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WO2024014023A1 - 酸素反応剤用鉄基粉末および酸素反応剤 - Google Patents

酸素反応剤用鉄基粉末および酸素反応剤 Download PDF

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Publication number
WO2024014023A1
WO2024014023A1 PCT/JP2023/005564 JP2023005564W WO2024014023A1 WO 2024014023 A1 WO2024014023 A1 WO 2024014023A1 JP 2023005564 W JP2023005564 W JP 2023005564W WO 2024014023 A1 WO2024014023 A1 WO 2024014023A1
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Prior art keywords
powder
iron
oxygen
carbonaceous
mass
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English (en)
French (fr)
Inventor
尚貴 山本
康佑 芦塚
繁 宇波
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JFE Steel Corp
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JFE Steel Corp
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Priority to JP2023544781A priority Critical patent/JP7643562B2/ja
Priority to PCT/JP2023/020709 priority patent/WO2024014177A1/ja
Priority to KR1020247035402A priority patent/KR20240165437A/ko
Priority to US18/865,336 priority patent/US20250312768A1/en
Priority to CN202380045487.2A priority patent/CN119325500A/zh
Priority to AU2023307735A priority patent/AU2023307735A1/en
Publication of WO2024014023A1 publication Critical patent/WO2024014023A1/ja
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/708—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23B2/712—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23B2/717—Oxygen absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F7/03—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • the present disclosure relates to iron-based powders and oxygen reactants for oxygen reactants.
  • Oxygen reactants that utilize the reaction between iron-based powder and oxygen are known to be used, for example, as oxygen scavengers and exothermic agents.
  • Oxygen scavengers are used to create a low-oxygen condition by sealing the container together with stored items such as foods and medicines, thereby suppressing quality deterioration due to oxidation of stored items and growth of mold, etc.
  • As a heat generating agent it is widely used as a disposable body warmer to warm the human body.
  • activated carbon, sodium chloride, silica powder, wood flour, water, sulfur powder, and the like are added to iron-based powder in order to further promote the oxygen reaction in these oxygen reactants.
  • reaction rate between iron and oxygen is important, and as a means to control the reaction rate, mixing powders of conductive substances other than iron with iron powder has been considered. ing.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2003-117385
  • the surface of the iron powder is partially coated with conductive carbonaceous substances such as conductive graphite, carbon black, graphite, and activated carbon.
  • Oxygen scavengers using active iron powder coated with weight percent are disclosed.
  • Patent Document 1 discloses that the so-called free carbon state liberated from iron powder has no effect on the oxygen absorption properties of the oxygen scavenger and requires an operation to partially coat the surface of the iron powder.
  • Patent Document 1 does not specify the components of the iron powder itself.
  • the surface of iron powder is oxidized, it becomes difficult to form iron ions and emit electrons. Therefore, when the surface of iron powder is oxidized as is commonly seen, the phenomenon described in Patent Document 1 where the iron powder becomes an anode and the carbon material becomes a cathode, promoting the oxidation reaction, does not occur. , there is a problem that it becomes less likely to occur.
  • the present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide an iron-based powder for an oxygen reactant and an oxygen reactant that have excellent oxygen reactivity.
  • carbonaceous powder such as graphite is said to have no effect on the oxygen absorbing properties of an oxygen scavenger in its free carbon state, and is considered not to function as an oxygen reactant.
  • iron powder and carbonaceous powder which is a conductive powder with a higher potential than the iron powder
  • a corrosion current flows from the high potential carbonaceous powder to the low potential iron powder.
  • a local battery mechanism occurs in which the corrosion current returns to the carbonaceous powder, which has a higher potential than the iron powder, via the electrolyte and then flows back to the iron powder. It is also believed that when such a mechanism occurs, the reaction between low-potential iron powder and oxygen is promoted.
  • the present disclosure is based on the above findings, and the gist of the disclosure is as follows. 1. iron powder having an atomic ratio O/Fe of oxygen and iron of 0.30 or less; Carbonaceous powder having a C content of 50% by mass or more, An iron-based powder for an oxygen reactant, wherein the content of the carbonaceous powder is 0.20% by mass or more and 30.00% by mass or less.
  • an iron-based powder for an oxygen reactant and an oxygen reactant having excellent oxygen reactivity can be obtained.
  • the reason why the iron-based powder for oxygen reactants of the present disclosure exhibits excellent oxygen reactivity is presumed to be as follows. That is, since the carbonaceous powder has a higher potential than the iron powder, when the carbonaceous powder and the iron powder come into contact with each other in the electrolytic solution, a corrosion current is generated and the oxidation reaction of the iron powder is promoted. Further, the iron-based powder for an oxygen reactant of the present disclosure has excellent reactivity with oxygen, and therefore is suitably used as the oxygen reactant of the present disclosure. Therefore, the oxygen reactant of the present disclosure can exhibit the same characteristics and effects as the iron-based powder for oxygen reactants of the present disclosure.
  • the potential of iron increases when it is oxidized, it is easier to increase the potential difference with the carbonaceous powder if the iron powder is not oxidized as much as possible before being used as an oxygen reactant. As a result, the corrosion current increases. Therefore, in the present disclosure, the atomic ratio of oxygen to iron (hereinafter also referred to as "O/Fe") in the iron powder of the iron-based powder for oxygen reactant needs to be 0.30 or less. If O/Fe is within this range, the potential difference between the carbonaceous powder and the iron powder in the electrolytic solution will be sufficiently large, and an effective (enough to promote the oxidation reaction of the iron powder) corrosion current amount will be obtained.
  • O/Fe oxygen to iron
  • O/Fe in the iron powder of the iron-based powder for an oxygen reactant is set to 0.30 or less.
  • the lower limit of O/Fe is not particularly determined, and may be 0, but from an industrial perspective, about 0.15 is preferable.
  • the value of O/Fe can be measured according to the method described later.
  • the iron powder used in the present disclosure can be produced by water atomization, gas atomization, a pulverization method, and an oxide reduction method. Further, in the present disclosure, carbonaceous powder is added to the iron powder, but the carbonaceous powder may be commercially available graphite powder, coke powder, carbon black powder, or the like.
  • the "iron-based powder” in the present disclosure refers to a metal powder containing 50.0% by mass or more of Fe. Moreover, the iron-based powder can further contain arbitrary elements such as C, S, O, N, Si, Na, Mg, and Ca in addition to the metal iron (Fe). Note that the metallic iron content of the iron-based powder can be measured in accordance with JIS A 5011-2 "Metallic iron quantitative determination method.”
  • the iron-based powder for oxygen reactants is a mixed powder of iron powder and carbonaceous powder, and the content of carbonaceous powder in the mixed powder is in the range of 0.20% by mass or more and 30.00% by mass or less. do. If the content of carbonaceous powder in the iron-based powder for oxygen reactant is less than 0.20% by mass, the amount of corrosion current will be small and there will be no effect on promoting the oxygen reaction of iron powder. On the other hand, since carbonaceous powder itself is difficult to oxidize, it reacts with less oxygen than iron powder.
  • the content of carbonaceous powder in iron-based powder for oxygen reactant is more than 30.00% by mass, iron powder
  • the oxygen reaction amount of the mixture of iron powder and carbonaceous powder becomes too low than the oxygen reaction amount of the iron powder alone.
  • the content of carbonaceous powder in the iron-based powder for oxygen reactant is preferably 0.50% by mass or more, and the content of carbonaceous powder is 15.00% by mass. It is preferable that it is below.
  • the present disclosure can achieve excellent oxygen reactivity by providing an iron-based powder for an oxygen reactant that satisfies the above requirements.
  • the particle size of the iron powder is not particularly limited as long as there is no problem in handling, but the median diameter (median value of particle size from cumulative volume frequency) D50 is 1 mm or less, preferably 400 ⁇ m or less, more preferably 200 ⁇ m or less. A particle size of . On the other hand, the lower limit is preferably about 5 ⁇ m from the viewpoint of handling. Additionally, D50 can be measured according to the method described below.
  • the carbonaceous powder of the present disclosure is carbonaceous powder in which the content of C component (carbon component) in the carbonaceous powder is 50% by mass or more. If the C content in the carbonaceous powder is less than 50% by mass, the amount of corrosion current will be small and there will be no effect on promoting the oxygen reaction of the iron powder.
  • the C content in the carbonaceous powder is preferably 60% by mass or more, more preferably 70% by mass or more.
  • the upper limit is not particularly limited, and the C content in the carbonaceous powder may be 100% by mass, but from an economic point of view, it is preferably about 95% by mass.
  • the particle size of the carbonaceous powder is not particularly limited as long as there is no problem in handling, but it is preferable to have a median diameter D50 of 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the lower limit of the particle size of the carbonaceous powder is preferably about 5 ⁇ m from the viewpoint of handling.
  • the method for measuring the median diameter D50 of iron powder and carbonaceous powder is as follows. Iron powder and carbonaceous powder to be measured are placed in ethanol as a solvent, dispersed by ultrasonic vibration for 30 seconds or more, and then measured using a laser diffraction particle size distribution analyzer using laser diffraction/scattering method. Measurement of particle size, ie volumetric particle size distribution of particles of iron powder and carbonaceous powder, respectively. A cumulative particle size distribution is calculated from the obtained particle size distribution, and the particle size of particles corresponding to 50% of the total volume of all particles is determined as the median diameter D50 . In the present disclosure, this median diameter D50 is used as a representative value of the particle size of the iron powder and carbonaceous powder, respectively.
  • the method for measuring O/Fe in powder in the present disclosure is preferably as follows. By performing X-ray diffraction measurement on the target powder and performing Rietveld analysis on the obtained diffraction data, the content of Fe alone, a compound of Fe and O, and other compounds in the powder can be determined. Since the number of atoms of Fe and O can be determined from the numerical value of the content, the value of O/Fe can be calculated.
  • iron powder used in manufacturing the iron powder used in the present disclosure, water or gas atomization methods are used, in which molten metal is sprayed with water or gas, pulverized, cooled, and solidified, and iron oxide (milled iron oxide) generated from the surface of steel sheets during hot rolling of steel materials is used. It is preferable to produce it by reducing iron ore powder (scale) or iron ore powder. Further, the produced powder may be classified or mixed using various methods to prepare iron powder according to the present disclosure. Note that in order to remove oxygen to achieve the O/Fe range described above, deoxidation may be performed using carbon such as coke or graphite or hydrogen gas at a temperature of 750° C. or higher.
  • the carbonaceous powder of the present disclosure may be a commercially available product such as graphite powder, coke powder, carbon black powder, etc.
  • coke powder it can be manufactured as follows. That is, in producing such coke powder, coal is carbonized at 1000° C. or higher for 10 hours or more to remove volatile matter and tar contained in the coal, and then pulverized or classified. Furthermore, recovered powder generated during pulverization and classification can also be suitably used.
  • the above-described iron-based powder for an oxygen reactant can be used as an oxygen reactant.
  • the oxygen reactant of the present disclosure can be obtained.
  • the constituents of the oxygen reactant other than the iron-based powder for oxygen reactants can be used without any particular restriction as long as they are used in conventionally known oxygen reactants. Examples of this structure include bags made of breathable packaging material made by laminating nonwoven fabric and perforated polyethylene, and bags made of breathable packaging material made by laminating paper and perforated polyethylene.
  • the iron-based powder for an oxygen reactant used in this example was produced using the following procedure. Iron ore powder was reduced with hydrogen to produce 39 types of iron powder with different O/Fe ratios. Such iron powder, two types of lignite (A, B), sub-bituminous coal, graphite powder (CPB, manufactured by Nippon Graphite Industries Co., Ltd.), and coke produced by carbonizing coal at 1200 ° C. for 15 hours are crushed. The produced coke powder and carbon black powder (REGAL 330R, manufactured by Cabot Corporation) were each put into a V-type mixer and mixed to produce each iron-based powder for an oxygen reactant. Here, the C content of the lignite A was 58.7% by mass.
  • the C content of the lignite B was 68.2% by mass.
  • the C content of the sub-bituminous coal was 75.7% by mass.
  • the C content of the graphite powder was 97.3% by mass.
  • the C content of the coke powder was 81.7% by mass.
  • the C content of the carbon black powder was 98.1% by mass. Note that O/Fe of the iron powder was calculated by measuring the content of Fe alone, a compound of Fe and O, and other compounds using an X-ray diffraction device (SmartLab manufactured by Rigaku Corporation).
  • the oxygen reaction rate of the iron-based powder for oxygen reactant was evaluated as follows. 0.6 g of an aqueous solution with a concentration of 12% by mass of sodium chloride was mixed with 1.5 g of zeolite (Shin Tohoku Chemical Industries, Zeofil 1424# with a particle size of 1.0 to 2.0 mm) and 0.1 g of activated carbon powder (Fujifilm Wa After adding it to the mixed powder made by Hikari Pure Chemical Industries (particle size 3.0 to 300 ⁇ m), 1.5 g of the mixture with the above iron-based powder for oxygen reactant was filled into a bag (50 mm long x 60 mm wide) of ventilation packaging material. Each oxygen reactant was obtained.
  • a laminated material composed of nonwoven fabric and open-pore polyethylene was used as the ventilation packaging material.
  • One of each oxygen reactant was sealed together with 3 L of air in a gas barrier bag made of a laminated material made of nylon/aluminum foil/polyethylene. After the bag was allowed to stand at 25° C. for 8 hours, the oxygen concentration inside the bag was measured using a gas chromatograph (GD3210D, manufactured by GL Sciences, Inc.). The oxygen reaction amount was calculated from the difference between the oxygen concentration thus measured and the oxygen concentration in the air, and the oxygen reaction amount per 1 g of the iron-based powder for oxygen reactant was calculated.
  • GD3210D gas chromatograph
  • Table 1 shows the results of the oxygen reaction amount of each iron-based powder for an oxygen reactant in Comparative Examples and Examples according to the present disclosure.
  • the iron-based powders of Examples 1 to 10 with a content of 0.20% by mass or more and 30.0% by mass or less have a higher oxygen reaction amount than the iron-based powders of Comparative Examples 1 to 29. It can be seen that the oxygen reaction amount per 1 g of base powder was 60 mL/g or more, indicating that the oxygen reaction amount was excellent.
  • Examples 7 to 10 in which the carbonaceous powder content is 0.50% by mass or more and 15.0% by mass or less have an oxygen reaction amount of 70mL/g or more per 1g of iron-based powder, and the oxygen It can be seen that the reaction amount is superior and the oxygen reactivity is excellent.

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Abstract

優れた酸素反応性を有する酸素反応剤用鉄基粉末を提供する。酸素反応剤用鉄基粉末は、酸素と鉄の原子数比Ｏ／Ｆｅが０．３０以下である鉄粉と、Ｃ分の含有量が５０質量％以上である炭素質粉と、を含み、前記炭素質粉の含有量が０．２０質量％以上３０．００質量％以下である。

Description

酸素反応剤用鉄基粉末および酸素反応剤
　本開示は、酸素反応剤用の鉄基粉末および酸素反応剤に関する。
　鉄基粉末と酸素の反応を利用した酸素反応剤として、例えば脱酸素剤や発熱剤の用途が知られている。脱酸素剤としては、食品および医薬品などの保存物とともに容器内に密封することで低酸素状態とし、保存物の酸化およびカビ等の繁殖などによる品質劣化の抑制に利用されている。発熱剤としては、人体などを温める使い捨てカイロとして広く利用されている。一般的に、これらの酸素反応剤は、酸素反応をより促進するため、鉄基粉末に対し、活性炭、塩化ナトリウム、シリカ粉末、木粉、水分および硫黄粉末などが添加されている。
　また、いずれの用途においても鉄と酸素との反応速度が重視されているところ、反応速度を制御するための手段として、従来から、鉄粉への鉄以外の導電性物質粉の混合が検討されている。
　例えば、特開２００３－１１７３８５号公報（特許文献１）には、鉄粉表面が導電性グラファイト、カーボンブラック、黒鉛および活性炭のような導電性炭素質物質が部分的に０．３～３．０重量％被覆された活性鉄粉を使用した脱酸素剤が開示されている。
　なお、特許文献１には、鉄粉から遊離したいわゆる遊離炭素状態では脱酸素剤の酸素吸収特性に効果が無く、鉄粉表面に部分被覆する操作が必要であることが開示されている。
特開２００３－１１７３８５号公報
　しかしながら、特許文献１の開示では、鉄粉自体の成分が規定されていない。特に鉄粉は表面が酸化していると鉄イオンとなりにくくなり、電子の放出がしにくくなる。そのため、一般に見られるように鉄粉の表面が酸化していると、特許文献１に記載されているような、鉄粉が陽極となり、炭素物質が陰極となって酸化反応が促進するという現象は、起こりにくくなるといった問題がある。
　本開示は、かかる実状に鑑みて為されたものであって、優れた酸素反応性を有する酸素反応剤用鉄基粉末および酸素反応剤を提供することを目的とする。
　黒鉛等の炭素質粉は、前述の通り、遊離炭素状態では脱酸素剤の酸素吸収特性に効果が無いとされており、酸素反応剤として機能しないと考えられる。
　黒鉛等の炭素質粉は、鉄よりも標準電極電位が高く、また鉄が酸化すると電位が上昇することが鉄の電位－ｐＨ図（プールベダイアグラム）からわかる。
　そして、鉄粉と鉄粉より高電位の導電性粉末である炭素質粉が電解液のような腐食環境下で接触すると、高電位の炭素質粉から低電位の鉄粉へ腐食電流が流れ、さらに腐食電流は電解液を経由して鉄粉より高電位の炭素質粉に戻った後に鉄粉に再び流れる、という局部電池機構が発生する。かかる機構が発生すると、低電位の鉄粉と酸素との反応が促進されるとも考えられる。
　そこで、発明者らは、鉄基粉末と酸素との反応を促進するため、あえて酸素と反応しにくい遊離炭素状態の炭素質粉を鉄粉に添加し混合することを想起し鋭意検討をした。その結果、優れた酸素反応性を呈する鉄基粉末の適正な混合割合があることを見出した。
　本開示は上記知見に基づくものであり、その要旨構成は次のとおりである。
１．酸素と鉄の原子数比Ｏ／Ｆｅが０．３０以下である鉄粉と、
　Ｃ分の含有量が５０質量％以上である炭素質粉と、を含み、
　前記炭素質粉の含有量が０．２０質量％以上３０．００質量％以下である酸素反応剤用鉄基粉末。
２．前記１に記載の酸素反応剤用鉄基粉末を用いた酸素反応剤。
　本開示によれば、優れた酸素反応性を有する酸素反応剤用鉄基粉末および酸素反応剤が得られる。
　以下、本開示の実施形態について説明する。なお、以下の実施の形態については、本開示を説明するための例示であり、本開示はその実施の形態のみに限定されない。
　本開示の酸素反応剤用鉄基粉末が、優れた酸素反応性を呈する理由としては、以下が推測される。すなわち、炭素質粉は鉄粉と比較して高電位であるため、電解液において炭素質粉と鉄粉とが接触すると腐食電流が発生して鉄粉の酸化反応が促進するからである。また、本開示の酸素反応剤用鉄基粉末は、酸素との反応性に優れるため、本開示の酸素反応剤に好適に用いられる。したがって、本開示の酸素反応剤は、本開示の酸素反応剤用鉄基粉末と同様の特徴および効果を奏することができる。
　ここで、鉄は酸化すると電位が上昇するため、酸素反応剤としての使用前の鉄粉はなるべく酸化していない方が炭素質粉との電位差を大きくしやすい。その結果、腐食電流が大きくなる。そのため、本開示では、酸素反応剤用鉄基粉末の鉄粉における酸素と鉄の原子数比（以下、「Ｏ／Ｆｅ」ともいう）を０．３０以下とする必要がある。かかるＯ／Ｆｅの範囲であれば、電解液中において、前記炭素質粉と鉄粉との電位差が十分大きくなり、効果的な（鉄粉の酸化反応を促進するのに十分な）腐食電流量を生じるからである。そのため、本開示では、酸素反応剤用鉄基粉末の鉄粉におけるＯ／Ｆｅを０．３０以下とする。なお、Ｏ／Ｆｅの下限は特に定めず、０であってもよいが、工業的には０．１５程度が好ましい。また、Ｏ／Ｆｅの値は、後述する手法に従って測定可能である。
　本開示に用いる鉄粉は、水アトマイズ、ガスアトマイズ、粉砕法および酸化物還元法によって製造可能である。また、本開示は、かかる鉄粉に対し、炭素質粉を添加するが、かかる炭素質粉は、市販品の、黒鉛粉、コークス粉およびカーボンブラック粉等でよい。
　ここで、本開示における「鉄基粉末」とは、５０．０質量％以上のＦｅを含む金属粉末を指すものとする。また、鉄基粉末は、上記金属鉄（Ｆｅ）の他に、例えば、Ｃ、Ｓ、Ｏ、Ｎ、Ｓｉ、Ｎａ、Ｍｇ、Ｃａ等の任意の元素を更に含むことができる。なお、鉄基粉末の金属鉄含有量は、ＪＩＳ Ａ ５０１１－２「金属鉄定量方法」に準じて測定可能である。
　酸素反応剤用鉄基粉末は、鉄粉と炭素質粉との混合粉であって、かかる混合粉中の炭素質粉の含有量を０．２０質量％以上３０．００質量％以下の範囲とする。酸素反応剤用鉄基粉末における炭素質粉の含有量が０．２０質量％未満だと腐食電流量が少なく鉄粉の酸素反応促進に効果が無い。一方、炭素質粉自身は酸化しにくいことから鉄粉より酸素と反応する量が少ないため、酸素反応剤用鉄基粉末における炭素質粉の含有量が３０．００質量％より多いと、鉄粉と炭素質粉の混合物の酸素反応量が鉄粉単体の酸素反応量よりも低くなり過ぎてしまう。なお、酸素反応性の観点から、酸素反応剤用鉄基粉末における炭素質粉の含有量は０．５０質量％以上であることが好ましく、また、炭素質粉の含有量は１５．００質量％以下であることが好ましい。
　本開示は、上記の要件を満たす酸素反応剤用鉄基粉末とすることで、優れた酸素反応性を達成することができる。
　鉄粉の粒径は、取扱いに問題がなければ、特に限定されないが、メジアン径（累積の体積頻度からの粒径の中央値）Ｄ５０で１ｍｍ以下、好ましくは４００μｍ以下、より好ましくは２００μｍ以下の粒径のものが良い。一方、下限は、取扱いの点で５μｍ程度とすることが好ましい。また、Ｄ５０は、後述の手法に従って測定可能である。
　本開示の炭素質粉は、炭素質粉中のＣ分（炭素分）の含有量が５０質量％以上の炭素質粉とする。炭素質粉中のＣ分の含有量が５０質量％未満だと腐食電流量が少なくなって鉄粉の酸素反応促進に効果が無い。炭素質粉中のＣ分は、好ましくは６０質量％以上、より好ましくは７０質量％以上である。一方、上限は特に限定されず、炭素質粉中のＣ分は１００質量％であってもよいが、経済的な点から９５質量％程度とすることが好ましい。
　また、炭素質粉の粒径は、取扱いに問題がなければ、特に限定されないが、メジアン径Ｄ５０で１００μｍ以下、好ましくは５０μｍ以下、より好ましくは３０μｍ以下の粒径のものが良い。一方、炭素質粉の粒径の下限は、取扱いの点で５μｍ程度とすることが好ましい。
　鉄粉および炭素質粉の、メジアン径Ｄ５０の測定方法は、次の通りである。測定対象とする鉄粉および炭素質粉を、溶媒としてのエタノール中に投入し、３０秒以上の超音波振動により分散させて、レーザー回折・散乱法を用いたレーザー回折式粒度分布測定機により、粒径の測定、すなわち、鉄粉および炭素質粉の粒子の体積基準の粒度分布をそれぞれ測定する。得られた粒度分布から累積粒度分布を算出し、全粒子の体積の総和の５０％に相当する粒子の粒径がメジアン径Ｄ５０として求める。本開示では、このメジアン径Ｄ５０を上記鉄粉および炭素質粉の粒径の代表値としてそれぞれ用いる。
［粉末中のＯ／Ｆｅの算出方法］
　本開示における粉末中のＯ／Ｆｅの測定方法は、次の通りとすることが好ましい。対象となる粉末をＸ線回折測定し、得られた回折データをリートベルト解析することで、粉末中のＦｅ単体やＦｅとＯの化合物、その他化合物の含有率がわかる。かかる含有率の数値からＦｅやＯの原子数が求められるので、Ｏ／Ｆｅの値が算出できる。
［鉄粉の製造］
　本開示に用いる鉄粉の製造に当たっては、金属溶湯に水やガスを吹き付け、粉化して冷却凝固させる水アトマイズ法やガスアトマイズ法、また、鋼材の熱間圧延時に鋼板表面から発生する酸化鉄（ミルスケール）や、鉄鉱石粉を還元して作製するのが好ましい。さらに、作製した粉末を様々な方法で分級または混合して本開示に従う鉄粉に調整しても良い。なお、前記したＯ／Ｆｅの範囲とするため酸素を除去するには、コークスや黒鉛などの炭素または水素ガスを用いて７５０℃以上の条件で脱酸すればよい。
［炭素質粉］
　本開示の炭素質粉は、黒鉛粉、コークス粉、カーボンブラック粉等の市販品でよいが、例えば、コークス粉の場合は以下の通りに製造することができる。すなわち、かかるコークス粉の製造に当たっては、石炭を１０００℃以上で１０時間以上乾留して石炭に含まれる揮発分やタールを除去したのち、粉砕や分級を施すことが挙げられる。さらに、粉砕や分級時に発生した粉末を回収したものでも好適に使用することができる。
［鉄基粉末の製造］
　酸素反応剤用鉄基粉末の製造に当たっては、前述した鉄粉と炭素質粉とを混合する必要がある。酸素反応剤用鉄基粉末において、鉄粉と炭素質粉との混合は、均一であると好ましい。そのため、Ｖ型混合機、ダブルコーンミキサー、コニカルブレンダーなどで混合する装置を用いるのが好ましい。なお、上記の装置およびその混合条件は公知のものを用いればよい。
［酸素反応剤］
　本開示では、上述した酸素反応剤用鉄基粉末を用いて酸素反応剤とすることができる。例えば、以下に記載する袋に、前記酸素反応剤用鉄基粉末を封入すれば、本開示の酸素反応剤とすることができる。なお、酸素反応剤における、酸素反応剤用鉄基粉末以外の構成物は、従来公知の酸素反応剤に用いられるものであれば、とくに制限なく使用することができる。この構成物として、例えば、不織布と開孔ポリエチレンを重ね合わせた通気包装材の袋や、紙と開孔ポリエチレンを重ね合わせた通気包装材の袋等が挙げられる。
　本実施例に供する酸素反応剤用鉄基粉末は、以下の手順で作製した。鉄鉱石粉を水素還元してＯ／Ｆｅの異なる鉄粉を３９種類作製した。かかる鉄粉並びに、石炭である褐炭２種（Ａ、Ｂ）や亜瀝青炭、黒鉛粉（ＣＰＢ、日本黒鉛工業株式会社製）、石炭を１２００℃かつ１５時間乾留して作製したコークスを粉砕して製造したコークス粉およびカーボンブラック粉（ＲＥＧＡＬ３３０Ｒ、Ｃａｂｏｔ　Ｃｏｒｐｏｒａｔｉｏｎ製）を、Ｖ型混合機に各々投入して混合し、各酸素反応剤用鉄基粉末を作製した。ここで、上記褐炭ＡのＣ分の含有量は５８．７質量％であった。上記褐炭ＢのＣ分の含有量は６８．２質量％であった。上記亜瀝青炭のＣ分の含有量は７５．７質量％であった。上記黒鉛粉のＣ分の含有量は９７．３質量％であった。上記コークス粉のＣ分の含有量は８１．７質量％であった。上記カーボンブラック粉のＣ分の含有量は９８．１質量％であった。なお、鉄粉のＯ／Ｆｅは、Ｘ線回折装置（株式会社リガク製ＳｍａｒｔＬａｂ）を用いて、Ｆｅ単体やＦｅとＯの化合物、その他化合物の含有率を測定して算出した。
　本実施例において、酸素反応剤用鉄基粉末の酸素反応率評価は、以下の通りとした。塩化ナトリウムの濃度が１２質量％の水溶液０．６ｇを１．５ｇのゼオライト（新東北化学工業製　粒径１．０～２．０ｍｍのゼオフィル１４２４♯）と０．１ｇの活性炭粉末（富士フイルム和光純薬製　粒径３．０～３００μｍ）の混合粉末に添加後、１．５ｇの上記酸素反応剤用鉄基粉末と混合した物を通気包装材の袋（縦５０ｍｍ×横６０ｍｍ）に充填して各酸素反応剤を得た。通気包装材には、不織布と開孔ポリエチレンから構成される積層材料を用いた。各酸素反応剤１個を、３Ｌの空気と共に、ナイロン／アルミ箔／ポリエチレンから構成される積層材料であるガスバリア性の袋に密封した。この袋を２５℃で８時間静置後、袋内の酸素濃度をガスクロマトグラフ（ジーエルサイエンス株式会社製ＧＤ３２１０Ｄ）で測定した。かように測定した酸素濃度と空気中の酸素濃度との差異から酸素反応量を算出し、酸素反応剤用鉄基粉末１ｇあたりの酸素反応量を算出した。
　表１に、比較例と本開示に従う実施例の各酸素反応剤用鉄基粉末の酸素反応量の結果をそれぞれ示す。
Figure JPOXMLDOC01-appb-T000001
　表１に記載のとおり、鉄粉における酸素と鉄の原子数比Ｏ／Ｆｅが０．３０以上、かつ鉄粉との混合粉中のＣ分の含有量が５０質量％以上の炭素質粉の含有量が０．２０質量％以上３０．０質量％以下である実施例１～１０の鉄基粉末の方が、比較例１～２９の鉄基粉末よりも酸素反応量が高く、さらに、鉄基粉末１ｇあたりの酸素反応量が６０ｍＬ／ｇ以上となって、酸素反応量に優れていることが分かる。
　中でも、炭素質粉の含有量が０．５０質量％以上１５．０質量％以下である実施例７～１０は、いずれも鉄基粉末１ｇあたりの酸素反応量が７０ｍＬ／ｇ以上であり、酸素反応量により優れており、優れた酸素反応性を有していることが分かる。

Claims (2)

  1. 　酸素と鉄の原子数比Ｏ／Ｆｅが０．３０以下である鉄粉と、
    　Ｃ分の含有量が５０質量％以上である炭素質粉と、を含み、
    　前記炭素質粉の含有量が０．２０質量％以上３０．００質量％以下である酸素反応剤用鉄基粉末。
  2. 　請求項１に記載の酸素反応剤用鉄基粉末を用いた酸素反応剤。
     
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