JP2001300306A - Carbon dioxide adsorbent - Google Patents

Carbon dioxide adsorbent

Info

Publication number
JP2001300306A
JP2001300306A JP2000130156A JP2000130156A JP2001300306A JP 2001300306 A JP2001300306 A JP 2001300306A JP 2000130156 A JP2000130156 A JP 2000130156A JP 2000130156 A JP2000130156 A JP 2000130156A JP 2001300306 A JP2001300306 A JP 2001300306A
Authority
JP
Japan
Prior art keywords
carbon dioxide
dioxide adsorbent
package
adsorbent according
film
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.)
Pending
Application number
JP2000130156A
Other languages
Japanese (ja)
Inventor
Tomonori Hosoda
友則 細田
Hiroyuki Oba
弘行 大場
Hiroko Sato
裕子 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kureha Corp filed Critical Kureha Corp
Priority to JP2000130156A priority Critical patent/JP2001300306A/en
Publication of JP2001300306A publication Critical patent/JP2001300306A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Landscapes

  • Packages (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a carbon dioxide adsorbent simple in handling and adsorption/dessorption of the carbon dioxide, capable of safely using regardless of food and nonfood. SOLUTION: The carbon dioxide adsorbent is composed of a chitin derivative element having D-glucosamine element or the composition containing the chitin derivative and the adsorbent is preferably used for the food.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、キチン誘導体、或
いは、該キチン誘導体を含有する組成物からなる炭酸ガ
ス吸着剤、それを同封した包装体、及びそれを用いた空
気清浄用資材に関する。TECHNICAL FIELD The present invention relates to a carbon dioxide adsorbent comprising a chitin derivative or a composition containing the chitin derivative, a package enclosing the same, and a material for cleaning air using the same.

【０００２】[0002]

【従来の技術】発酵食品であるナチュラルチーズ、それ
自体炭酸ガスを発生するコーヒー豆などの炭酸ガス発生
食品は、貯蔵時、流通段階での保存時、店頭陳列時に、
水蒸気、酸素などのガスに対しては直接の接触をしない
よう考慮した包装形態がとられている。コーヒー豆で
は、例えば、ポリ塩化ビニリデン、エチレン・酢酸ビニ
ル共重合体ケン化物などを主体にした高分子フィルム、
アルミ箔、アルミ蒸着膜などの金属蒸着膜などの包装材
料による包装である。しかしながら、これらの包装材料
は、酸素、窒素、水蒸気等の気体に対するバリヤー性が
優れているとともに、発生する炭酸ガスに対するバリヤ
ー性も有するので、発生する炭酸ガスのために包装体が
膨らみ、店頭陳列時に棚から落ちたり、膨らみのため見
栄えの悪化をきたしたりする不具合が生じる。このよう
な問題に対し、例えば、特開平９−３１６２０８号公報
では、ポリアクリル酸と脂肪族ジアミンからなる反応混
合物を熱処理することにより得られる皮膜が水に対する
耐性を有し、且つ、炭酸ガス透過度と酸素ガス透過度と
の比が１５以上である包装材料が提案されている。ま
た、実開平５−８９２７４号公報では、炭酸ガスを発生
する食品を収納する包装体において、少なくとも一層の
マグネシウム、またはマグネシウム酸化物の薄膜を設け
た包装用フィルムの考案を提案されている。又、特開平
１１−２０６２６６号公報では、酸素発生剤及び炭酸ガ
ス吸収剤を輸送袋に封入する活魚の輸送方法に関する発
明が記載されており、ここでは炭酸ガス吸収剤として水
酸化カルシウム、水酸化マグネシウム、酸化マグネシウ
ム、酸化カルシウムから選ばれた少なくとも１種を用い
ることが記載されている。このように炭酸ガスを発生す
る被包装物の包装材料として、炭酸ガスを透過するが、
酸素、水蒸気を遮蔽するフィルム、或いは炭酸ガス吸収
剤など炭酸ガスの処理に関する技術が種々提案されてい
る。このような状況の下で食品に対して安全であり、リ
サイクル使用できる炭酸ガス吸着剤の出現は、有用なも
のとして期待される。2. Description of the Related Art Natural cheese, which is a fermented food, and carbon dioxide-generating foods such as coffee beans that generate carbon dioxide itself, are stored, stored at a distribution stage, and displayed at stores.
Packaging forms are taken in consideration of preventing direct contact with gas such as water vapor and oxygen. In coffee beans, for example, polyvinylidene chloride, polymer film mainly composed of saponified ethylene-vinyl acetate copolymer,
It is a package made of a packaging material such as a metal vapor-deposited film such as an aluminum foil or an aluminum-deposited film. However, these packaging materials have excellent barrier properties against gases such as oxygen, nitrogen, and water vapor, and also have a barrier property against generated carbon dioxide gas. At times, there is a problem that the product falls off the shelf or the appearance is deteriorated due to bulging. To cope with such a problem, for example, in Japanese Patent Application Laid-Open No. 9-316208, a film obtained by heat-treating a reaction mixture composed of polyacrylic acid and an aliphatic diamine has resistance to water, Packaging materials in which the ratio between the degree and the oxygen gas permeability is 15 or more have been proposed. Further, Japanese Utility Model Laid-Open No. 5-89274 proposes a packaging film in which at least one thin film of magnesium or magnesium oxide is provided in a package for storing foods that generate carbon dioxide gas. Japanese Patent Application Laid-Open No. 11-206266 describes an invention relating to a method for transporting live fish in which an oxygen generating agent and a carbon dioxide absorbent are sealed in a transport bag. It is described that at least one selected from magnesium, magnesium oxide, and calcium oxide is used. As a packaging material for the packaged object that generates carbon dioxide in this way, it transmits carbon dioxide,
Various techniques relating to the treatment of carbon dioxide such as a film for shielding oxygen and water vapor or a carbon dioxide absorbent have been proposed. Under these circumstances, the emergence of a carbon dioxide adsorbent that is safe for food and can be recycled is expected to be useful.

【０００３】[0003]

【発明が解決しようとする課題】本発明は、取り扱い及
び炭酸ガスの吸着・脱離が簡単で、食品、非食品に関わ
らず安全に使用でき、且つ再生使用が可能な炭酸ガス吸
着剤を提供することにある。SUMMARY OF THE INVENTION The present invention provides a carbon dioxide adsorbent which is easy to handle and adsorb and desorb carbon dioxide, can be used safely regardless of foods and non-foods, and can be reused. Is to do.

【０００４】[0004]

【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、特定のキチン誘導
体、又は該キチン誘導体からなる組成物が優れた炭酸ガ
ス吸着能を有することを見い出し、本発明を完成するに
至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific chitin derivative or a composition comprising the chitin derivative has an excellent carbon dioxide adsorbing ability. And completed the present invention.

【０００５】すなわち本発明は、Ｄ−グルコサミン単位
を有するキチン誘導体（以下、「キチン誘導体」と略記
することもある）単体、或いは、該キチン誘導体を含有
する組成物からなる炭酸ガス吸着剤を提供する。前記発
明において組成物が、キチン誘導体２０〜１００重量％
と他の成分０〜８０重量％からなる炭酸ガス吸着剤を提
供する。また、前記発明においてキチン誘導体がＤ−グ
ルコサミン単位を５０モル％以上有する炭酸ガス吸着剤
を提供する。組成物を構成する他の成分がポリオレフィ
ン、ポリエステル、又はポリアミドから選ばれた少なく
とも１種である前記発明の炭酸ガス吸着剤を提供する。
シート状、ペレット状、顆粒状、粉体状のいずれかに成
形されている前記発明の炭酸ガス吸着剤を提供する。炭
酸ガスを発生する食品用である前記発明の炭酸ガス吸着
剤を提供する。炭酸ガスを発生する食品がチーズ、長
芋、レンコン、キムチ、漬け物、生味噌、コーヒーから
選ばれた食品である前記発明の炭酸ガス吸着剤を提供す
る。前記発明の炭酸ガス吸着剤が食品とともに同封され
た包装体を提供する。前記発明の炭酸ガス吸着剤が非食
品とともに同封された包装体を提供する。更に、脱酸素
剤が同封された前記発明の包装体を提供する。さらに、
前記発明の炭酸ガス吸着剤を用いた空気清浄用資材を提
供する。That is, the present invention provides a carbon dioxide adsorbent consisting of a chitin derivative having a D-glucosamine unit (hereinafter sometimes abbreviated as "chitin derivative") alone or a composition containing the chitin derivative. I do. In the above invention, the composition comprises 20 to 100% by weight of a chitin derivative.
And 0 to 80% by weight of other components. Further, the invention provides a carbon dioxide adsorbent wherein the chitin derivative has D-glucosamine units in an amount of 50 mol% or more. Another object of the present invention is to provide the carbon dioxide adsorbent according to the invention, wherein the other component constituting the composition is at least one selected from polyolefin, polyester, and polyamide.
The present invention provides the carbon dioxide adsorbent according to the invention, which is formed into any one of a sheet, a pellet, a granule, and a powder. The present invention provides the carbon dioxide adsorbent according to the invention, which is used for foods that generate carbon dioxide. The present invention provides the carbon dioxide adsorbent according to the invention, wherein the food generating carbon dioxide is a food selected from cheese, yam, lotus root, kimchi, pickles, raw miso, and coffee. Provided is a package in which the carbon dioxide adsorbent of the invention is enclosed together with food. Provided is a package in which the carbon dioxide adsorbent of the invention is enclosed together with a non-food. Further, the present invention provides a package according to the present invention in which an oxygen scavenger is enclosed. further,
An air cleaning material using the carbon dioxide adsorbent of the invention is provided.

【０００６】[0006]

【発明の実施の形態】以下、本発明について、詳しく説
明する。本発明で用いるＤ−グルコサミン単位を有する
キチン誘導体とは、海老や蟹などの殻の構成成分として
自然界に広く分布するキチンを濃アルカリ中で固体状態
で脱アセチル化して得ることができ、完全脱アセチル化
したものは構成単位分子内に２個の水酸基と１個のアミ
ノ基を有する塩基性多糖類である。遊離のものは水や有
機溶媒に溶けないが、塩酸等の無機塩、酢酸、プロピオ
ン酸、蓚酸、酪酸、乳酸、酒石酸、コハク酸、クエン酸
等の有機酸の存在で塩を生成し酸塩溶液となる。本発明
では、Ｄ−グルコサミン単位を有するキチン誘導体であ
れば、特に制限はないが、Ｄ−グルコサミン単位を５０
モル％以上（以下、キトサンと称することがある。）、
更には７０〜１００モル％有するものがＣＯ2吸着性能
及び価格の観点から好ましい。Ｄ−グルコサミン単位が
５０モル％に満たないと価格が高価であったり、酢酸等
の酸に溶解しないため成形が困難であるという点で好ま
しくない。また、分子量１００００〜１００００００、
更には１００００〜５０００００（又は粘度３〜２００
００ｍＰａ・ｓ、更には３〜２０００ｍＰａ・ｓ）のも
のが好ましい。キトサンの粘度は、１重量％、もしくは
０．５重量％の酢酸塩水溶液にして、２０℃に保持した
水溶液をＢ型粘度計で測定する。キトサンは取り扱い易
さの点から、キトサン酸塩水溶液として取り扱うとよ
い。これらの中で、酢酸塩及び乳酸塩が価格及び食品衛
生の点から好ましい。キトサン酸塩水溶液にメタノー
ル、エタノール、イソプロピルアルコール等の親水性有
機溶剤を希釈剤として用いてもよい。キトサン酸塩水溶
液を基材に塗布する際、基材表面でキトサン酸塩水溶液
が濡れ難く、はじかれてしまう場合に、上記希釈剤又は
少量の界面活性剤を用いると塗布し易くなる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The chitin derivative having a D-glucosamine unit used in the present invention can be obtained by deacetylating chitin, which is widely distributed in nature as a constituent of shells such as shrimp and crab, in a solid state in a concentrated alkali, and can be completely dehydrated. The acetylated product is a basic polysaccharide having two hydroxyl groups and one amino group in the constituent unit molecule. Free form is insoluble in water and organic solvents, but forms salts in the presence of inorganic salts such as hydrochloric acid and organic acids such as acetic acid, propionic acid, oxalic acid, butyric acid, lactic acid, tartaric acid, succinic acid, and citric acid. It becomes a solution. In the present invention, there is no particular limitation as long as the chitin derivative has a D-glucosamine unit.
Mol% or more (hereinafter, may be referred to as chitosan),
More preferable from the viewpoint that is CO 2 adsorption performance and price with 70 to 100 mol%. If the D-glucosamine unit content is less than 50 mol%, it is not preferable in that the price is high and the molding is difficult because it is not dissolved in an acid such as acetic acid. Moreover, the molecular weight of 10,000 to 1,000,000,
Further, 10,000 to 500,000 (or a viscosity of 3 to 200)
00 mPa · s, and more preferably 3 to 2000 mPa · s). The viscosity of chitosan is measured by using a B-type viscometer with a 1% by weight or 0.5% by weight aqueous solution of an acetate kept at 20 ° C. Chitosan is preferably handled as an aqueous solution of chitosan salt from the viewpoint of easy handling. Among these, acetate and lactate are preferred from the viewpoint of price and food hygiene. A hydrophilic organic solvent such as methanol, ethanol, or isopropyl alcohol may be used as a diluent in the chitosan salt aqueous solution. When the aqueous solution of chitosanate is applied to a substrate, the aqueous solution of chitosanate is difficult to wet and repels on the surface of the substrate, and if the diluent or a small amount of surfactant is used, the application becomes easier.

【０００７】本発明の組成物を構成する他の成分として
は、例えば、ポリエステル、ポリオレフィン、ポリスチ
レン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアミ
ド、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフ
ルオロエチレン等の樹脂を挙げることができるが、これ
らのうち、ポリオレフィン、ポリエステル、ポリアミド
から選ばれた少なくとも１種が好ましい。Other components constituting the composition of the present invention include, for example, resins such as polyester, polyolefin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyvinylidene fluoride (PVDF), and polytetrafluoroethylene. Among them, at least one selected from polyolefin, polyester, and polyamide is preferable.

【０００８】ポリオレフィンとしては、オレフィン類の
単独重合体や共重合体、オレフィン類と他の共重合可能
な単量体、例えばビニル系単量体との共重合体、及びこ
れらの変性重合体などを例示することができる。具体的
には、高密度ポリエチレン、低密度ポリエチレン（以
下、「ＬＤＰＥ］と略記）、直鎖状低密度ポリエチレン
（以下、［ＬＬＤＰＥ］と略記）、超高密度ポリエチレ
ン（以下、「ＶＬＤＰＥ］と略記）、ポリプロピレン、
エチレン・プロピレン共重合体、ポリ４−メチルペンテ
ン−１（以下、「ＰＭＰ］と略記）、アイオノマー樹
脂、エチレン・酢酸ビニル共重合体（以下、｛ＥＶ
Ａ］｝と略記）、エチレン・アクリル酸共重合体、エチ
レン・メタクリル酸共重合体、（以下、［ＥＭＡＡ］と
略記）、エチレン・アクリル酸メチル共重合体、エチレ
ン・メタクリル酸メチル共重合体、変性ポリオレフィン
（例えば、オレフィン類の単独重合体または共重合体な
どとマレイン酸やフマル酸などの不飽和カルボン酸や酸
無水物やエステルもしくは金属塩などとの反応生成物な
ど）などである。上記オレフィンは、単独或いは２種以
上混合して用いることができる。これらの中では、ＰＭ
Ｐ、ＶＬＤＰＥ、ＥＶＡ、ＥＭＡＡ、ＬＬＤＰＥ、エチ
レン・アクリル酸共重合体などが得られる組成物の物性
の点から好ましい。Examples of the polyolefin include homopolymers and copolymers of olefins, copolymers of olefins with other copolymerizable monomers, for example, copolymers with vinyl monomers, and modified polymers thereof. Can be exemplified. Specifically, high-density polyethylene, low-density polyethylene (hereinafter abbreviated as “LDPE”), linear low-density polyethylene (hereinafter abbreviated as “LLDPE”), and ultra-high-density polyethylene (hereinafter abbreviated as “VLDPE”) ),polypropylene,
Ethylene / propylene copolymer, poly 4-methylpentene-1 (hereinafter abbreviated as “PMP”), ionomer resin, ethylene / vinyl acetate copolymer (hereinafter, “EV”)
A]｝), ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, (hereinafter abbreviated as [EMAA]), ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer And modified polyolefins (for example, reaction products of homopolymers or copolymers of olefins with unsaturated carboxylic acids such as maleic acid and fumaric acid, acid anhydrides, esters, metal salts, and the like). The above olefins can be used alone or in combination of two or more. Among these, PM
P, VLDPE, EVA, EMAA, LLDPE, ethylene-acrylic acid copolymer, etc. are preferred from the viewpoint of physical properties of the composition.

【０００９】ポリエステルとしては、ポリエチレンテレ
フタレート（ＰＥＴ）、ポリエチレンイソフタレート、
ポリブチレンテレフタレート、ポリ（１，４−シクロヘ
キシレンジメチレンテレフタレート）、ポリエチレン
２，６−ナフタレンジカルボキシレート等、及びこれら
の共重合体又はこれらと少量の他の樹脂とのブレンド物
が含まれる。ポリアミドとしては、ナイロン６、ナイロ
ン６６、ナイロン６・６６共重合体、ナイロン６・１２
共重合体等が含まれる。As the polyester, polyethylene terephthalate (PET), polyethylene isophthalate,
Polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), polyethylene 2,6-naphthalenedicarboxylate, and the like, and copolymers thereof or a blend thereof with a small amount of another resin are included. As the polyamide, nylon 6, nylon 66, nylon 6.66 copolymer, nylon 6.12
And copolymers.

【００１０】これらの樹脂成分は、キチン誘導体に加え
て組成物として用いることができる。樹脂成分の割合
は、０〜８０重量％、更には０〜５０重量％、（キチン
誘導体とその他の成分の合計は１００重量％）が好まし
い。組成物にすることにより、取り扱い性の向上や価格
が安価となる利点がある。このキチン誘導体、及び組成
物には、本発明の性能を損なわない範囲で、充填剤、添
加剤、紙等を加えてもよい。[0010] These resin components can be used as a composition in addition to the chitin derivative. The proportion of the resin component is preferably from 0 to 80% by weight, more preferably from 0 to 50% by weight, (the total of the chitin derivative and other components is 100% by weight). The use of the composition has an advantage that the handleability is improved and the price is reduced. Fillers, additives, paper and the like may be added to the chitin derivative and the composition as long as the performance of the present invention is not impaired.

【００１１】本発明の炭酸ガス吸着剤を得るには、フィ
ルム、シート又は板等の基材に前記のキトサン酸塩水溶
液又は組成物溶液（又は分散液）を塗布し、基材フィル
ムと共に乾燥（例えば、３０℃、２４時間）してキトサ
ン酸塩の乾燥皮膜を得る溶液流延法、高濃度のキトサン
酸塩水溶液をエキストルーダーにより吐出圧力をかけな
がら細隙から膜状に流延し、含水フィルムを回転ドラム
またはベルト上で乾燥する押出法、プラスチックフィル
ムにキトサン酸塩水溶液を塗工した後、塗工したフィル
ムを加熱下で乾燥する方法などにより成形する。これら
の製法のうち、特に、溶液流延法（キャスト法、コーテ
ィング法）は、透明性に優れた成形膜（乾燥皮膜）を容
易に得ることができるため好ましく用いられる。得られ
た乾燥皮膜は、アルカリ処理後、皮膜、またはフレーク
状として用いることもできる。本発明の炭酸ガス吸着剤
の形態は、特に制限はないが、フィルム基材に塗布され
た形態、シート状、ペレット状、顆粒状、フレーク状、
粉体状で炭酸ガスの透過性の大きい他の樹脂、及び紙等
からなる袋に収納されたり、或いはシート状、フレーク
状、ペレット状、顆粒状、粉体状のままで用いられる。
ペレット状、顆粒状、フレーク状、粉体状の場合は、キ
トサン単独でもよいし、その組成物を押出機等で賦形
し、更に粉砕して得ることができる。粉砕しないで適当
な形状に成形しても構わない。In order to obtain the carbon dioxide adsorbent of the present invention, the above-mentioned chitosan salt aqueous solution or composition solution (or dispersion) is applied to a substrate such as a film, sheet or plate and dried together with the substrate film ( (Eg, 30 ° C., 24 hours), a solution casting method for obtaining a dried film of chitosanate, a high-concentration aqueous solution of chitosanate is cast in a film form from the slits while applying a discharge pressure by an extruder, and then containing water. Molding is performed by an extrusion method of drying the film on a rotating drum or a belt, a method of coating a plastic film with an aqueous solution of chitosanate, and drying the coated film under heating. Among these production methods, particularly, the solution casting method (casting method, coating method) is preferably used because a molded film (dry film) having excellent transparency can be easily obtained. The resulting dried film can be used as a film or flake after alkali treatment. The form of the carbon dioxide adsorbent of the present invention is not particularly limited, but a form applied to a film substrate, a sheet, a pellet, a granule, a flake,
It is stored in a bag made of another resin that is powdery and has high permeability to carbon dioxide gas, paper, or the like, or used as a sheet, flake, pellet, granule, or powder.
In the case of pellets, granules, flakes, and powders, chitosan alone may be used, or the composition may be obtained by shaping the composition with an extruder or the like and further pulverizing the composition. It may be formed into an appropriate shape without pulverization.

【００１２】本発明の炭酸ガス吸着剤を使用する際、吸
着剤を含む雰囲気の条件は、温度２〜１００℃程度の範
囲、湿度４０〜１００％ＲＨの範囲であることが好まし
い。湿度が４０％未満では、炭酸ガス吸着能が低下す
る。When the carbon dioxide adsorbent of the present invention is used, the condition of the atmosphere containing the adsorbent is preferably a temperature range of about 2 to 100 ° C. and a humidity range of 40 to 100% RH. If the humidity is less than 40%, the ability to adsorb carbon dioxide decreases.

【００１３】本発明の炭酸ガス吸着剤は、使用が済んだ
際には、容易に吸着した炭酸ガスを脱離し、再生するこ
とがでる。再生したものは、再び支障無く炭酸ガス吸着
剤として使用できる。炭酸ガスの脱離の方法は、例え
ば、使用済みの吸着剤を水中に１時間浸漬し、次いで大
気雰囲気下で自然乾燥させることで、赤外線吸収スペク
トル法で吸着剤に吸着している炭酸ガスを測定しても、
炭酸ガスが検出されない程度に脱離していることが確か
められた。When the carbon dioxide adsorbent of the present invention has been used, the adsorbed carbon dioxide can be easily desorbed and regenerated. The regenerated product can be used again as a carbon dioxide adsorbent without any trouble. As a method of desorbing carbon dioxide, for example, a used adsorbent is immersed in water for 1 hour, and then naturally dried in an air atmosphere, thereby removing carbon dioxide adsorbed on the adsorbent by infrared absorption spectroscopy. Even if you measure,
It was confirmed that carbon dioxide was desorbed to the extent that it was not detected.

【００１４】次に、炭酸ガス吸着剤の使用について説明
する。炭酸ガスを発生する食品、例えば、ナチュラルチ
ーズ等を酸素バリヤー性を有する塩化ビニリデンフィル
ムを積層したフィルムで包装し、少量の炭酸ガス・窒素
ガス混合気体を封入（通常の市販品で行われている）
し、気密シールして１５℃の雰囲気で保存する。この包
装体は、２週間程度で包装体が炭酸ガスの発生により膨
らむことが観察される。ところが、本発明の炭酸ガス吸
着剤を同封しておくと同じ条件で保存しても膨らみは起
こらない。また、長芋は、切断した一部を真空包装し
て、店頭に出されるが、２０℃で１週間の保存で、後記
のように発生したガスによる真空の戻り現象が包装体内
に認められ、味も変化してくる。これに対し、本発明の
炭酸ガス吸着剤を充填物に同封し真空包装し、同じ条件
で保存した場合には、１週間の保存ではこのような現象
が認められない。これらは炭酸ガス吸着剤の効果の一つ
として確認されている。Next, the use of the carbon dioxide adsorbent will be described. Foods that generate carbon dioxide gas, such as natural cheese, are packaged with a laminated film of vinylidene chloride film having oxygen barrier properties, and a small amount of a mixed gas of carbon dioxide and nitrogen gas is enclosed (this is a common commercial product. )
Then, the container is hermetically sealed and stored in an atmosphere at 15 ° C. It is observed that this package expands in about two weeks due to the generation of carbon dioxide gas. However, if the carbon dioxide adsorbent of the present invention is enclosed and stored under the same conditions, no swelling occurs. In addition, the cut yam is vacuum-packaged in a part of the cut potatoes and put out at the store. After storage at 20 ° C. for one week, the phenomenon of vacuum return caused by the gas generated as described below is observed in the package, Will also change. On the other hand, when the carbon dioxide adsorbent of the present invention is enclosed in a filling, vacuum-packaged, and stored under the same conditions, such a phenomenon is not observed after storage for one week. These have been confirmed as one of the effects of the carbon dioxide adsorbent.

【００１５】本発明の炭酸ガス吸着剤の使用量を決める
際の目安としては、Ｄ−グルコサミン単位を有するキチ
ン誘導体１グラム当たり２３℃、１００％ＲＨの条件で
３０ｃｍ3以上の炭酸ガスを吸着するものがよい。但
し、炭酸ガスの吸着量は、キチン誘導体のＤ−グルコサ
ミン単位の含有割合、製膜方法等で変わるものであり、
前記の数値は、単に本発明の吸着剤使用量の目安を決め
る数値である。As a guide for determining the amount of the carbon dioxide adsorbent used in the present invention, carbon dioxide of 30 cm 3 or more is adsorbed at 23 ° C. and 100% RH per gram of a chitin derivative having a D-glucosamine unit. Things are good. However, the amount of carbon dioxide adsorbed varies depending on the content of D-glucosamine units in the chitin derivative, the film forming method, and the like.
The above numerical values are merely numerical values that determine the standard of the amount of the adsorbent used in the present invention.

【００１６】[0016]

【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。尚、
評価方法は以下のように行った。 チーズ包装試験：チーズの包装された包装体を、水平な
台の上に１８ｃｍ×１９．５ｃｍの面を下にして置く。
次いで、上部に厚さ５ｍｍ、大きさが２０ｃｍ×２０ｃ
ｍのアクリル板を載せて、このアクリル板が水平になる
ように調整した。この状態で、水平な台から垂直に定規
を当て、台とアクリル板の距離を測定し包材高さとし
た。包材高さの数値が大きいものは、包装体の膨らみが
大きいことを示す。 長芋包装試験の評価 「膨張の程度」の評価は、以下の通りである。 ０：「減圧」とは真空状態のことを云う。 １：「ゆるみ」とは、包装体内に少量のガスが充填され
ているが、大気よりは減圧状態であることを云う。 ２：「戻り」とは、大気圧と平衡な状態を云う。包装体
に針で穴を開けても包装体の形状に変化がない状態を云
う。 ３：「弱膨張」とは、包装体内で少し圧力がかかってい
る状態を云う。 ４：「中膨張」とは、包装体内の圧力により、フィルム
に張りがある状態を云う。５：「強膨張」とは、包装体
内の圧力により、フィルムに強い張りがある状態を云
う。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. still,
The evaluation method was performed as follows. Cheese packaging test: The packaged package of cheese is placed on a horizontal table, 18 cm x 19.5 cm face down.
Then, the thickness is 5mm and the size is 20cm x 20c
m was placed on the acrylic plate, and the acrylic plate was adjusted to be horizontal. In this state, a ruler was applied vertically from a horizontal table, and the distance between the table and the acrylic plate was measured to obtain the packaging material height. A larger value of the packaging material height indicates that the package has a larger bulge. Evaluation of yam packaging test The evaluation of "degree of expansion" is as follows. 0: “Depressurization” refers to a vacuum state. 1: “Loose” means that the package is filled with a small amount of gas but is in a reduced pressure state compared to the atmosphere. 2: "Return" refers to a state of equilibrium with atmospheric pressure. This refers to a state in which the shape of the package does not change even if a hole is made in the package with a needle. 3: "Weak expansion" refers to a state where a slight pressure is applied in the package. 4: "Medium expansion" refers to a state in which the film has tension due to the pressure in the package. 5: "Strong swelling" refers to a state in which the film has strong tension due to the pressure in the package.

【００１７】（実施例１）キトサンとして大日精化工業
（株）の１００ＤＶＬ（Ｄ−グルコサミン単位：１００
モル％、粘度５〜７ｃｐｓ｛１．０質量％酢酸水溶液中
の１．０質量％キトサン濃度で温度２０℃で測定｝）を
使用した。キトサン１００ＤＶＬの形状はフレーク状で
あった。出光石油化学（株）製のＰＥ不織布（６０ｇ／
ｍ2）から製袋した５ｃｍ×１０ｃｍの３方をシールし
たパウチに上記キトサン２０ｇを入れ、上部をシールし
た。これを炭酸ガス吸着剤とした。チーズは、雪印
（株）から市販されている「とろけるナチュラルチーズ
TM」（ピザ用）を用いた。チーズが充填されている市販
品の包材（表１に包装体として厚み＃（μｍ）とともに
示す。）の上部を開封し、フレーク状のキトサン２０ｇ
を充填した上記炭酸ガス吸着剤を入れ、再シールした。
このとき包装体内部のガス組成がＣＯ2：Ｎ2＝３０：７
０になるように調整した。包装体内の圧力は、包装体外
の圧力と同じになるようにした。包材のサイズは１８ｃ
ｍ×１９．５ｃｍであり、チーズの充填量は４１４ｇで
あった。この包装体を１５℃の雰囲気に置き、包材を横
置きにしたときの高さ（チーズ包装試験）と目視による
色調の変化を調べた。Example 1 As a chitosan, 100 DVL (D-glucosamine unit: 100) manufactured by Dainichi Seika Kogyo Co., Ltd.
Mol.%, Viscosity 5-7 cps {measured at a temperature of 20 ° C. at a concentration of 1.0% by weight of chitosan in an aqueous solution of 1.0% by weight of acetic acid}). The shape of chitosan 100DVL was a flake shape. PE nonwoven fabric manufactured by Idemitsu Petrochemical Co., Ltd. (60 g /
m2), 20 g of the chitosan was placed in a pouch sealed on three sides of 5 cm × 10 cm, which was made from m 2 ), and the upper part was sealed. This was used as a carbon dioxide adsorbent. Cheese is commercially available from Snow Brand Co., Ltd.
TM "(for pizza). The upper part of a commercially available packaging material filled with cheese (shown in Table 1 as a package with a thickness of # (μm)) is opened and 20 g of flaky chitosan is opened.
The above-mentioned carbon dioxide adsorbent filled with was charged and resealed.
At this time, the gas composition inside the package is CO 2 : N 2 = 30: 7.
It was adjusted to be zero. The pressure inside the package was the same as the pressure outside the package. The packaging material size is 18c
mx 19.5 cm, cheese filling 414 g. This package was placed in an atmosphere of 15 ° C., and the height (cheese packaging test) when the packaging material was laid horizontally and a change in color tone visually were examined.

【００１８】（実施例２）実施例１で使用したフレーク
状キトサン１０ｇを実施例１と同様なＰＥ不織布製のパ
ウチに入れ、上部をシールし炭酸ガス吸着剤とした。チ
ーズの種類及び充填量は実施例１と同様にした。上記炭
酸ガス吸着剤をチーズが充填された包材に入れ、包装体
内を実施例１と同様なガス組成となるように調整して、
包材の上部を再シールした。この包装体を１５℃の雰囲
気に置き、包材を横置きにしたときの高さと目視による
色調の変化を調べた。Example 2 10 g of the flaky chitosan used in Example 1 was placed in a pouch made of PE non-woven fabric as in Example 1, and the upper portion was sealed to serve as a carbon dioxide adsorbent. The type and amount of cheese were the same as in Example 1. The carbon dioxide adsorbent is placed in a packaging material filled with cheese, and the inside of the package is adjusted to have the same gas composition as in Example 1,
The top of the packaging was resealed. This package was placed in an atmosphere of 15 ° C., and changes in height and visual color tone when the package was placed horizontally were examined.

【００１９】（実施例３）酢酸は水を加えて７質量％酢
酸水溶液に調整した。次いで、実施例１で用いたキトサ
ンを、この７質量％酢酸水溶液９０質量部に１０質量部
添加し、マグネチックスターラーを用いて、回転数２０
０回転／分の速度で撹拌し、混合水溶液を得た。次い
で、この混合水溶液を厚さ１ｍｍのアクリル板に流延し
た。これを３０℃で２４時間乾燥し、アクリル板から剥
離し、厚さ５０μｍの乾燥皮膜を得た。予め調製してお
いた１規定の水酸化ナトリウム水溶液に、上記キトサン
皮膜を浸漬した。次いで、これを１２時間水道水に浸漬
し、７０℃、３０分間乾燥器で乾燥し、水を蒸発させ、
厚さ５０μｍのキトサン単独乾燥皮膜を得た。得られた
キトサン乾燥皮膜そのままを炭酸ガス吸着剤とした。チ
ーズの種類及び充填量は実施例１と同様にした。キトサ
ン乾燥皮膜２０ｇをチーズが充填された包材に入れ、包
装体内を実施例１と同様なガス組成となるように調整し
て、包材の上部を再シールした。この包装体を１５℃の
雰囲気に置き、包材を横置きにしたときの高さと目視に
よる色調の変化を調べた。Example 3 Acetic acid was adjusted to a 7% by mass aqueous acetic acid solution by adding water. Next, 10 parts by mass of the chitosan used in Example 1 was added to 90 parts by mass of the 7% by mass aqueous acetic acid solution, and the number of rotations was 20 using a magnetic stirrer.
The mixture was stirred at a speed of 0 rotation / minute to obtain a mixed aqueous solution. Next, the mixed aqueous solution was cast on an acrylic plate having a thickness of 1 mm. This was dried at 30 ° C. for 24 hours and peeled from the acrylic plate to obtain a dry film having a thickness of 50 μm. The chitosan film was immersed in a 1N aqueous sodium hydroxide solution prepared in advance. Next, this was immersed in tap water for 12 hours, dried in a dryer at 70 ° C. for 30 minutes, and the water was evaporated.
A dry film of chitosan alone having a thickness of 50 μm was obtained. The obtained dried chitosan film was used as a carbon dioxide adsorbent as it was. The type and amount of cheese were the same as in Example 1. 20 g of the dried chitosan film was placed in a packaging material filled with cheese, the interior of the packaging was adjusted to have the same gas composition as in Example 1, and the upper portion of the packaging material was resealed. This package was placed in an atmosphere of 15 ° C., and changes in height and visual color tone when the package was placed horizontally were examined.

【００２０】（実施例４）実施例３で用いたものと同様
なキトサン単独皮膜１０ｇを炭酸ガス吸着剤とした。こ
の１０ｇのキトサン単独皮膜をチーズが充填された包材
に入れ、実施例１と同様なガス組成に調整し、上部をシ
ールした。チーズの種類、充填量及び評価項目は実施例
１と同様とした。この包装体を１５℃の雰囲気に置き、
包材を横置きにしたときの高さと目視による色調の変化
を調べた。Example 4 10 g of a chitosan single film similar to that used in Example 3 was used as a carbon dioxide adsorbent. 10 g of the chitosan single film was placed in a packaging material filled with cheese, the gas composition was adjusted to the same as in Example 1, and the upper portion was sealed. The type of cheese, the filling amount, and the evaluation items were the same as in Example 1. Place this package in an atmosphere of 15 ° C.
The height when the packaging material was placed horizontally and the change in color tone by visual observation were examined.

【００２１】（比較例１）実施例１で用いたのと同様な
チース及び包材を用いた。このチーズが充填されている
包材の上部を開封し、キトサンを入れずに再シールし
た。このとき、包材内のガス組成はＣＯ2：Ｎ2＝３０：
７０になるように調整した。包装体内の圧力は、包装体
外の圧力と同じになるようにした。包材のサイズは１８
ｃｍ×１９．５ｃｍであり、チーズの充填量は４１４ｇ
であった。この包装体を１５℃の雰囲気に置き、包材を
横置きにしたときの高さ（チーズ包装試験）と目視によ
る色調の変化を調べた。実施例１〜４及び比較例１の包
装試験結果及び色調変化の観察結果を表１に示した。Comparative Example 1 The same cheese and packaging material as used in Example 1 were used. The top of the packaging material filled with this cheese was opened and resealed without chitosan. At this time, the gas composition in the packaging material is CO 2 : N 2 = 30:
It was adjusted to be 70. The pressure inside the package was the same as the pressure outside the package. The packaging size is 18
cm x 19.5cm, cheese filling 414g
Met. This package was placed in an atmosphere of 15 ° C., and the height (cheese packaging test) when the packaging material was laid horizontally and a change in color tone visually were examined. Table 1 shows the results of the packaging tests and the observation results of the color tone changes of Examples 1 to 4 and Comparative Example 1.

【００２２】（実施例５及び６）実施例１で用いたフレ
ーク状キトサンをＰＥ不織布からなる３方シールしたパ
ウチ充填した炭酸ガス吸着剤（実施例５）及び実施例３
で用いたキトサン乾燥皮膜の炭酸ガス吸着剤（実施例
６）を用いた。長芋２００ｇを厚さ１５μｍのナイロン
（Ｎｙ）フィルムと厚さ８０μｍのＰＥフィルムとの積
層フィルムからなる包材に充填した。次いで、実施例１
及び３で用いたキトサンからなる炭酸ガス吸着剤を同封
し、真空包装した長芋包装体を得た。包材の面積は５０
０ｃｍ2とし、２０℃で１週間保存し、目視による包材
の外観と切り口の色調及び生食による味の評価を行っ
た。尚、味の評価で、「よい」とは、官能試験でスーパ
ー、八百屋で購入直後の味に近いことを意味する。(Examples 5 and 6) A pouch-filled carbon dioxide adsorbent (Example 5) in which the flaky chitosan used in Example 1 is sealed on three sides and made of a PE nonwoven fabric (Example 5) and Example 3
The carbon dioxide adsorbent (Example 6) for the dried chitosan film used in (1) was used. 200 g of yam was filled in a packaging material composed of a laminated film of a nylon (Ny) film having a thickness of 15 μm and a PE film having a thickness of 80 μm. Then, Example 1
The carbon dioxide adsorbent composed of chitosan used in (3) and (3) was enclosed, and a vacuum-packaged yam package was obtained. Packaging material area is 50
And 0 cm 2, and stored for 1 week at 20 ° C., was evaluated taste by tone and saline appearance and cut the packaging material visually. In the taste evaluation, “good” means that the taste is close to the taste immediately after purchase at a supermarket or greengrocer in a sensory test.

【００２３】（比較例２）厚さ１５μｍのＮｙフィルム
と厚さ８０μｍのＰＥフィルム塗料の積層フィルムを用
い、長芋の包装試験を行った。包材の面積は５００ｃｍ
2とし、長芋２００ｇを真空包装した。２０℃で１週間
保存し、目視による包材の外観と切り口の色調及び生食
による味の評価を行った。実施例５、６及び比較例２の
包装試験結果を表２に示した。(Comparative Example 2) A packaging test of a yam was performed using a laminated film of a 15 μm thick Ny film and a 80 μm thick PE film paint. The packaging material area is 500cm
2, and 200 g of yam was vacuum-packaged. After storing at 20 ° C. for 1 week, the appearance of the packaging material, the color tone of the cut edge, and the taste of the raw food were evaluated visually. Table 2 shows the packaging test results of Examples 5 and 6 and Comparative Example 2.

【００２４】（実施例７及び８）実施例１及び３で使用
した炭酸ガス吸着剤を１ヶ月の包装試験が終了した後、
水の中に１時間浸漬させた。この炭酸ガス吸着剤を２３
℃、１００％ＲＨの雰囲気下に２４時間放置し、炭酸ガ
ス吸着剤に吸着していた炭酸ガスを脱離させた。炭酸ガ
スが吸着剤から脱離したことは、赤外線吸収スペクトル
を測定し確認した。この炭酸ガス吸着剤を実施例１及び
実施例３と同様な方法でチーズ入りの包材に同封した
後、包材の上部を再シールし包装体を得た。この包装体
を１５℃の雰囲気に置き、包材を横置きにしたときの高
さと色調の変化を調べた。実施例７及び８の包装試験結
果を表３に示した。(Examples 7 and 8) The carbon dioxide adsorbent used in Examples 1 and 3 was subjected to a one-month packaging test.
It was immersed in water for 1 hour. This carbon dioxide adsorbent is
The mixture was allowed to stand in an atmosphere of 100 ° C. and 100% RH for 24 hours to desorb carbon dioxide adsorbed on the carbon dioxide adsorbent. The desorption of carbon dioxide from the adsorbent was confirmed by measuring an infrared absorption spectrum. This carbon dioxide adsorbent was enclosed in a cheese-containing packaging material in the same manner as in Examples 1 and 3, and the upper portion of the packaging material was resealed to obtain a package. This package was placed in an atmosphere of 15 ° C., and changes in height and color tone when the package was placed horizontally were examined. Table 3 shows the results of the packaging tests of Examples 7 and 8.

【００２５】[0025]

【表１】 [Table 1]

【００２６】[0026]

【表２】 [Table 2]

【００２７】[0027]

【表３】 [Table 3]

【００２８】[0028]

【発明の効果】本発明により、Ｄ−グルコサミン単位を
有するキチン誘導体単体が実施例で示した如く炭酸ガス
吸着剤としての機能を有し、取り扱いが簡単な炭酸ガス
吸着剤を提供することができる。また、本発明の炭酸ガ
ス吸着剤は、原料であるキチンが自然界に広く分布する
ことから、非食品の分野のみならず食品分野へ適用して
も安全であり、且つ吸着した炭酸ガスの脱離を簡単に行
なうことができるリサイクル型の炭酸ガス吸着剤であ
る。According to the present invention, a chitin derivative having a D-glucosamine unit alone has a function as a carbon dioxide adsorbent as shown in the examples, and a carbon dioxide adsorbent which is easy to handle can be provided. . Further, the carbon dioxide adsorbent of the present invention is safe to apply not only to the non-food field but also to the food field because chitin as a raw material is widely distributed in nature, and desorbs the adsorbed carbon dioxide. Is a recyclable carbon dioxide adsorbent that can easily perform

───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 3E067 AB08 AB14 AB23 BB14A BB25A CA06 EE21 EE25 FB11 GD02 4D012 BA01 4G066 AC01B AC13D AC23D AC26D BA03 BA09 BA12 BA36 CA35 DA03 DA20 EA07  ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3E067 AB08 AB14 AB23 BB14A BB25A CA06 EE21 EE25 FB11 GD02 4D012 BA01 4G066 AC01B AC13D AC23D AC26D BA03 BA09 BA12 BA36 CA35 DA03 DA20 EA07

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】 Ｄ−グルコサミン単位を有するキチン誘
導体単体、或いは、該キチン誘導体を含有する組成物か
らなる炭酸ガス吸着剤。1. A carbon dioxide adsorbent comprising a chitin derivative alone having a D-glucosamine unit or a composition containing the chitin derivative. 【請求項２】 組成物が、キチン誘導体２０〜１００重
量％と他の成分０〜８０重量％からなる請求項１記載の
炭酸ガス吸着剤。2. The carbon dioxide adsorbent according to claim 1, wherein the composition comprises 20 to 100% by weight of the chitin derivative and 0 to 80% by weight of other components. 【請求項３】 キチン誘導体がＤ−グルコサミン単位を
５０モル％以上有する請求項１又は２記載の炭酸ガス吸
着剤。3. The carbon dioxide adsorbent according to claim 1, wherein the chitin derivative has at least 50 mol% of D-glucosamine units. 【請求項４】 組成物を構成する他の成分がポリオレフ
ィン、ポリエステル、又はポリアミドから選ばれた少な
くとも１種である請求項２記載の炭酸ガス吸着剤。4. The carbon dioxide adsorbent according to claim 2, wherein the other component constituting the composition is at least one selected from polyolefin, polyester, and polyamide. 【請求項５】 シート状、フレーク状、ペレット状、顆
粒状、粉体状のいずれかに成形されている請求項１〜４
のいずれかに記載の炭酸ガス吸着剤。5. A sheet, a flake, a pellet, a granule, or a powder, which is formed in any one of the following forms:
The carbon dioxide adsorbent according to any one of the above. 【請求項６】 炭酸ガスを発生する食品用である請求項
５記載の炭酸ガス吸着剤。6. The carbon dioxide adsorbent according to claim 5, which is for foods that generate carbon dioxide. 【請求項７】 炭酸ガスを発生する食品がチーズ、長
芋、レンコン、キムチ、漬け物、生味噌、コーヒーから
選ばれた食品である請求項６記載の炭酸ガス吸着剤。7. The carbon dioxide adsorbent according to claim 6, wherein the food generating carbon dioxide is a food selected from cheese, yam, lotus root, kimchi, pickles, raw miso, and coffee. 【請求項８】 請求項６記載の炭酸ガス吸着剤が食品と
ともに同封された包装体。8. A package in which the carbon dioxide adsorbent according to claim 6 is enclosed together with food. 【請求項９】 請求項５記載の炭酸ガス吸着剤が非食品
とともに同封された包装体。9. A package in which the carbon dioxide adsorbent according to claim 5 is enclosed together with non-food items. 【請求項１０】 更に、脱酸素剤が同封された請求項８
又は９記載の包装体。10. The method according to claim 8, further comprising an oxygen scavenger.
Or the package according to 9. 【請求項１１】 請求項１〜５のいずれかに記載の炭酸
ガス吸着剤を用いた空気清浄用資材。11. An air purifying material using the carbon dioxide adsorbent according to claim 1. Description:
JP2000130156A 2000-04-28 2000-04-28 Carbon dioxide adsorbent Pending JP2001300306A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012121022A (en) * 2012-01-23 2012-06-28 Mitsubishi Gas Chemical Co Inc Moisture resistant deoxidizer
WO2018207633A1 (en) * 2017-05-09 2018-11-15 川崎重工業株式会社 Carbon dioxide absorbent and method for producing same, and carbon dioxide separation system
CN108946835A (en) * 2018-07-12 2018-12-07 浙江正洁环境科技有限公司 A kind of absorption-flocculating settling agent and its preparation method and application
CN115779860A (en) * 2022-11-29 2023-03-14 华中科技大学 Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012121022A (en) * 2012-01-23 2012-06-28 Mitsubishi Gas Chemical Co Inc Moisture resistant deoxidizer
WO2018207633A1 (en) * 2017-05-09 2018-11-15 川崎重工業株式会社 Carbon dioxide absorbent and method for producing same, and carbon dioxide separation system
CN108946835A (en) * 2018-07-12 2018-12-07 浙江正洁环境科技有限公司 A kind of absorption-flocculating settling agent and its preparation method and application
CN108946835B (en) * 2018-07-12 2021-06-29 浙江正洁环境科技有限公司 Preparation method of adsorption-flocculation precipitator
CN115779860A (en) * 2022-11-29 2023-03-14 华中科技大学 Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof

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