JP2011183255A - Calcium-alkaline type adsorptive material and method for manufacturing this material - Google Patents
Calcium-alkaline type adsorptive material and method for manufacturing this material Download PDFInfo
- Publication number
- JP2011183255A JP2011183255A JP2010048472A JP2010048472A JP2011183255A JP 2011183255 A JP2011183255 A JP 2011183255A JP 2010048472 A JP2010048472 A JP 2010048472A JP 2010048472 A JP2010048472 A JP 2010048472A JP 2011183255 A JP2011183255 A JP 2011183255A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- acetic acid
- alkali
- activated carbon
- filter
- 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.)
- Granted
Links
Abstract
Description
本発明はＣａ−アルカリ型吸着性材料およびその製造方法法に係り、特に、添着剤と反応せず、活性炭で問題となっているような蓄熱発火に対する危険性を低減でき、かつ低コスト化も可能とする、Ｃａ−アルカリ型吸着性材料およびその製造方法に関する。 The present invention relates to a Ca-alkali-type adsorbent material and a method for producing the same, and in particular, it does not react with an additive and can reduce the risk of regenerative ignition that is a problem with activated carbon, and can also reduce costs. The present invention relates to a Ca-alkaline adsorbent material and a method for producing the same.
昨今の住環境は、エネルギー問題を反映して、断熱性・気密性を向上させる傾向にある。そのため、一度汚れた室内の空気は外部に排出されずに室内に滞留してしまう恐れがある。このような問題を解決し、健康的な生活を送るために、空気清浄機の設置は有意義である。 Recent living environments tend to improve heat insulation and airtightness, reflecting energy problems. For this reason, the indoor air once contaminated may stay in the room without being discharged to the outside. In order to solve such problems and lead a healthy life, the installation of an air purifier is meaningful.
空気清浄機には、脱臭機能と、除菌・アレルゲン除去等の集塵機能とがある。このうち脱臭の方式には、活性炭などの濾材フィルターによる吸着脱臭、オゾン分解などの原理を利用した放電・触媒利用型の脱臭、紫外線ランプと光触媒フィルターを組み合わせた光触媒脱臭がある。また集塵の方式には、ＨＥＰＡ（Ｈｉｇｈ Ｅｆｆｉｃｉｅｎｃｙ Ｐａｒｔｉｃｕｌａｔｅ Ａｉｒ）フィルター、ＵＬＰＡ（Ｕｌｔｒａ Ｌｏｗ Ｐｅｎｅｔｒａｔｉｏｎ Ａｉｒ Ｆｉｌｔｅｒ）フィルター、電気集塵方式等がある。 The air cleaner has a deodorizing function and a dust collecting function such as sterilization and allergen removal. Among them, the deodorization methods include adsorption deodorization using a filter medium filter such as activated carbon, discharge / catalyst-type deodorization utilizing a principle such as ozone decomposition, and photocatalytic deodorization combining an ultraviolet lamp and a photocatalytic filter. Examples of the dust collection method include a high efficiency particulate air (HEPA) filter, an ultra low penetration air filter (ULPA) filter, and an electric dust collection method.
さて、空気清浄機の脱臭対象となる脱臭ガスにはさまざまなものがあるが、代表的なものを挙げると、体臭、タバコ臭、ペット臭、生ごみ臭、さらにはシックハウスの原因物質であるホルムアルデヒド等である。とりわけタバコ臭は、従来の空気清浄機の脱臭対象ガスとして、最も多く挙げられているものである。公共の場における喫煙規制の拡大傾向と、それに伴い狭小化する喫煙可能区域・箇所におけるタバコ臭の激化・高密度化により、空気清浄機におけるタバコ臭脱臭機能の位置づけは、今後ますます重要になると考えられる。 There are various types of deodorizing gases that can be deodorized by air purifiers. Typical examples include body odor, tobacco odor, pet odor, garbage odor, and formaldehyde, which is the cause of sick house. Etc. In particular, tobacco odor is the most frequently cited gas for deodorization of conventional air purifiers. The positioning of tobacco odor deodorizing function in air purifiers will become more and more important in the future due to the increasing trend of smoking restrictions in public places and the intensification and increase in density of tobacco odors in smoking areas and places that are becoming narrower accordingly. Conceivable.
タバコ臭の主な成分は、アセトアルデヒド、アンモニア、および酢酸である。したがって空気清浄機の脱臭機能としては、これらの物質を吸着できる吸着材を用いる必要がある。従来、アセトアルデヒド用吸着材としては活性炭にアミンとリン酸を添着したもの、アンモニア用吸着材としては活性炭にリン酸を添着したもの、酢酸用吸着材としては活性炭に水酸化ナトリウムや水酸化カリウムを添着したものが用いられている。 The main components of tobacco odor are acetaldehyde, ammonia, and acetic acid. Therefore, it is necessary to use an adsorbent capable of adsorbing these substances as the deodorizing function of the air cleaner. Conventionally, the adsorbent for acetaldehyde is an activated carbon impregnated with amine and phosphoric acid, the adsorbent for ammonia is an activated carbon impregnated with phosphoric acid, and the adsorbent for acetic acid is sodium hydroxide or potassium hydroxide. Attached ones are used.
なお、タバコ臭を脱臭対象ガスとする脱臭技術については従来、種々の考案もなされている。たとえば後掲特許文献１は、アルカリ分を含有しかつ細孔が発達している活性炭と、リンゴ酸と鉄塩とを添着した活性炭とが配合された空気浄化剤を基体に担持してなる脱臭フィルターを開示している。 Various devices have been conventionally devised for deodorizing technology using tobacco odor as a gas to be deodorized. For example, Patent Document 1 listed below describes a deodorizing method in which an air purification agent containing an alkali component and having fine pores and an activated carbon impregnated with malic acid and an iron salt is supported on a substrate. A filter is disclosed.
また、特許文献２は、針葉樹で極性ガス吸着に適したＰＥＧ修飾炭、および高温焼成炭、非極性の揮発性有害化学物質ガスの吸着に適した低温焼成炭、および化学修飾炭といった炭化材と、無機粘土物質やパルブ繊維等の補助材とを混合、積層あるいは成形してなる空気浄化用吸着材を開示している。 Patent Document 2 discloses PEG-modified charcoal suitable for polar gas adsorption in coniferous trees, and carbonized materials such as high-temperature calcined charcoal, low-temperature calcined charcoal suitable for adsorption of non-polar volatile hazardous chemical gas, and chemically-modified charcoal. In addition, an air purification adsorbent obtained by mixing, laminating or molding an auxiliary material such as an inorganic clay substance or a pulp fiber is disclosed.
しかし、タバコ臭脱臭も可能な吸着性材料として特に有効なものである活性炭には、次のような問題がある。
〈１〉吸着した有機物の酸化反応熱等による蓄熱発火が懸念されること。
〈２〉空気清浄機での利用に必要な程度の吸着性能を得るには添着剤の添着は不可欠であるが、水酸化ナトリウム等を添着した酢酸用活性炭は、他の吸着剤と比較してガス吸着や吸湿等に起因する発熱の危険性があること。
〈３〉賦活処理等の処理が必要であるため、高コストとなること。
したがって、活性炭を用いることなくタバコ臭を含む脱臭機能を有効に備えた新規な吸着性材料が得られることは、産業上利用性も高く有意義なことである。
However, activated carbon which is particularly effective as an adsorptive material capable of deodorizing tobacco odor has the following problems.
<1> There is concern about heat storage ignition due to oxidation reaction heat or the like of the adsorbed organic matter.
<2> To obtain the adsorption performance necessary for use in an air cleaner, it is indispensable to add an adsorbent. However, activated carbon for acetic acid with sodium hydroxide or the like is compared with other adsorbents. There is a risk of heat generation due to gas adsorption or moisture absorption.
<3> Since processing such as activation processing is necessary, the cost is high.
Therefore, it is highly industrially meaningful to obtain a novel adsorbent material that effectively has a deodorizing function including tobacco odor without using activated carbon.
さて、青森県はホタテガイ養殖の一大産地であり、従来からホタテガイの加工も盛んに行われている。しかし、産業廃棄物として水産加工場等から排出されるホタテガイ貝殻の量は、毎年約５万ｔｏｎにも及び、これらの利活用はなかなか進まない。また、貝殻は野積み状態のまま放置され続けているため、今や膨大な累積量を抱える状況となっている。したがって、ホタテガイ貝殻の新たな利活用方法は、青森県の地域産業・経済における重要なテーマの一つである。 Now, Aomori Prefecture is a large production area for scallop farming, and scallops have been actively processed. However, the amount of scallop shells that are discharged as industrial waste from fisheries processing plants and the like reaches about 50,000 tons every year, and the utilization of these is difficult. In addition, since shells continue to be left unstacked, they now have a huge cumulative amount. Therefore, the new utilization method of scallop shells is one of the important themes in local industry and economy in Aomori Prefecture.
本発明が解決しようとする課題は、かかる従来技術の問題点や状況を踏まえ、添着剤と反応せず、活性炭において問題となっているような蓄熱発火の危険性を低減でき、かつ低コスト化も可能とし、さらに、ホタテガイ貝殻のような産業廃棄物の有効活用にもなり得る、タバコ臭を含む脱臭機能を有効に備えたＣａ−アルカリ型吸着性材料およびその製造方法を提供することである。 The problem to be solved by the present invention is based on the problems and situations of the prior art, and does not react with the additive, can reduce the risk of heat storage and ignition, which is a problem with activated carbon, and lowers the cost. It is also possible to provide a Ca-alkali-type adsorbent material effectively having a deodorizing function including tobacco odor, which can be used effectively for industrial waste such as scallop shells, and a method for producing the same. .
本願発明者らはこれまで、ホタテ貝殻焼成粉末と石灰石のホルムアルデヒド軽減機能を比較し、ホタテガイ貝殻をアルデヒド吸着剤用担持体に利用する技術を発明してきた（特開２００９−２１３９８７：吸着剤およびその製造方法、他）が、空気清浄機用の吸着剤として活用するためには、添着剤を添着してその能力を向上させることは不可欠である。したがって本発明においても、担持体としてのホタテガイ貝殻等に添着剤を添着することが基本となる。 The inventors of the present application have so far compared the formaldehyde reduction function of scallop shell calcined powder and limestone, and have invented a technology that uses scallop shell as a carrier for an aldehyde adsorbent (JP 2009-213987 A: Adsorbent and its) In order for a manufacturing method, etc.) to be used as an adsorbent for an air purifier, it is essential to add an additive to improve its capacity. Therefore, in the present invention, it is fundamental to attach an additive to a scallop shell as a carrier.
さて、ホタテガイ貝殻はアルカリ性である。したがって、添着剤としてアミンとリン酸を用いるアセトアルデヒド用吸着材や、添着剤としてリン酸を用いるアンモニア用吸着材は、貝殻との反応性を有するため除外し、添着剤として、貝殻との反応性を有しない水酸化ナトリウムや水酸化カリウムを用いる酢酸用吸着材を、本発明検討開始に際しての、基本的な着想とした。そして検討の結果、活性炭のようにこれらの添着剤と反応せず、活性炭で問題となっている蓄熱発火の危険性が少なく、かつ低コスト化も可能な吸着性材料を得られることを実証確認し、本発明の完成に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は、以下の通りである。 Now, scallop shells are alkaline. Therefore, the adsorbent for acetaldehyde that uses amine and phosphoric acid as an additive and the adsorbent for ammonia that uses phosphoric acid as an additive are excluded because they have reactivity with shells and are reactive with shells as additives. The adsorbent for acetic acid using sodium hydroxide or potassium hydroxide that does not have a basic idea was taken as the basic idea at the start of the study of the present invention. As a result of verification, it has been verified that it is possible to obtain an adsorbent material that does not react with these additives like activated carbon, has a low risk of thermal storage ignition, which is a problem with activated carbon, and can be reduced in cost. Thus, the present invention has been completed. That is, the invention claimed in the present application, or at least the disclosed invention, as means for solving the above-described problems is as follows.
〔１〕 Ｃａ高含有生体材料にアルカリを添着させてなる、吸着性材料。
〔２〕 前記Ｃａ高含有生体材料はホタテガイ貝殻、またはその他の貝殻であることを特徴とする、〔１〕に記載の吸着性材料。
〔３〕 前記アルカリは水酸化ナトリウム、水酸化カリウムまたはその他の強アルカリであることを特徴とする、〔１〕または〔２〕に記載の吸着性材料。
〔４〕 酸性ガス吸着用であることを特徴とする、〔１〕ないし〔３〕のいずれかに記載の吸着性材料。
〔５〕 酢酸吸着用であることを特徴とする、〔１〕ないし〔３〕のいずれかに記載の吸着性材料。
[1] An adsorptive material obtained by adding alkali to a Ca-rich biomaterial.
[2] The adsorptive material according to [1], wherein the high Ca-containing biomaterial is a scallop shell or other shell.
[3] The adsorptive material according to [1] or [2], wherein the alkali is sodium hydroxide, potassium hydroxide or other strong alkali.
[4] The adsorptive material according to any one of [1] to [3], which is for acidic gas adsorption.
[5] The adsorptive material according to any one of [1] to [3], which is for acetic acid adsorption.
〔６〕 吸着性材料中に占めるアルカリの割合である添着率が２．５重量％以上であることを特徴とする、〔１〕ないし〔５〕のいずれかに記載の吸着性材料。
〔７〕 〔１〕ないし〔６〕のいずれかに記載の吸着性材料を用いたフィルター。
〔８〕 Ｃａ高含有生体材料にアルカリを添着させる、吸着性材料の製造方法。
〔９〕 前記Ｃａ高含有生体材料はホタテガイ貝殻、またはその他の貝殻であり、前記アルカリは水酸化ナトリウム、水酸化カリウムまたはその他の強アルカリであることを特徴とする、〔８〕に記載の吸着性材料の製造方法。
[6] The adsorptive material according to any one of [1] to [5], wherein an adhesion rate, which is a proportion of alkali in the adsorbent material, is 2.5% by weight or more.
[7] A filter using the adsorbent material according to any one of [1] to [6].
[8] A method for producing an adsorptive material, wherein alkali is attached to a Ca-rich biomaterial.
[9] The adsorption according to [8], wherein the high Ca-containing biomaterial is a scallop shell or other shell, and the alkali is sodium hydroxide, potassium hydroxide or another strong alkali. Method for producing a functional material.
本発明のＣａ−アルカリ型吸着性材料およびその製造方法は上述のように構成されるため、これによれば、添着剤と反応しないため、活性炭において問題となっているような蓄熱発火の危険性を低減しつつ、タバコ臭を含む臭気の脱臭を行うことができる。また、タバコ臭の主成分の一つは上述の通り酢酸だが、本発明によれば酢酸以外の酸性ガス、たとえば硫化水素、塩素ガス等の吸着脱臭、吸着除去にも用いることができる。しかも、従来の活性炭と同等、あるいはそれ以上に優れた酢酸その他酸性ガス吸着脱臭性能を備えた吸着性材料を実現できる。 Since the Ca-alkaline adsorbent material and the method for producing the same according to the present invention are configured as described above, according to this, there is a risk of regenerative ignition that is a problem in activated carbon because it does not react with the additive. It is possible to deodorize odors including tobacco odor while reducing the odor. One of the main components of tobacco odor is acetic acid as described above, but according to the present invention, it can be used for adsorption deodorization and adsorption removal of acid gases other than acetic acid, such as hydrogen sulfide and chlorine gas. Moreover, it is possible to realize an adsorbent material having acetic acid and other acidic gas adsorption / deodorization performance equivalent to or better than that of conventional activated carbon.
また本発明によれば、担持体であるＣａ高含有生体材料としてはホタテガイ貝殻その他の貝殻等の産業廃棄物を用いることができるため、低コスト化につながるとともに、産業廃棄物であるホタテガイ貝殻等の有効活用とすることもできる。 In addition, according to the present invention, industrial waste such as scallop shells and other shells can be used as the Ca-rich biomaterial that is the carrier, leading to cost reduction and scallop shells that are industrial waste. It can also be used effectively.
本発明について、さらに詳細に説明する。
本発明においてＣａ高含有生体材料とは、カルシウムを高度に含有している生体材料であり、ホタテガイを初めとする貝類の貝殻は全てこれに該当し、本発明において好適に用いることができる。しかしながら本発明がこれに限定されるものではない。たとえば、エビ、カニ、フジツボといった甲殻類、その他も含まれる。
The present invention will be described in further detail.
In the present invention, a high Ca-containing biomaterial is a biomaterial that contains calcium at a high level, and all shells of shellfish including scallops fall under this and can be suitably used in the present invention. However, the present invention is not limited to this. For example, shrimp, crabs, crustaceans such as barnacles, and others.
なお、貝類としてはホタテガイの他に、マガキも用いることができる。その他、アカガイ、サルボウガイ、イガイ、ムラサキイガイ、タイラギ、ヒオウギガイ、ツキヒガイ、イワガキ、トリガイ、マテガイ類、サラガイ、アゲマキガイ、シジミ類、バカガイ、ミルクイ、アサリ、チョウセンハマグリ、ウチムラサキ、ナミガイ、アワビ類、サザエ、エゾバイ、シライトマキバイ、エゾボラ類、エッチュウバイ、オオエッチュウバイ、ツバイハマグリ等も含む。 In addition to scallops, oysters can also be used as shellfish. Others, red mussels, snakeskin, mussels, mussels, oysters, snails, tsukihigai, swordfish, Triggery, mategai, saragai, swallowtail, swordfish, stingrays, milkfish, clams, clams, prickly pears, sea bream, abalone , Syrite Makibai, Ezobora, Etchubai, Giant Etchubai, Atsubai Clam and the like.
特に、ホタテガイ他養殖や食品加工等において大量の貝殻が産業廃棄物として排出される種類の貝の貝殻を用いることは、本発明吸着性材料のコスト低下に大いに寄与するものであり、かつ廃棄物の有効利用の観点からも望ましいことである。 In particular, the use of shells of a kind of shellfish in which a large amount of shells are discharged as industrial waste in aquaculture, food processing, etc. contribute greatly to the cost reduction of the adsorbent material of the present invention, and waste This is also desirable from the viewpoint of effective use.
本発明創作の発端は、タバコ臭を有効に吸着脱臭でき、従来の活性炭を用いた製品に代替する吸着性材料であるから、添着するアルカリとしては、水酸化ナトリウムや水酸化カリウムが第一に想定されるものである。しかしながら本発明の吸着性材料に係るアルカリがこれらに限定されるものではなく、添着剤として使用可能なアルカリは、強アルカリを初めとして全て該当する。 Since the creation of the present invention is an adsorptive material that can effectively adsorb and deodorize tobacco odors and replace products using conventional activated carbon, sodium hydroxide and potassium hydroxide are the primary alkalis to be added. It is assumed. However, the alkali related to the adsorptive material of the present invention is not limited to these, and alkalis that can be used as an additive are all applicable to strong alkalis and the like.
なお添着方法は、従来公知の方法を適宜用いることができる。また、吸着性材料中に占めるアルカリの割合である添着率を、特に、２．５重量％以上とすることができる。かかる添着率にすることにより、本発明吸着性材料の吸着性能を一層充分に発揮させることができるからである。しかしながら２．５重量％未満の添着率であっても本発明の範囲内である。 In addition, a conventionally well-known method can be used suitably for the attachment method. Further, the adhesion rate, which is the proportion of alkali in the adsorbing material, can be set to 2.5% by weight or more. This is because the adsorption performance of the adsorbent material of the present invention can be more fully exhibited by setting the adhesion rate to this value. However, even an adhesion rate of less than 2.5% by weight is within the scope of the present invention.
また上述のとおり、本発明吸着性材料はタバコ臭の主成分の一つである酢酸を効果的に吸着脱臭できるものだが、酢酸以外の酸性ガスをも吸着脱臭あるいは吸着除去の対象とすることができる。たとえば硫化水素、塩素ガス等の吸着脱臭、吸着除去等である。 In addition, as described above, the adsorbent material of the present invention can effectively adsorb and deodorize acetic acid, which is one of the main components of tobacco odor, but acid gases other than acetic acid may also be targeted for adsorption deodorization or adsorption removal. it can. For example, adsorption deodorization and adsorption removal of hydrogen sulfide, chlorine gas and the like.
図１は、本発明の吸着性材料の製造方法を示す説明図である。図示するように本発明製造方法は、添着処理Ｐによって、Ｃａ高含有生体材料１に対してアルカリ２を添着することで、吸着性材料３を得るものである。Ｃａ高含有生体材料１として特にホタテガイ貝殻その他の貝殻を用いることとし、またアルカリ２として特に水酸化ナトリウム、水酸化カリウムまたはその他の強アルカリを用いる構成を取れることは、上述のとおりである。このようにして得られた吸着性材料を、空気清浄機や、他の装置に組み込む空気清浄化ユニット等のフィルターとして用いることができる。 FIG. 1 is an explanatory view showing a method for producing an adsorptive material of the present invention. As shown in the figure, the production method of the present invention is to obtain the adsorbent material 3 by attaching alkali 2 to the high Ca-containing biomaterial 1 by the attaching treatment P. As described above, scallop shells and other shells are particularly used as the Ca-rich biomaterial 1, and sodium hydroxide, potassium hydroxide or other strong alkalis are particularly used as the alkali 2. The adsorptive material thus obtained can be used as a filter for an air purifier or an air purifying unit incorporated in another device.
以下、本発明を実施例によってさらに説明するが、本発明はかかる実施例に限定されるものではない。なお本実施例は、本発明に至る研究経過を示すものである。また実施例の説明においては、図表を含め、ホタテガイ貝殻を単に「ホタテ貝殻」ともいう。また同じく、ホタテガイ貝殻製の吸着性材料の吸着性材料を単に「ホタテ貝殻吸着剤」ともいう。
１．テーマ
ホタテ貝殻を基材として水酸化ナトリウムを添着した吸着性材料の酢酸除去特性、およびそれを用いた空気清浄機用フィルター脱臭特性評価
２．基材および活性炭の分級方法と評価
（１）供試材料
実施例基材としては、ホタテ貝殻（長慶社製、有機石灰ブロック用）を用いた。また比較例の活性炭としては、酢酸用活性炭（クラレケミカル社製、クラレコールＧＧ）を破砕して用いた。これらは、０．５ｍｍ〜１ｍｍの範囲で１分間分級したものを用いた。
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this Example. This example shows the progress of research leading to the present invention. In the description of the examples, the scallop shell is also simply referred to as “scallop shell” including the chart. Similarly, the adsorbent material of the adsorbent material made of scallop shell is also simply referred to as “scallop shell adsorbent”.
1. Theme Acetic acid removal characteristics of adsorbent material with scallop shell as base material and sodium hydroxide attached, and evaluation of filter deodorization characteristics for air purifiers using it Substrate classification method and evaluation of activated carbon (1) Test material As a base material of an example, scallop shell (manufactured by Changkei Co., Ltd., for organic lime block) was used. Moreover, as the activated carbon of the comparative example, activated carbon for acetic acid (Kuraray Chemical Co., Ltd., Kuraray Coal GG) was crushed and used. These used what was classified for 1 minute in the range of 0.5 mm-1 mm.
（２）測定
比表面積は、比表面積測定装置（島津製作所社製、フローソーブＩＩ）を用い、無破砕条件にて測定した。また熱分析は、熱分析装置（リガク社製、ＴＧ８１２０）を用いて行った。実施例・比較例両サンプルを遊星ミル（伊藤製作所社製、ｍｉｎｉ ＣＵＰ ＭＩＬＬ）で１分間粉砕し、１０５℃、２４時間乾燥後、白金パンに５ｍｇ入れ、昇温速度２０℃／ｍｉｎ、最高温度８００℃の条件で行った。
(2) Measurement The specific surface area was measured under a non-crushing condition using a specific surface area measuring device (manufactured by Shimadzu Corporation, Flowsorb II). Thermal analysis was performed using a thermal analyzer (TG8120, manufactured by Rigaku Corporation). Example / Comparative Example Both samples were pulverized with a planetary mill (manufactured by Ito Seisakusho, mini CUP MILL) for 1 minute, dried at 105 ° C. for 24 hours, put in a platinum pan, 5 mg heating rate 20 ° C./min, maximum temperature The test was performed at 800 ° C.
３．ホタテ貝殻を基材とした吸着性材料の調製
図２は、実施例における吸着性材料の吸着性材料調製方法を示す説明図である。図示するように、ホタテ貝殻を基材とした吸着性材料（ホタテ貝殻吸着性材料、ホタテ貝殻吸着剤）は、次のように調製した。すなわち、１００ｍｌビーカーにホタテ貝殻５０ｇを入れ、これにＮａＯＨ５０ｍｌを加え、デシケーター中で１時間減圧し、２時間放置した。その後ビーカー内容物をろ過し、ステンレス製バット上にホタテ貝殻を並べ置き、乾燥処理、分級処理をして、ホタテ貝殻吸着剤とした。
3. Preparation of adsorptive material based on scallop shell FIG. 2 is an explanatory view showing a method for preparing an adsorbent material for an adsorbent material in Examples. As shown in the figure, an adsorbent material (scallop shell adsorbent material, scallop shell adsorbent) based on scallop shell was prepared as follows. That is, 50 g of scallop shells were put in a 100 ml beaker, 50 ml of NaOH was added thereto, and the pressure was reduced in a desiccator for 1 hour and left for 2 hours. Thereafter, the contents of the beaker were filtered, scallop shells were placed on a stainless steel vat, dried and classified, and used as a scallop shell adsorbent.
なお添着剤として用いた水酸化ナトリウムＮａＯＨ（関東化学社製）の濃度は下記４条件とした。
条件１：１．２５ｍｏｌ／Ｌ、条件２：２．５０ｍｏｌ／Ｌ、条件３：３．７５ｍｏｌ／Ｌ、条件４：５．００ｍｏｌ／Ｌ
The concentration of sodium hydroxide NaOH (manufactured by Kanto Chemical Co., Inc.) used as an additive was the following four conditions.
Condition 1: 1.25 mol / L, Condition 2: 2.50 mol / L, Condition 3: 3.75 mol / L, Condition 4: 5.00 mol / L
４．ホタテ貝殻吸着性材料の添着率評価
添着率は、吸着剤中に占める水酸化ナトリウムの割合とし、次のように求めた。すなわち、まず前処理として、ホタテ貝吸着剤を粉末化し、その後、プレス機を用いて２６ｔｏｎ／ｍ２の圧力で、ホタテ貝吸着剤を円盤状に成型した。これを試料とし、エネルギー分散形蛍光Ｘ線分析装置（島津製作所社製、Ｒａｙｎｙ ＥＤＸ−８００ＨＳ）を用いて、貝殻由来のＣａと水酸化ナトリウム由来のＮａを分析対象として測定した。
4). Evaluation of Adhesion Rate of Scallop Shell Adsorbing Material The adhesion rate was determined as follows, with the proportion of sodium hydroxide in the adsorbent. That is, as a pretreatment, the scallop adsorbent was first pulverized, and then the scallop adsorbent was formed into a disk shape at a pressure of 26 ton / m 2 using a press. Using this as a sample, Ca-shell-derived Ca and sodium hydroxide-derived Na were measured for analysis using an energy dispersive X-ray fluorescence analyzer (manufactured by Shimadzu Corporation, Rayny EDX-800HS).
水酸化ナトリウムの添着率（％）の計算式は、下式のとおりである。
〔Ｎａ（％）×４０／２３〕／｛〔Ｃａ（％）×１００／４０〕＋〔Ｎａ（％）×４０／２３〕｝×１００
計算式中の各数字は、下記のとおり分子量である。
ＮａＯＨ：４０、 Ｎａ：２３
ＣａＣＯ３：１００、 Ｃａ：４０
The formula for calculating the deposition rate (%) of sodium hydroxide is as follows.
[Na (%) × 40/23] / {[Ca (%) × 100/40] + [Na (%) × 40/23]} × 100
Each number in the calculation formula is molecular weight as follows.
NaOH: 40, Na: 23
CaCO 3 : 100, Ca: 40
５．吸着性材料の除去能力評価
吸着性材料として、添着率０％の場合も含めた５条件による実施例のホタテ貝殻吸着剤、および比較例の活性炭について、酢酸除去能力評価を行った。なお活性炭は、１０５℃、２４時間乾燥処理したものを用いた。
図３は、実施例における吸着性材料の除去能力評価試験方法を示す説明図である。図示するように除去能力評価試験は、ガラスシャーレに吸着剤０．０３ｇを入れ、これを、１０ｐｐｍ酢酸、または５０ｐｐｍ酢酸雰囲気下としたデシケーター中に置き、２３℃で５時間放置した。その後、検知管（ガステック社製、酢酸Ｎｏ８１ 以下の実験でも同様）にてデシケーター中の酢酸濃度を測定した。なお、計算式は次のとおりである。
［除去率（％）］＝［測定値（ｐｐｍ）］／［ブランク（ｐｐｍ）］×１００
5. Evaluation of removing ability of adsorptive material As an adsorbing material, acetic acid removing ability was evaluated for the scallop shell adsorbent of the example and the activated carbon of the comparative example under five conditions including the case where the adhesion rate was 0%. The activated carbon used was dried at 105 ° C. for 24 hours.
FIG. 3 is an explanatory view showing the adsorptive material removal ability evaluation test method in Examples. As shown in the figure, in the removal capability evaluation test, 0.03 g of the adsorbent was put in a glass petri dish, which was placed in a desiccator in an atmosphere of 10 ppm acetic acid or 50 ppm acetic acid, and left at 23 ° C. for 5 hours. Thereafter, the acetic acid concentration in the desiccator was measured with a detector tube (manufactured by GASTECH, the same as in the experiment of acetic acid No 81 or lower). The calculation formula is as follows.
[Removal rate (%)] = [Measured value (ppm)] / [Blank (ppm)] × 100
６．空気清浄機用フィルターの作製
図４は、実施例吸着性材料を用いた空気清浄機用フィルターの作製方法を示す説明図である。図示するように、実施例・比較例の吸着剤を円柱状の筒が集合したいわゆるハニカム構造が形成された段ボール（紙製）に充填し、これを不織布で被覆して、空気清浄機用フィルターとした。説明図中には作製したフィルターの概観図および一部拡大図も併せ記載している。なおフィルター１枚当たりの吸着剤使用量は、表１のとおりとした。
6). Production of Air Cleaner Filter FIG. 4 is an explanatory view showing a production method of an air cleaner filter using an example adsorptive material. As shown in the figure, the adsorbents of Examples and Comparative Examples are filled into corrugated cardboard (made of paper) in which a so-called honeycomb structure in which cylindrical cylinders are gathered, and this is covered with a nonwoven fabric, and a filter for an air cleaner. It was. In the explanatory diagram, an overview of the produced filter and a partially enlarged view are also shown. The amount of adsorbent used per filter was as shown in Table 1.
７．脱臭試験
脱臭性能を評価する脱臭試験は、日本電機工業会規格 ＪＥＭ１４６７（家庭用空気清浄機）に準拠して行った。すなわち、容積１ｍ３の立方体形状の密閉したアクリル樹脂製ボックス内に、所定仕様の空気清浄機、吸煙機およびかくはんファンの各装置を設置し、吸煙機にはタバコ５本をセットしてこれに火をつけ、各装置を運転し、ボックス内の酢酸濃度を測定した。検知管による酢酸濃度測定は、後述する各実施例および比較例等について、それぞれ、空気清浄機使用前、使用開始後０．５分、１分、３分、５分、７分、１０分および３０分の各時点で測定した。なお各実施例・比較例等については、３連にて試験した。
7). Deodorization test The deodorization test for evaluating the deodorization performance was carried out in accordance with JEM 1467 (household air purifier) of the Japan Electrical Manufacturers' Association. That is, the acrylic resin box sealed cubical volume 1 m 3, given specification of the air purifier, installing the apparatuses puff machines and agitation fan, to set the five cigarettes to puff machine Turn on the fire, operate each device, and measure the acetic acid concentration in the box. The acetic acid concentration measurement by the detector tube was carried out for each of Examples and Comparative Examples described later, before use of the air cleaner, after use, 0.5 minutes, 1 minute, 3 minutes, 5 minutes, 7 minutes, 10 minutes and Measurements were taken at 30 minutes. Each Example / Comparative Example was tested in triplicate.
実施例としては、ＮａＯＨを５．００ｍｏｌ／Ｌ添着した（条件４）ホタテ貝殻吸着剤を、それぞれ５０ｇ、１００ｇ、１５０ｇ充填したフィルターを脱臭試験に供した。また比較例として、活性炭をそれぞれ５０ｇ、１００ｇ、１５０ｇ充填したフィルターを供した他、フィルター既存品としてペット用フィルタ（アイリスオーヤマ社製）も脱臭試験に供した。 As an example, filters filled with 50 g, 100 g, and 150 g of scallop shell adsorbent adsorbed with 5.00 mol / L of NaOH (Condition 4) were subjected to a deodorization test. In addition, as a comparative example, a filter filled with 50 g, 100 g, and 150 g of activated carbon was used, and a pet filter (manufactured by Iris Ohyama) was also used for the deodorization test as an existing filter product.
８．試験結果と考察
（１）基材の物性
表２に、実施例ホタテ貝殻吸着剤および比較例活性炭それぞれの基材（担持体）の比表面積測定結果を示す。ここに示されるとおり、ホタテ貝殻は活性炭と比較して顕著に比表面積が小さく、吸着剤用の基材としてはかなり低いレベルであると認められた。
8). Test Results and Discussion (1) Physical Properties of Substrate Table 2 shows the results of measuring the specific surface area of each of the base materials (supports) of Example scallop shell adsorbent and Comparative Example activated carbon. As shown here, the scallop shell has a remarkably small specific surface area compared with activated carbon, and it was recognized that it is a considerably low level as a base material for adsorbents.
図５は、実施例および比較例の各基材の熱分析結果を示すグラフである。図示するように、比較例の基材である活性炭では、３００℃付近より重量減少が始まり、７００℃付近で熱分解が完了した。一方、実施例の基材であるホタテ貝殻では、７００℃付近までほとんど重量減少が認められなかった。これにより、ホタテ貝殻は高い耐熱性を備えており、活性炭と比較して耐熱性に優れた吸着剤の基材であることがわかった。 FIG. 5 is a graph showing the thermal analysis results of the base materials of Examples and Comparative Examples. As shown in the figure, in the activated carbon which is the base material of the comparative example, weight reduction started from around 300 ° C., and thermal decomposition was completed at around 700 ° C. On the other hand, in the scallop shell which is the base material of the example, almost no weight reduction was observed up to around 700 ° C. As a result, it was found that the scallop shell had high heat resistance and was a base material for the adsorbent superior in heat resistance compared to activated carbon.
（２）添着剤の濃度と添着率
図６は、実施例において添着剤として用いたＮａＯＨの溶液濃度と添着率の関係を示すグラフである。図示するように、溶液濃度を高くするほど添着率は高くなり、上述条件４：５．００ｍｏｌ／Ｌ添着においては、添着率２．５％であった。なお、添着率が添着剤濃度に依存する傾向は活性炭でも同様に報告されており、添着剤濃度と添着率の関係は、基材の種類によらないものと判断された。
(2) Concentration of Additive and Adhesion Rate FIG. 6 is a graph showing the relationship between the concentration of NaOH used as an additive in the examples and the adhesion rate. As shown in the figure, the higher the solution concentration, the higher the deposition rate. In the above condition 4: 5.00 mol / L deposition, the deposition rate was 2.5%. The tendency of the adhesion rate to depend on the additive concentration was also reported for activated carbon, and the relationship between the additive concentration and the adhesion rate was determined not to depend on the type of substrate.
（３）吸着剤の酢酸除去特性
図７は、実施例において、低濃度（１０ｐｐｍ酢酸）における添着率と酢酸除去率との関係を示すグラフである。また、
図８は、実施例において、高濃度（５０ｐｐｍ酢酸）における添着率と酢酸除去率との関係を示すグラフである。これらに図示するように、添着率２．５％とした実施例ホタテ貝殻吸着剤は、活性炭と同等以上の酢酸除去特性を備えていることがわかった。
(3) Acetic acid removal characteristics of adsorbent FIG. 7 is a graph showing the relationship between the adhesion rate and the acetic acid removal rate at a low concentration (10 ppm acetic acid) in Examples. Also,
FIG. 8 is a graph showing the relationship between the adhesion rate and acetic acid removal rate at a high concentration (50 ppm acetic acid) in Examples. As shown in these figures, it was found that the scallop shell adsorbent of Example having an adhesion rate of 2.5% had an acetic acid removal property equal to or higher than that of activated carbon.
（４）脱臭フィルターの脱臭（酢酸除去）特性
図９は、実施例において、ホタテ貝殻吸着剤を使用したフィルターの脱臭（酢酸除去）特性を示すグラフである。また、
図１０は、実施例において、活性炭を使用したフィルターの脱臭（酢酸除去）特性を示すグラフである。いずれも、既存品と比較したグラフであり、脱臭試験開始前〜開始３０分時点での酢酸濃度を示したものである。これらに図示するように、実施例ホタテ貝殻吸着剤を用いた脱臭フィルターでは、空気清浄機運転開始後速やかに酢酸除去性能が発揮され、３分時点でボックス内酢酸濃度は２０％以下、７分時点でほぼ完全に０％となった。
(4) Deodorization (Acetic Acid Removal) Characteristics of Deodorization Filter FIG. 9 is a graph showing the deodorization (acetic acid removal) characteristics of the filter using the scallop shell adsorbent in the examples. Also,
FIG. 10 is a graph showing deodorization (acetic acid removal) characteristics of a filter using activated carbon in Examples. All are graphs compared with existing products, and show the acetic acid concentration before 30 minutes from the start of the deodorization test. As shown in these figures, in the deodorizing filter using the scallop shell adsorbent of Example, the acetic acid removing performance is exhibited immediately after the start of the air cleaner operation, and the acetic acid concentration in the box is 20% or less, 7 minutes at 3 minutes. At that time, it was almost completely 0%.
特に、ホタテ貝殻吸着剤を１００ｇまたは１５０ｇ用いたフィルターでは、５分時点で残存酢酸濃度がほとんど０％となり、既存品と同等あるいはそれを超える速度の酢酸除去特性を示した。また５０ｇ充填のフィルターは他の実施例に比べると若干緩やかな除去速度だったが、それでも開始１０分時点では、酢酸濃度は０％となった。 In particular, in the filter using 100 g or 150 g of the scallop shell adsorbent, the residual acetic acid concentration was almost 0% at 5 minutes, and the acetic acid removing characteristics at a rate equivalent to or exceeding that of existing products were exhibited. Moreover, the 50 g filter had a slightly slower removal rate compared with the other examples, but at the start of 10 minutes, the acetic acid concentration was 0%.
また図１０に示すように、比較例活性炭の場合、既存品に最も近い酢酸除去性能を示したのは１５０ｇ充填のものだけであり、しかも、それも既存品を超えるものではなく、空気清浄機運転開始１０分の時点でようやく酢酸濃度０％となるものだった。また、５分時点での残存酢酸濃度は１０数％〜３０％以上もあった。また、５０ｇあるいは１００ｇ充填のものでは、１０分の時点でも数％の酢酸が残存する結果だった。 As shown in FIG. 10, in the case of the comparative activated carbon, the acetic acid removal performance closest to that of the existing product is only 150g filled, and it does not exceed the existing product. At 10 minutes from the start of operation, the acetic acid concentration finally reached 0%. Moreover, the residual acetic acid concentration at the time of 5 minutes was 10 tens% to 30% or more. In addition, when 50 g or 100 g was filled, several% acetic acid remained even at 10 minutes.
以上のことから、本発明実施例のホタテ貝殻吸着剤を用いた脱臭フィルターの脱臭（酢酸除去）特性は、既存品と同等あるいはそれを超えるものであり、活性炭よりも優れたものであることが確認された。特に、１００ｇまたは１５０ｇの充填量とした場合は、運転開始直後５分でほとんど酢酸除去され、本発明によれば迅速な酢酸除去が可能であることがわかった。 From the above, the deodorizing (acetic acid removal) characteristics of the deodorizing filter using the scallop shell adsorbent of the embodiment of the present invention is equivalent to or exceeding that of existing products, and is superior to activated carbon. confirmed. In particular, when the filling amount was 100 g or 150 g, most of the acetic acid was removed in 5 minutes immediately after the start of operation, and it was found that the acetic acid can be removed quickly according to the present invention.
９．まとめ
以上のとおり、ホタテ貝殻の物性、それを基材とし水酸化ナトリウムを添着した酢酸用吸着剤の除去特性、および吸着剤を用いた脱臭フィルターの脱臭特性について、活性炭と比較、検討し、以下の結論を得た。
１）活性炭は３００℃付近より重量減少が始まったのに対してホタテ貝殻は７００℃付近まで重量減少が確認されなかった。つまり、ホタテ貝殻基材は高い耐熱性を備えている。
２）ホタテ貝殻への水酸化ナトリウム添着率は濃度が高くなるに従って高くなる。
３）ホタテ貝殻吸着性材料の酢酸除去能力は添着率が高くなるに従って高くなり、添着率２．５％で活性炭とほぼ同等、あるいはそれ以上の性能を備える。
４）フィルター化した吸着剤では、ホタテ貝殻吸着剤は活性炭よりも高い酢酸除去性能を備える。
9. Summary As described above, the properties of scallop shells, the removal characteristics of the adsorbent for acetic acid using it as the base material, and the deodorization characteristics of the deodorization filter using the adsorbent were compared and examined with activated carbon. The conclusion was obtained.
1) Weight loss of activated carbon started at around 300 ° C, whereas scallop shell did not show weight reduction to around 700 ° C. That is, the scallop shell base material has high heat resistance.
2) The rate of sodium hydroxide attached to the scallop shell increases as the concentration increases.
3) The acetic acid removing ability of the scallop shell adsorbing material increases as the adhesion rate increases, and the adhesion rate is 2.5%, which is almost equal to or higher than that of activated carbon.
4) With filtered adsorbents, scallop shell adsorbents have higher acetic acid removal performance than activated carbon.
本発明のＣａ−アルカリ型吸着性材料およびその製造方法によれば、従来の活性炭と同等、あるいはそれ以上に優れた酢酸その他酸性ガス吸着脱臭性能を備えた吸着性材料を実現できる。また、担持体（基材）としてホタテガイ貝殻その他の貝殻等の産業廃棄物を用いた場合、低コスト化および廃棄物の有効活用ともなり、環境関連機器製造・その他関連する産業分野において、利用性の高い発明である。 According to the Ca-alkali type adsorbent material and the method for producing the same of the present invention, an adsorbent material having acetic acid or other acidic gas adsorption / deodorization performance equivalent to or better than conventional activated carbon can be realized. In addition, when industrial waste such as scallop shells and other shells is used as the carrier (base material), it also reduces costs and makes effective use of waste, and is useful in the manufacture of environment-related equipment and other related industrial fields. It is a high invention.
１…Ｃａ高含有生体材料
２…アルカリ
３…吸着性材料
Ｐ…添着処理
DESCRIPTION OF SYMBOLS 1 ... Biomaterial 2 with high Ca content 2 ... Alkali 3 ... Adsorbent material P ... Adhesion process
Claims (9)
The adsorbent material according to claim 8, wherein the Ca-rich biomaterial is a scallop shell or other shell, and the alkali is sodium hydroxide, potassium hydroxide or other strong alkali. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010048472A JP5696338B2 (en) | 2010-03-04 | 2010-03-04 | Ca-alkaline adsorbent material and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010048472A JP5696338B2 (en) | 2010-03-04 | 2010-03-04 | Ca-alkaline adsorbent material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011183255A true JP2011183255A (en) | 2011-09-22 |
| JP5696338B2 JP5696338B2 (en) | 2015-04-08 |
Family
ID=44790186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010048472A Expired - Fee Related JP5696338B2 (en) | 2010-03-04 | 2010-03-04 | Ca-alkaline adsorbent material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5696338B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020076690A (en) * | 2018-11-09 | 2020-05-21 | 矢崎エナジーシステム株式会社 | Filter for gas sensor and gas sensor |
| CN116440866A (en) * | 2023-03-13 | 2023-07-18 | 武汉工程大学 | Preparation method and application of three-dimensional spongy porous heavy metal ion adsorbent based on activated eggshells |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938889A (en) * | 1972-08-18 | 1974-04-11 | ||
| JPS6152871A (en) * | 1984-08-22 | 1986-03-15 | 甲竜工業株式会社 | Ceramic material having deadorizing effect |
| JPS62179465A (en) * | 1986-01-31 | 1987-08-06 | 松下 敏子 | Deodorant for refrigerator and freezer |
| JPH09201513A (en) * | 1996-01-29 | 1997-08-05 | Kawabe Shiyokuriyouhin Kogyo Kk | In-furnace desulfurizing agent |
| JP2002327523A (en) * | 2001-02-14 | 2002-11-15 | Masao Miura | Building indoor surface finishing material and finishing method using the same |
| JP2003053144A (en) * | 2001-08-20 | 2003-02-25 | Chafflose Corporation | Air cleaning method |
| JP2005305201A (en) * | 2004-03-25 | 2005-11-04 | Mie Prefecture | Production method for molding having adsorptivity from pearl oyster shell |
| JP2008212205A (en) * | 2007-02-28 | 2008-09-18 | Azumi Roshi Kk | Deodorization sheet and honeycomb filter |
| JP2009213987A (en) * | 2008-03-08 | 2009-09-24 | Aomori Prefectural Industrial Technology Research Center | Adsorbent and method for manufacturing the same |
-
2010
- 2010-03-04 JP JP2010048472A patent/JP5696338B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938889A (en) * | 1972-08-18 | 1974-04-11 | ||
| JPS6152871A (en) * | 1984-08-22 | 1986-03-15 | 甲竜工業株式会社 | Ceramic material having deadorizing effect |
| JPS62179465A (en) * | 1986-01-31 | 1987-08-06 | 松下 敏子 | Deodorant for refrigerator and freezer |
| JPH09201513A (en) * | 1996-01-29 | 1997-08-05 | Kawabe Shiyokuriyouhin Kogyo Kk | In-furnace desulfurizing agent |
| JP2002327523A (en) * | 2001-02-14 | 2002-11-15 | Masao Miura | Building indoor surface finishing material and finishing method using the same |
| JP2003053144A (en) * | 2001-08-20 | 2003-02-25 | Chafflose Corporation | Air cleaning method |
| JP2005305201A (en) * | 2004-03-25 | 2005-11-04 | Mie Prefecture | Production method for molding having adsorptivity from pearl oyster shell |
| JP2008212205A (en) * | 2007-02-28 | 2008-09-18 | Azumi Roshi Kk | Deodorization sheet and honeycomb filter |
| JP2009213987A (en) * | 2008-03-08 | 2009-09-24 | Aomori Prefectural Industrial Technology Research Center | Adsorbent and method for manufacturing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020076690A (en) * | 2018-11-09 | 2020-05-21 | 矢崎エナジーシステム株式会社 | Filter for gas sensor and gas sensor |
| JP7090016B2 (en) | 2018-11-09 | 2022-06-23 | 矢崎エナジーシステム株式会社 | Filters for gas sensors and gas sensors |
| CN116440866A (en) * | 2023-03-13 | 2023-07-18 | 武汉工程大学 | Preparation method and application of three-dimensional spongy porous heavy metal ion adsorbent based on activated eggshells |
| CN116440866B (en) * | 2023-03-13 | 2023-09-22 | 武汉工程大学 | Preparation method and application of three-dimensional spongy porous heavy metal ion adsorbent based on activated eggshells |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5696338B2 (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4911706B2 (en) | Deodorant filter | |
| KR101755377B1 (en) | Graphene Oxide Having Excellent Adsorption Property Toward Heavy Metal Ions and Preparing Method Thereof | |
| KR101931088B1 (en) | Method of preparing activated carbon for filter using biomass and method of preparing filter using the same | |
| CN103480330B (en) | Biomass-modified adsorbent for adsorbing coking wastewater, and preparation method and application thereof | |
| KR100945371B1 (en) | Natural oil adsorbents and their preparation methods | |
| CN106861642B (en) | A kind of preparation and application of the biomass-based hydrogel with high absorption capacity | |
| JP2017119658A (en) | Virus deactivating agent and method for producing the same, and resin, fiber, garment, filter, and mask containing virus deactivating agent | |
| CN103418344B (en) | Nano zine oxide honeycomb type purification activated carbon and preparation method thereof | |
| JP5696338B2 (en) | Ca-alkaline adsorbent material and method for producing the same | |
| CA2511497A1 (en) | Carbon nanoball for deodorization | |
| KR100985846B1 (en) | Deodorizing filter for removing stench of food waste disposer system | |
| JP2014047087A (en) | Method of producing chemical-carrying active carbon, chemical-carrying active carbon and filter using the carbon | |
| JP6066176B2 (en) | Cigarette odor deodorant filter | |
| JP5610329B2 (en) | Titanium oxide volatile organic compound decomposition material coated with silicate | |
| CN114146689B (en) | Aluminum/cerium bimetal organic framework material, preparation method and application thereof in adsorption dephosphorization | |
| JP3138749B2 (en) | Method for producing carbides having deodorizing ability, ion exchange ability, and catalytic ability using plant materials | |
| JP2017064048A (en) | Deodorant and deodorant filter with the deodorant | |
| JP2016154640A (en) | Deodorant filter | |
| JP2017119015A (en) | Deodorant using layered double hydroxide and method for producing the same, and deodorant resin, deodorant fiber, deodorant garment, deodorant filter, and deodorant mask using layered double hydroxide | |
| JP2009279522A (en) | Oxide catalyst and method for preparing oxide catalyst, as well as deodorant and deodorizing filter | |
| KR20140137055A (en) | Preparation Method of Formaldehyde Adsorbent in Indoor Air | |
| JP2016034620A (en) | Metal oxide catalyst and deodorant | |
| JP2009240889A (en) | Gas adsorbent and gas adsorbing filter using the same | |
| JP2011212539A (en) | Deodorizing system and method of using deodorizing system | |
| WO2018203796A1 (en) | A sorbent and a filter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130118 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130607 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130726 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130924 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140319 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140513 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150109 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150122 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5696338 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |