrogen atmosphere.
The oxygen absorption amount and hydrogen gas generation amount of the iron powder thus obtained were measured.
[0019]
[Example 8]
(Heat treatment + immersion)
A rotary kiln reduced iron (average 45 μm) is placed in a static electric furnace and subjected to a reduction heat treatment at 600 ° C. for 2 hours in a hydrogen atmosphere.
CaCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of the heat-treated rotary kiln reduced iron (average 43 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal temperature, put into a universal stirrer, and dried by heating at 100 ° C. in a nitrogen gas atmosphere.
The oxygen absorption amount and hydrogen gas generation amount of the iron powder thus obtained were measured.
[0020]
[Example 9]
(Heat treatment + immersion)
A rotary kiln reduced iron (average 23 μm) is placed in a static electric furnace and subjected to a reduction heat treatment at 600 ° C. for 2 hours in a hydrogen atmosphere.
CaCl 2 is dissolved in 18 g of methanol 300 g to form a metal salt organic solvent. In this solution, 1000 g of the heat-treated rotary kiln reduced iron (average 23 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to normal temperature, put into a universal stirrer, and dried by heating at 100 ° C. in a nitrogen gas atmosphere.
The oxygen absorption amount and hydrogen gas generation amount of the iron powder thus obtained were measured.
[0021]
[Comparative Example 1]
(mixture)
The CaCl 2 mixed for 30 minutes 20g with a V mixer as a rotary kiln reduced iron (average 45 [mu] m) 1000 g and a metal halide.
The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0022]
[Comparative Example 2]
(mixture)
A rotary kiln reduced iron (average 23 μm) 1000 g and 20 g of FeCl 2 as a metal halide are mixed in a V-type mixer for 30 minutes.
The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0023]
[Comparative Example 3]
(mixture)
A rotary kiln reduced iron (average 45 μm) 1000 g and 20 g of FeCl 2 as a metal halide are mixed in a V-type mixer for 30 minutes.
The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0024]
[Comparative Example 4]
(mixture)
The CaCl 2 20 g mixed for 30 minutes in V-blender as rotary kiln reduced iron (average 45 [mu] m) 1000 g and a metal halide.
The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0025]
[Comparative Example 5]
(Immersion)
CaCl 2 is dissolved in 300 g of 18 g water to form a metal salt organic solvent. In this solution, 1000 g of reduced iron kiln reduced iron (average 45 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to room temperature, put into a universal stirrer and dried by heating at 100 ° C. in a nitrogen gas atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0026]
[Comparative Example 6]
(Immersion)
FeCl 2 is dissolved in 18 g of water 300 g to form a metal salt organic solvent. In this solution, 1000 g of reduced iron kiln reduced iron (average 45 μm) is immersed and held for 30 minutes under reduced pressure of the rotary pump. This is returned to room temperature, put into a universal stirrer and dried by heating at 100 ° C. in a nitrogen gas atmosphere. The oxygen absorption, hydrogen gas generation, and halogen content of the iron powder thus obtained were measured.
[0027]
【The invention's effect】
The above results are summarized in Table 1. In the embodiment according to the present invention, the amount of hydrogen generated is low because the oxygen content as an impurity is low, the strain is relaxed and the residual stress is eliminated.
Moreover, in the Example by this invention, compared with the mixing method shown in the comparative example, and the immersion method using water, since the chlorine compound has adhered uniformly to the particle | grain depth, oxygen absorption amount is high.
Thus, the oxygen absorber according to the present invention is kneaded into an air-permeable resin or wrapped in a similar packaging material, whereby a safe and high oxygen absorbing ability can be produced.
[0028]
[Table 1]
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09410499A JP3991073B2 (en) | 1999-03-31 | 1999-03-31 | Method for producing oxygen scavenger |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09410499A JP3991073B2 (en) | 1999-03-31 | 1999-03-31 | Method for producing oxygen scavenger |
Publications (2)
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|---|---|
| JP2000279147A JP2000279147A (en) | 2000-10-10 |
| JP3991073B2 true JP3991073B2 (en) | 2007-10-17 |
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| JP09410499A Expired - Lifetime JP3991073B2 (en) | 1999-03-31 | 1999-03-31 | Method for producing oxygen scavenger |
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| JP5378639B2 (en) * | 2006-04-20 | 2013-12-25 | 東洋製罐株式会社 | Oxygen absorbent for resin blending and method for producing the same |
| CN104028209A (en) * | 2014-06-09 | 2014-09-10 | 应关雄 | Water film oxygen absorbent and preparation method thereof |
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