JP3570513B2 - Use of activated iron powder as a deoxidizer - Google Patents
Use of activated iron powder as a deoxidizer Download PDFInfo
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- JP3570513B2 JP3570513B2 JP2002173919A JP2002173919A JP3570513B2 JP 3570513 B2 JP3570513 B2 JP 3570513B2 JP 2002173919 A JP2002173919 A JP 2002173919A JP 2002173919 A JP2002173919 A JP 2002173919A JP 3570513 B2 JP3570513 B2 JP 3570513B2
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- iron powder
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Description
【０００１】
【産業上の利用分野】
本発明は、活性鉄粉の脱酸素剤としての使用に関する。
【０００２】
【従来の技術】
鉄粉と反応助剤等の混合物に空気（酸素）を作用させて使用する製品としては、一般には各種食品の包装体中に装着して包装体中の酸素を効率よく吸収して食品の鮮度を保持する、いわゆる脱酸素剤が良く知られている。
【０００３】
これらの製品に使用される金属粉としては鉄粉が最も一般的であることは公知であり、反応助剤としては食塩、水等が用いられ、これらの物質を担持する保水剤として活性炭、バーミキュライト、珪藻土、木粉あるいは吸水性高分子等を混合して使用されることも良く知られている。また脱酸素剤の中には反応助剤として食塩のみを使用し、水分は食品から吸収して脱酸素を行なうものもある。
【０００４】
これらの製品における鉄粉の役割は、脱酸素剤にあっては包装内にある空気（酸素）を鉄粉に吸収させてその目的を果たすことにある。従って、この製品の性能は鉄粉の特性によって左右され、換言すれば活性の高い鉄粉を使用することにより良質の製品が生産されることになる。
【０００５】
市場におけるかかる要望に応えるための方策として、原材料である鉄鉱石は還元され易いヘマタイト（赤鉄鉱）を１５〜２０ｍｍに粉砕して用い、比較的低温（約１０５０℃）で還元が行なわれるロータリキルン法によって製造した鉄粉が好ましく使用されている。ロータリキルン法により低温で還元した鉄粉の活性度が高い理論的根拠については明らかでないが、原料である酸化鉄が還元される際、酸素原子のあった場所が空格子となり、生成された空格子へ鉄原子が移動していない不安定状態にある、いわば安定状態にはない原子構造において酸素との反応性を高めているものと推論される。
【０００６】
ところで上記のロータリキルン法で製造した鉄粉は脱酸素剤やカイロ等の製品用原料としては好適であるが、これを粉末冶金用、溶接棒用あるいは各種ショットブラスト用鉄粉として使用するためには、さらに高温度での熱処理を重ねることが必要で、鉄粉産業全般を考えた場合、経済的に有利とは言えない。さりとて、脱酸素剤やカイロ用鉄粉をロータリキルン法で、その他の用途の鉄粉は別の方法で製造することは往々にして一層経済的に不利を招く場合が多い。
【０００７】
【発明が解決しようとする課題】
本発明は、脱酸素剤の原料として好適で、かつ経済性に優れた活性鉄粉を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明の上記目的は、脱酸素剤を構成し、鉄粉表面が、導電性グラファイト、カーボンブラック、黒鉛及び活性炭からなる群から選択される０．３〜３．０重量％の導電性炭素質物質で部分的に被覆された活性鉄粉により達成される。
【０００９】
すなわち、本発明の活性鉄粉の脱酸素剤としての使用は、鉄粉表面が、導電性グラファイト、カーボンブラック、黒鉛及び活性炭からなる群から選択される０．３〜３．０重量％の導電性炭素質物質で部分的に被覆されたことを特徴とする。
【００１０】
本発明で用いられる鉄粉としては、市販の鉄粉でよく、還元鉄粉、スポンジ鉄粉等が例示されるが、還元鉄粉が最も好ましく用いられる。また、脱酸素剤の用途には、アトマイズ鉄粉も使用される。
【００１１】
本発明では、この鉄粉の表面に導電性炭素質物質が部分的に被覆されている。導電性炭素質物質としては、電気抵抗が抵抗が小さく、かつ鉄粉被膜を形成し易いものがよく、導電性グラファイト、カーボンブラックあるいは微粉の活性炭等が挙げられる。この導電性炭素質物質の被覆量は、鉄粉全体の０．３〜３．０重量％、好ましくは０．３〜１．０重量％であり、０．３重量％未満では脱酸素剤の酸素吸収特性に寄与できず、３．０重量％を超えても特別の効果が増進せず、逆に不経済である。
【００１２】
通常、還元鉄粉は０．０１〜０．３重量％の還元剤、すなわち炭素分が残留しているが、これらの炭素分は鉄粉中に固溶しているか、あるいは鉄粉から遊離したいわゆる遊離炭素として存在するため、これらの形態での炭素分では脱酸素剤の酸素吸収特性に寄与することはない。
【００１３】
また、導電性炭素質物質被覆を効率よく行なうために鉄粉の流動性を害さない程度に０．０１〜０．０５重量％の油分、例えばスピンドル油（商品名：スピノックスＳ５、Ｓ１０、いずれも日本石油（株）製）等を添加することは好ましいことである。
【００１４】
本発明の要点は、鉄粉表面に導電性炭素質物質の薄膜を局部的に形成せしめることにより、地鉄と導電材料の間に形成される局部電池により酸化反応を促進せしめるものである。
【００１５】
図１にその原理図を示す。Ａは鉄粉、Ｂは炭素質導電材料を示す。鉄粉は塩水の存在により鉄イオンとなり、この際、次式に従って２個の電子が放出されるため、鉄粉が陽極となり炭素物質が陰極となって、この間に形成された電池が酸化反応を促進させることになる。
Ｆｅ→Ｆｅ＋＋＋２ｅ−
【００１６】
鉄粉表面をこれらの導電性炭素質物質で局部的に被覆するには各種の装置が適用できるが、ボールミル、コニカルブレンダ等でも３０分〜３時間の被覆処理により陰極薄膜を形成させることが可能である。被膜形成機としては（株）奈良機械製作所から市販されている“ハイブリダイゼーション”等を使用すれば処理時間が短縮できるが、特に被覆処理装置により制約を受けるものではない。
【００１７】
本発明において、例えばトンネルキルンを用いて還元された鉄粉を適用すれば、酸素との反応性が改善され、脱酸素剤、特に水分活性の高い食品に用いられる高水分型（自己反応型）脱酸素剤に用いれば、短時間で酸素濃度は０．１容量％以下となり、食品の鮮度保持が効率よく行なわれる。
【００１８】
他目的、溶接棒用あるいは粉末冶金用鉄粉は従来通りの工程で生産されることは言うまでもなく、本発明の適用によってこれらの鉄粉が品質的にも経済的にも不利となることは全くない。
【００１９】
すなわち本発明は、現在一般的に製造されている鉄粉を用い、その機能を脱酸素剤の原料として好適な活性鉄粉に改質することにある。
【００２０】
【実施例】
以下、実施例等に基づいて本発明をさらに詳細に説明する。
【００２１】
参考例１
表１に示す性状を有する市販の溶接棒用鉄粉１０ｋｇと粉末黒鉛（固定炭素９７．０重量％、平均粒径７．０μｍ、商品名ＣＰ、日本黒鉛工業（株）製）５０ｇを小型ボールミルに入れ２４時間被膜処理を行ない活性鉄粉を得た。
【００２２】
【表１】
この活性鉄粉１００ｇを２５０ｃｃポリ瓶に入れ、さらに塩水（２０．５％）８ｃｃを注ぎ、１分間手でよく振って混合した。ポリ瓶は５ケ準備し、上記の操作を繰り返し温度測定用サンプル５ケを作った（ポリ瓶は蓋を閉じてなるべく空気が入らないようにした）。準備が終れば各々のポリ瓶から内容物を１００ｃｃのビーカーに移し替えビーカーのほぼ中央部の温度をサーモカップルにて測定した。
【００２４】
測温結果は図２の曲線に見られるごとく、１０分後で約６５℃（５ケの平均）であった。
【００２５】
比較例１
参考例１で用いた溶接棒用鉄粉を導電性炭素質物質処理を行なわず、そのまま参考例１と同様の方法で塩水（２０．５％）８ｃｃを混ぜて測温を行なった結果、図２の曲線のごとくなり１０分後の温度は約３０℃と参考例１に用いた活性鉄粉に比べ著しく昇温速度は遅かった。
【００２６】
参考例２
トンネルキルンで還元されたスポンジ鉄を表２に示す粒度に粉砕した鉄粉１トンに、１０ｋｇの活性炭（商品名ゼオコールＳ、パウダーテック（株）製）の微粉（−４５μｍ以下９０重量％）をコーン型ミキサーに入れ２時間被覆処理を行ない活性鉄粉を得た。
【００２７】
【表２】
この活性鉄粉に参考例１で説明した方法で塩水（２０．５％）８ｃｃを混ぜ、測温を行なった結果、図２の曲線のごとくなり１０分後の温度は約７５℃となった。
【００２９】
また、この鉄粉３０ｇと反応助燃剤２７．７ｇ（活性炭４ｇ、バーミキュライト６ｇ、木粉２ｇ、塩０．７ｇ、水１５ｍｌの混合物）をよく混合し、通常の使い捨てカイロに用いられる不織布に入れ１０ケのカイロを作成しこれをタオル２枚に包んでカイロの中央部の温度を測定した結果、図３のＡに示す棒グラフが得られた。すなわち測定開始より５分後の温度差は約４５℃（１０ケの平均）、最高温度８３℃（１０ケの平均）、４０℃以上の持続時間は約１９時間であった。
【００３０】
比較例２
参考例２において導電性炭素質物質被覆処理を行なわず、参考例２と同様の方法で発熱特性を評価した。
【００３１】
その結果、図２の曲線ならびに図３のＢに示す棒グラフのごとくなり、いずれも参考例２の活性鉄粉を使用した場合に比べ、発熱特性が劣った。
【００３２】
参考例３
参考例１において使用した導電性炭素質物質（粉末黒鉛）に代えて、粉末黒鉛（固定炭素９２．５重量％、平均粒径２μｍ、商品名青Ｐ、日本黒鉛工業（株）製）を用い、かつ被覆量を鉄粉１０ｋｇに対し２００ｇに増加したことを除いては、参考例１と全く同様の方法で発熱特性を評価した結果、１０分後の温度は７９℃であった。
【００３３】
実施例１
アトマイズ鉄粉（商品名アトメル３００Ｍ、神戸製鋼社製）１トンに、１０ｋｇの活性炭（商品名ゼオコールＳ、パウダーテック（株）製）の微粉（−４５μｍ以下９０重量％）をコーン型ミキサーに入れ２時間被覆処理を行ない活性鉄粉を得た。
【００３４】
この活性鉄粉約２．６ｇに市販の食塩１３ｍｇをよく混合し、有孔ポリエチレンフィルムをラミネートした不織布内に入れて水分依存型脱酸素剤を作成した。
【００３５】
この脱酸素剤をガスバリアフィルム袋に入れ、さらに５００ｍｌの空気と水を含ませた脱脂綿を同封して所定時間毎に酸素濃度を脱酸素が完了するまで測定し、表３の結果を得た。
【００３６】
【表３】
比較例３
実施例１において炭素質物質の被覆処理前のアトマイズ鉄粉を使用したことを除いては、実施例１と全く同様の方法で脱酸素速度を評価した結果、表４のごとくであった。
【００３８】
【表４】
【発明の効果】
以上の説明から明らかなごとく、現在、溶接棒用あるいは粉末冶金用等として市場に出ている鉄粉またはそれらの中間工程品として産出される鉄粉の表面に、導電性炭素質物質の薄膜を局部的に一定量形成せしめることにより、脱酸素剤用原料として酸化反応が促進されるように表面改質された本発明の活性鉄粉が得られる。
【図面の簡単な説明】
【図１】本発明による鉄粉が効果を発揮する根拠を説明する原理図である。
【図２】本発明の活性鉄粉と比較鉄粉の発熱立上り特性を比較したグラフである。
【図３】本発明の鉄粉と比較鉄粉を用いて作った使い捨てカイロの発熱特性を比較したグラフである。[0001]
[Industrial applications]
The present invention relates to the use of activated iron powders as oxygen scavengers .
[0002]
[Prior art]
As a product to be used by applying air (oxygen) to a mixture of iron powder and a reaction aid, etc., it is generally installed in various food packages to efficiently absorb oxygen in the packages and to make the food fresh. So-called oxygen scavengers are well known.
[0003]
It is known that iron powder is the most common metal powder used in these products, and salt and water are used as reaction aids. Activated carbon, vermiculite is used as a water retention agent to support these substances. It is also well known that diatomaceous earth, wood flour or a water-absorbing polymer is used as a mixture. Some oxygen scavengers use only salt as a reaction aid and absorb moisture from food to perform oxygen scavenging.
[0004]
The role of iron powder in these products is to serve the purpose of absorbing oxygen (oxygen) in the package of the oxygen absorber into the iron powder. Therefore, the performance of this product depends on the characteristics of the iron powder. In other words, the use of highly active iron powder results in the production of a high quality product.
[0005]
As a measure to respond to such a demand in the market, a rotary kiln is used in which iron ore as a raw material is reduced at a relatively low temperature (about 1050 ° C.) using hematite (hematite), which is easily reduced, crushed to 15 to 20 mm. Iron powder produced by the method is preferably used. The theoretical basis for the high activity of the iron powder reduced at low temperature by the rotary kiln method is not clear, but when the iron oxide as the raw material is reduced, the places where oxygen atoms were present become vacancies, and the vacancies generated It is inferred that the reactivity with oxygen is increased in an unstable state where iron atoms do not move to the child, that is, in an atomic structure that is not in a stable state.
[0006]
By the way, iron powder produced by the above-mentioned rotary kiln method is suitable as a raw material for products such as an oxygen scavenger and a warmer.However, in order to use this as iron powder for powder metallurgy, welding rods or various shot blasts, Requires further heat treatment at a higher temperature, which is not economically advantageous when considering the iron powder industry in general. Incidentally, it is often more economical disadvantageous to produce the oxygen scavenger and the iron powder for the body warmer by the rotary kiln method and the iron powder for other uses by another method.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide an activated iron powder which is suitable as a raw material for an oxygen scavenger and is excellent in economic efficiency.
[0008]
[Means for Solving the Problems]
The object of the present invention is to provide a deoxidizer, wherein the surface of iron powder has a conductive carbonaceous content of 0.3 to 3.0% by weight selected from the group consisting of conductive graphite, carbon black, graphite and activated carbon. Achieved by activated iron powder partially coated with the substance.
[0009]
That is, the use of the activated iron powder of the present invention as an oxygen scavenger is characterized in that the iron powder surface has a conductivity of 0.3 to 3.0% by weight selected from the group consisting of conductive graphite, carbon black, graphite and activated carbon. Characterized by being partially coated with a carbonaceous material.
[0010]
The iron powder used in the present invention may be a commercially available iron powder, such as reduced iron powder and sponge iron powder. Of these, reduced iron powder is most preferably used. In addition, atomized iron powder is also used for the purpose of the oxygen scavenger.
[0011]
In the present invention, the surface of the iron powder is partially covered with the conductive carbonaceous substance. As the conductive carbonaceous substance, a substance having low electric resistance and easy to form an iron powder coating is preferable, and examples thereof include conductive graphite, carbon black, and activated carbon of fine powder. The coating amount of the conductive carbonaceous material is from 0.3 to 3.0% by weight, preferably from 0.3 to 1.0% by weight of the whole iron powder. It cannot contribute to the oxygen absorption characteristics, and if it exceeds 3.0% by weight, the special effect is not enhanced, which is uneconomical.
[0012]
Usually, the reduced iron powder contains 0.01 to 0.3% by weight of a reducing agent, that is, a carbon content, which is dissolved in the iron powder or released from the iron powder. Since it exists as so-called free carbon, carbon in these forms does not contribute to the oxygen absorption characteristics of the oxygen scavenger.
[0013]
Further, in order to efficiently coat the conductive carbonaceous material, an oil content of 0.01 to 0.05% by weight, for example, spindle oil (trade name: Spinox S5, S10, any of which does not impair the fluidity of the iron powder) It is preferable to add Nippon Oil Co., Ltd.).
[0014]
The gist of the present invention is to form a thin film of a conductive carbonaceous substance locally on the surface of iron powder, thereby promoting an oxidation reaction by a local battery formed between the ground iron and the conductive material.
[0015]
FIG. 1 shows the principle diagram. A indicates iron powder, and B indicates a carbonaceous conductive material. Iron powder is converted into iron ions due to the presence of salt water. At this time, two electrons are emitted according to the following formula. The iron powder becomes an anode and the carbon material becomes a cathode. Will promote it.
Fe → Fe ++ + 2e −
[0016]
Various devices can be applied to locally coat the surface of the iron powder with these conductive carbonaceous materials. However, it is possible to form a cathode thin film by a coating process for 30 minutes to 3 hours using a ball mill, a conical blender, or the like. It is. If a "hybridization" commercially available from Nara Machinery Co., Ltd. is used as a film forming machine, the processing time can be shortened, but there is no particular restriction on the coating processing apparatus.
[0017]
In the present invention, for example, if iron powder reduced by using a tunnel kiln is applied, reactivity with oxygen is improved, and a high moisture type (self-reaction type) used for food products having high oxygen activity, particularly high water activity. When used as an oxygen scavenger, the oxygen concentration becomes 0.1% by volume or less in a short time, and the freshness of the food is efficiently maintained.
[0018]
It is needless to say that iron powder for welding rods or powder metallurgy for other purposes is produced in a conventional process, and that application of the present invention does not make these iron powders disadvantageous in terms of quality or economy. Absent.
[0019]
That is, the present invention is to use an iron powder which is generally produced at present, and to improve its function to an active iron powder suitable as a raw material for an oxygen scavenger.
[0020]
【Example】
Hereinafter, the present invention will be described in more detail based on examples and the like.
[0021]
Reference Example 1
10 kg of commercially available iron powder for a welding rod having the properties shown in Table 1 and 50 g of powdered graphite (fixed carbon: 97.0% by weight, average particle size: 7.0 μm, trade name: CP, manufactured by Nippon Graphite Industry Co., Ltd.) And subjected to a coating treatment for 24 hours to obtain activated iron powder.
[0022]
[Table 1]
100 g of the activated iron powder was placed in a 250 cc plastic bottle, and 8 cc of salt water (20.5%) was further poured into the bottle and shaken by hand for 1 minute to mix. Five plastic bottles were prepared, and the above operation was repeated to prepare five samples for temperature measurement (the plastic bottle was closed to prevent air from entering as much as possible). When the preparation was completed, the contents from each of the poly bottles were transferred to a 100 cc beaker, and the temperature at the approximate center of the beaker was measured by a thermocouple.
[0024]
As shown in the curve of FIG. 2, the temperature measurement result was about 65 ° C. (average of 5 samples) after 10 minutes.
[0025]
Comparative Example 1
The iron powder for a welding rod used in Reference Example 1 was treated with 8 cc of salt water (20.5%) in the same manner as in Reference Example 1 without conducting the conductive carbonaceous material treatment. Curve 2 shows that the temperature after 10 minutes was about 30 ° C., and the rate of temperature rise was significantly slower than that of the activated iron powder used in Reference Example 1.
[0026]
Reference Example 2
10 kg of activated carbon (trade name: Zeocoll S, manufactured by Powder Tech Co., Ltd.) (90 wt%) was added to 1 ton of iron powder obtained by grinding sponge iron reduced in a tunnel kiln to the particle size shown in Table 2. Activated iron powder was obtained by placing the mixture in a cone type mixer for 2 hours.
[0027]
[Table 2]
As a result of mixing the activated iron powder with 8 cc of salt water (20.5%) by the method described in Reference Example 1 and measuring the temperature, the curve was as shown in FIG. 2 and the temperature after 10 minutes was about 75 ° C. .
[0029]
In addition, 30 g of the iron powder and 27.7 g of a reaction auxiliary agent (a mixture of 4 g of activated carbon, 6 g of vermiculite, 2 g of wood flour, 0.7 g of salt, and 15 ml of water) are mixed well, and put in a nonwoven fabric used for ordinary disposable warmers. As shown in FIG. 3A, the bar graph shown in FIG. 3A was obtained. That is, the
[0030]
Comparative Example 2
The heat generation characteristics were evaluated in the same manner as in Reference Example 2 without performing the conductive carbonaceous substance coating treatment in Reference Example 2.
[0031]
As a result, the curve shown in FIG. 2 and the bar graph shown in FIG. 3B were obtained, and both were inferior in heat generation characteristics to the case where the activated iron powder of Reference Example 2 was used.
[0032]
Reference Example 3
Instead of the conductive carbonaceous substance (powder graphite) used in Reference Example 1, powder graphite (fixed carbon: 92.5% by weight, average particle diameter: 2 μm, trade name: Blue P, manufactured by Nippon Graphite Industry Co., Ltd.) was used. Except that the coating amount was increased to 200 g per 10 kg of iron powder, the heat generation characteristics were evaluated in the same manner as in Reference Example 1. As a result, the temperature after 10 minutes was 79 ° C.
[0033]
Example 1
To 1 ton of atomized iron powder (trade name: Atmel 300M, manufactured by Kobe Steel Co., Ltd.), 10 kg of activated carbon (trade name: Zeocoll S, manufactured by Powdertech Co., Ltd.) is put into a cone mixer with a fine powder (-45 μm or less 90% by weight). Activated iron powder was obtained by coating for 2 hours.
[0034]
About 2.6 g of the activated iron powder was mixed well with 13 mg of commercially available salt, and placed in a nonwoven fabric laminated with a perforated polyethylene film to prepare a water-dependent oxygen scavenger.
[0035]
This oxygen absorber was put in a gas barrier film bag, and 500 ml of air and water-containing absorbent cotton was enclosed. The oxygen concentration was measured at predetermined time intervals until oxygen was completely removed, and the results shown in Table 3 were obtained.
[0036]
[Table 3]
Comparative Example 3
Except that the atomized iron powder before the coating treatment with the carbonaceous substance was used in Example 1, the deoxygenation rate was evaluated in the same manner as in Example 1, and the results are as shown in Table 4.
[0038]
[Table 4]
【The invention's effect】
As is clear from the above description, a thin film of a conductive carbonaceous substance is formed on the surface of iron powder currently on the market for welding rods or powder metallurgy, or iron powder produced as an intermediate product thereof. By forming a certain amount locally, the activated iron powder of the present invention, whose surface has been modified so as to promote the oxidation reaction, can be obtained as a raw material for the oxygen scavenger.
[Brief description of the drawings]
FIG. 1 is a principle diagram for explaining the grounds on which an iron powder according to the present invention exhibits an effect.
FIG. 2 is a graph comparing the exothermic rising characteristics of the activated iron powder of the present invention and a comparative iron powder.
FIG. 3 is a graph comparing the heat generation characteristics of disposable warmers made using the iron powder of the present invention and comparative iron powder.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002173919A JP3570513B2 (en) | 2002-06-14 | 2002-06-14 | Use of activated iron powder as a deoxidizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002173919A JP3570513B2 (en) | 2002-06-14 | 2002-06-14 | Use of activated iron powder as a deoxidizer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5458893A Division JP3341020B2 (en) | 1993-02-22 | 1993-02-22 | Activated iron powder |
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| JP2003117385A JP2003117385A (en) | 2003-04-22 |
| JP3570513B2 true JP3570513B2 (en) | 2004-09-29 |
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| CN101803786B (en) * | 2010-04-09 | 2013-07-17 | 王力 | Dual-effect anti-staling agent and preparation method thereof |
| WO2024014023A1 (en) * | 2022-07-11 | 2024-01-18 | Ｊｆｅスチール株式会社 | Iron-based powder for oxygen reactant, and oxygen reactant |
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