JPH01148341A - Ethylene adsorbent - Google Patents
Ethylene adsorbentInfo
- Publication number
- JPH01148341A JPH01148341A JP62306758A JP30675887A JPH01148341A JP H01148341 A JPH01148341 A JP H01148341A JP 62306758 A JP62306758 A JP 62306758A JP 30675887 A JP30675887 A JP 30675887A JP H01148341 A JPH01148341 A JP H01148341A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- zeolite
- molar ratio
- high silica
- crystalline high
- 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
Links
- 239000005977 Ethylene Substances 0.000 title claims abstract description 55
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003463 adsorbent Substances 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010457 zeolite Substances 0.000 claims abstract description 55
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 125000002091 cationic group Chemical group 0.000 claims description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- -1 silver ions Chemical class 0.000 abstract description 21
- 239000004332 silver Substances 0.000 abstract description 15
- 229910052709 silver Inorganic materials 0.000 abstract description 15
- 238000005342 ion exchange Methods 0.000 abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005995 Aluminium silicate Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 235000012211 aluminium silicate Nutrition 0.000 abstract description 2
- 239000000440 bentonite Substances 0.000 abstract description 2
- 229910000278 bentonite Inorganic materials 0.000 abstract description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004927 clay Substances 0.000 abstract description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 abstract description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000367 silver sulfate Inorganic materials 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 19
- 235000012055 fruits and vegetables Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、青果物および花き類（以下これらを青果物類
という）の鮮度保持の作用を呈するエチレン吸着剤に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an ethylene adsorbent that maintains the freshness of fruits, vegetables, and flowers (hereinafter referred to as fruits and vegetables).
従来の技術
青果物類は、呼吸作用によって熟成を促進させるエチレ
ンを発生する。殊に、密閉包装の状態においては、エチ
レン濃度がより高くなる為、著しく熟成が促進する。BACKGROUND OF THE INVENTION Fruits and vegetables produce ethylene, which accelerates ripening, through respiration. In particular, in a sealed packaging state, the ethylene concentration becomes higher, so ripening is significantly accelerated.
これまでに、エチレンによる障害を防止する為に、青果
物類の容器内にクリノプチロライトのような天然ゼオラ
イト、モレキュラーシーブと呼ばれる汎用の合成ゼオラ
イト、あるいは活性炭を入れることにより、発生するエ
チレンを吸着させる方法が知られている。So far, in order to prevent damage caused by ethylene, natural zeolite such as clinoptilolite, a general-purpose synthetic zeolite called molecular sieve, or activated carbon has been placed in containers for fruits and vegetables to adsorb the generated ethylene. There are known ways to do this.
しかしながら、これらの天然ゼオライト合成ゼオライト
あるいは活性炭は、水分の吸着性が高い為、水分が共存
している青果物類の保存にあっては、その水分の吸着に
よりエチレンに対する吸着力が低下したり、また−度吸
着したエチレンを水分の吸着の進行とともに放出するの
で、エチレン除去を充分なし得ない。その為、比較的短
時間のうちに容器内のエチレン濃度が増大し、青果物類
の熟成が促進される難点があった。（特開昭５５−６４
７５０号及び同５２−３８０５３号公報参照）また、前
記の欠点を解消する手段として、これらゼオライトある
いは活性炭に過マンガン酸カリウムを含浸あるいは配合
させておき、これによってエチレンを酸化分解させる方
法が提案されている。（特開昭５５−１５４９０１号、
同５６−１８９０１号、同５６−６８３４６号、同５７
−４０４０１号及び特公昭６１−１７４６１号公報参照
）
発明が解決しようとする問題点
天然ゼオライト合成ゼオライトあるいは活性炭に過マン
ガン酸カリウムを含浸あるいは配合させて、発生するエ
チレンを酸化分解させる方法によれば、酸化剤である過
マンガン酸カリウムの貯蔵性に問題があり、使用前に酸
化力が減少しやすい為、エチレンに対する酸化反応が極
めて緩慢なものとなり、青果物類の鮮度を十分に保持す
ることができなかった。However, these natural zeolite synthetic zeolites and activated carbon have high water adsorption properties, so when preserving fruits and vegetables that coexist with water, the adsorption power for ethylene may decrease due to the adsorption of water. - Ethylene cannot be removed sufficiently because the adsorbed ethylene is released as moisture adsorption progresses. As a result, the ethylene concentration within the container increases within a relatively short period of time, resulting in accelerated ripening of fruits and vegetables. (Unexamined Japanese Patent Publication No. 55-64
No. 750 and No. 52-38053) In order to solve the above-mentioned drawbacks, a method has been proposed in which zeolite or activated carbon is impregnated with or mixed with potassium permanganate, thereby causing oxidative decomposition of ethylene. ing. (Unexamined Japanese Patent Publication No. 55-154901,
No. 56-18901, No. 56-68346, No. 57
(Refer to Japanese Patent Publication No. 40401 and Japanese Patent Publication No. 61-17461) Problems to be Solved by the Invention According to the method of impregnating or blending potassium permanganate into natural zeolite synthetic zeolite or activated carbon and oxidatively decomposing the generated ethylene. The oxidizing agent, potassium permanganate, has a storage problem, and its oxidizing power tends to decrease before use, so the oxidation reaction against ethylene is extremely slow, making it difficult to maintain the freshness of fruits and vegetables. could not.
また、水分濃度が比較的高い容器の中においては、過マ
ンガン酸カリウムが溶出する為、汚染の原因となり、食
品衛生上からも好ましくない。Furthermore, potassium permanganate will be eluted in a container with a relatively high moisture concentration, causing contamination, which is undesirable from a food hygiene perspective.
問題を解決するための手段
本発明者等はこのような事情に鑑み、水分濃度の高い密
閉包装状態の青果物類におけるエチレンを除去する方法
について、種々の試験を行い克明な検討を重ねた結果、
カチオン種が銀イオンであり、且つＳｉＯ□／＾１２０
３のモル比が約２５以上である結晶性高シリカゼオライ
トが、水分が高濃度で共存する場合においても充分なエ
チレンの吸着除去機能を維持できることを知見し、過マ
ンガン酸カリウム等の他の酸化剤の添加を必要としない
新規な青果物類の鮮度保持剤として使用できることを見
い出した。Means to Solve the Problem In view of the above circumstances, the inventors of the present invention have conducted various tests and made detailed studies regarding methods for removing ethylene from tightly packaged fruits and vegetables with high moisture concentration.
The cation species is silver ion, and SiO□/^120
It was discovered that crystalline high-silica zeolite with a molar ratio of 3 to 3 of about 25 or more can maintain sufficient ethylene adsorption and removal function even when water coexists at high concentrations, and other oxidized zeolites such as potassium permanganate It has been found that the present invention can be used as a novel freshness-preserving agent for fruits and vegetables without the need for the addition of additives.
本発明の実施に適する結晶性高シリカゼオライトは、ｓ
ｉｏ！／ａｔ！ｏ３のモル比が約２５以上のものであり
、例えばペンタシル型高シリカゼオライト、常法による
脱アルミ等の処理によってＳｉＯ□／Ａｌ２Ｏ，のモル
比を約２５以上に増大させた高シリカモルデナイトゼオ
ライト、高シリカフォージャサイトゼオライト、高シリ
カエリオナイトゼオライト高シリカオフレタイトゼオラ
イト及び高シリカフェリエライトゼオライト等であり、
これらのうちＺＳＭ−５型ゼオライト等として知られて
いるペンタシル型ゼオライト及び高シリカモルデナイト
ゼオライトは、脱アルミ処理を行わなくても、５ｔ（ｈ
／Ａｈａｓのモル比が約２５以上のものが直接合成でき
るので有利である。Crystalline high silica zeolites suitable for the practice of the present invention include s
io! /at! O3 molar ratio is about 25 or more, for example, pentasil type high silica zeolite, high silica mordenite zeolite whose molar ratio of SiO□/Al2O has been increased to about 25 or more by treatment such as dealumination by a conventional method, High silica faujasite zeolite, high silica erionite zeolite, high silica offretite zeolite, high silica faujasite zeolite, etc.
Among these, pentasil type zeolite known as ZSM-5 type zeolite and high silica mordenite zeolite can produce up to 5 tons (h) without dealumination treatment.
/Ahas molar ratio of about 25 or more can be advantageously synthesized directly.
本発明の実施に用いる銀イオンをカチオン種とする結晶
性高シリカゼオライトは、硝酸銀水溶液及び硫酸銀水溶
液等のような水溶性銀塩の水溶液を用い、イオン交換反
応をすることにより得られる。イオン交換反応の条件は
、結晶性高シリカゼオライトの種類及び５１０ｇ／Ａｈ
０３のモル比に応じて適宜決定されるべきであるが、−
船釣に銀塩の水溶液濃度は０．０１〜０．５モル、液温
は２０〜５０°Ｃ，イオン交換反応時間は攪拌する場合
３０分〜１時間。The crystalline high-silica zeolite containing silver ions as the cationic species used in the practice of the present invention can be obtained by carrying out an ion exchange reaction using an aqueous solution of a water-soluble silver salt such as an aqueous silver nitrate solution and an aqueous silver sulfate solution. The conditions for the ion exchange reaction were the type of crystalline high silica zeolite and 510 g/Ah.
It should be determined appropriately depending on the molar ratio of 03, but -
For boat fishing, the silver salt aqueous solution concentration is 0.01 to 0.5 mol, the liquid temperature is 20 to 50°C, and the ion exchange reaction time is 30 minutes to 1 hour when stirring.
撹拌しない場合３〜６時間の条件で通常のイオン交換操
作を行えば充分である。カチオン種とする銀イオンの量
は、結晶性高シリカゼオライト中に１０重量％以下であ
り、好ましくは０．１〜５重量％の範囲である。銀イオ
ンの量が０．１重量％以下では、エチレン吸着の効果が
充分に表われず、一方５重量％以上では、銀イオンの量
を増加させてもエチレン吸着量はほとんど変化しない為
、経済性からみても５重世％以下が好ましい。If stirring is not used, it is sufficient to carry out a normal ion exchange operation for 3 to 6 hours. The amount of silver ions used as cationic species in the crystalline high-silica zeolite is 10% by weight or less, preferably in the range of 0.1 to 5% by weight. If the amount of silver ions is less than 0.1% by weight, the effect of ethylene adsorption will not be sufficiently exhibited, while if it is more than 5% by weight, the amount of ethylene adsorption will hardly change even if the amount of silver ions is increased, making it economical. From the viewpoint of sex, it is preferable that it is less than 5%.
本発明の実施に適する銀イオンをカチオン種とする結晶
性高シリカゼオライトとしては、５ｉ０２／Ａ１．０３
のモル比が約２５以上から無限大までのものがあるが、
ＳｉＯ□／Ａｌ□０３のモル比が約５００以上のものに
ついては、銀イオンの含有量が少なくなる為、エチレン
の吸着量力５少なくなり、使用量を増加しなければ十分
な効果が得られない。The crystalline high silica zeolite containing silver ions as a cationic species suitable for carrying out the present invention includes 5i02/A1.03
There are cases where the molar ratio of is from about 25 or more to infinity,
For those with a SiO□/Al□03 molar ratio of about 500 or more, the content of silver ions decreases, so the adsorption capacity of ethylene decreases by 5, and a sufficient effect cannot be obtained unless the amount used is increased. .
一方、Ｓｉｎｇ／＾ｈ０３のモル比が約２５以下では、
水分に対する選択吸着特性が残る為、本発明が目的とす
るエチレン吸着剤には適さない。On the other hand, when the molar ratio of Sing/^h03 is about 25 or less,
Since selective adsorption characteristics for water remain, it is not suitable as an ethylene adsorbent targeted by the present invention.
本発明の実施においては、銀イオンをカチオン種とする
結晶性高シリカゼオライトの１種類あるいは数種類のも
のを組み合わせて使用することができる。また、必要に
応じて、これに酸性白土。In carrying out the present invention, one type or a combination of several types of crystalline high silica zeolites containing silver ions as cationic species can be used. Also, if necessary, add acid clay to this.
ベントナイト、カオリン等の天然粘土鉱物及びシリカゲ
ル等の吸湿剤を混合してもよい。使用形状としては、粉
末状、顆粒状あるいはベレット状として用いることがで
きる。Natural clay minerals such as bentonite and kaolin and hygroscopic agents such as silica gel may be mixed. It can be used in the form of powder, granules, or pellets.
本発明のエチレン吸着剤を青果物類の鮮度保持の目的に
使用する方法としては、容器内に直接投入する方法９通
気性のある袋に収納して容器内に入れる方法９合成樹脂
に混練してフィルム化して用いる方法９合成樹脂に混練
してシート状に成型して用いる方法及び合成樹脂に混練
したものを容器表面に展着する方法などがある。Methods of using the ethylene adsorbent of the present invention for the purpose of preserving the freshness of fruits and vegetables include a method of directly introducing it into a container, a method of storing it in a breathable bag and placing it in a container, and a method of kneading it with a synthetic resin. Method 9: Method 9: Use by kneading into a synthetic resin and molding into a sheet, and using by kneading into a synthetic resin and spreading on the surface of a container.
本発明のエチレン吸着剤を青果物類の鮮度保持の目的に
使用する場合の使用量は、青果物類の種類によって多少
異なるが、通常は青果物￥！Ｉ １ ｋｇ当たり０．１
−１０ｇの範囲が好適である。When using the ethylene adsorbent of the present invention for the purpose of preserving the freshness of fruits and vegetables, the amount used varies somewhat depending on the type of fruits and vegetables, but it is usually ¥! I 0.1 per kg
A range of -10g is preferred.
作用
本発明のエチレン吸着剤は、優れたエチレンの吸着性能
を有し、水分が高濃度で共存している場合でも、エチレ
ンの吸着作用が殆ど影響されない特異な挙動を示す。そ
の現象の理由について本発明者等は、後述の実施例及び
比較例の試験結果から次のように推測している。Effect The ethylene adsorbent of the present invention has excellent ethylene adsorption performance, and exhibits a unique behavior in which the ethylene adsorption effect is hardly affected even when water coexists at a high concentration. The inventors of the present invention conjecture the reason for this phenomenon as follows from the test results of Examples and Comparative Examples described below.
水分が低濃度の場合には、銀イオンをカチオン種とする
ゼオライトは、そのＳｉＯ，／Ａ１．０．のモル比に関
係なく、エチレンをよく吸着する。ところが、水分が高
濃度の場合には、銀イオンをカチオン種とするゼオライ
トであっても、そのＳｉＯ□／ＡｈＯｉのモル比が約２
５以下のものは、エチレンをほとんど吸着しないか、あ
るいは−度吸着したエチレンのほとんどを放出する為、
エチレン吸着の機能を果たさない。一方、ＳｉＯ□／Ａ
ｈ（ｈのモル比が約２５以上のものは、水分が高濃度で
共存する場合でも、エチレンをよく吸着する。When the water concentration is low, the zeolite containing silver ions as the cation species has a SiO, /A1.0. Adsorbs ethylene well regardless of its molar ratio. However, when the water concentration is high, even if the zeolite has silver ions as the cation species, the molar ratio of SiO□/AhOi is about 2.
Those below 5 either hardly adsorb ethylene or release most of the adsorbed ethylene.
It does not perform the function of ethylene adsorption. On the other hand, SiO□/A
Those with a molar ratio of h (h) of about 25 or more adsorb ethylene well even when water is present at a high concentration.
ＳｉＯ，／Ａ１．Ｏ，のモル比が約２５以上の結晶性高
シリカゼオライトが疎水性を示すことは既に知られてい
るが、天然ゼオライトあるいは５ｉＯ１／＾１ｚＯ，の
モル比が約２５以下であるモレキュラーシーブと呼ばれ
ているゼオライトには、疎水性は見られない。SiO,/A1. It is already known that crystalline high-silica zeolites with a molar ratio of O, of about 25 or more exhibit hydrophobicity, but they are called natural zeolites or molecular sieves, which have a molar ratio of 5iO1/^1zO of about 25 or less. The zeolite used in this study does not show any hydrophobicity.
例えば、水分吸着量についてその性質をみると、５ｉＯ
ｆｉ／Ａ１ｇ０３のモル比が約２５以上の結晶性高シリ
カゼオライトの場合、モル比が大きくなるにしたがって
水分吸着量が減少し、ＳｉＯ□／Ａｌｚ０３のモル比が
約２５〜約５００の場合、水分吸着量は約ｌθ〜約０．
１重曖％である。一方、天然ゼオライトあるいはモレキ
ュラーシーブと呼ばれるゼオライトの水分吸着量は、約
２５〜約３５重量％と高吸湿性を示す。For example, looking at the properties of water adsorption, 5iO
In the case of crystalline high-silica zeolite with a molar ratio of fi/A1g03 of about 25 or more, the amount of water adsorption decreases as the molar ratio increases, and when the molar ratio of SiO□/Alz03 is about 25 to about 500, the amount of water adsorption decreases. The adsorption amount is about lθ to about 0.
It is 1% ambiguous. On the other hand, zeolite called natural zeolite or molecular sieve has a high moisture adsorption amount of about 25 to about 35% by weight.
銀イオンをカチオン種とするゼオライトであり、且つＳ
ｉＯ□／Ａｌ□０．のモル比が約２５以上の結晶性高シ
リカゼオライトの場合は、疎水性がある為に、水よりも
むしろエチレンを選択的に吸着し、水分が高濃度で共存
する場合でもエチレンをよく吸着すると考えられる。A zeolite with silver ions as the cationic species, and S
iO□/Al□0. Crystalline high-silica zeolite with a molar ratio of about 25 or more has hydrophobicity, so it selectively adsorbs ethylene rather than water, and it adsorbs ethylene well even when water coexists at a high concentration. Conceivable.
実施例１〜５及び比較例１〜３
本発明エチレン吸着剤及び比較試料をエチレンガスと接
触させて、そのエチレン吸着作用を調べたものである。Examples 1 to 5 and Comparative Examples 1 to 3 The ethylene adsorbent of the present invention and a comparative sample were brought into contact with ethylene gas, and their ethylene adsorption effects were investigated.
容積５１のガラス製密封容器の中に、第１表に示した各
種ゼオライト５ｇを入れたシャーレと水５０ｍ ｌを入
れたビーカーを収納して、室温（平均気温２０°Ｃ）に
２４時間保った。その後、密封容器にエチレンガス１Ｉ
ＩＩＩｌを注入し、３時間後及び２４時間後の容器内の
エチレンガス濃度をＦＩＤ式ガスクロマトグラフにより
測定した。このときの容器内の相対湿度は９５〜１００
％であった。A petri dish containing 5 g of the various zeolites shown in Table 1 and a beaker containing 50 ml of water were placed in a sealed glass container with a volume of 51, and kept at room temperature (average temperature 20°C) for 24 hours. . Then, put 1 I of ethylene gas into a sealed container.
IIIl was injected, and the ethylene gas concentration in the container was measured 3 hours and 24 hours later using an FID gas chromatograph. The relative humidity inside the container at this time is 95-100
%Met.
次に、上述のビーカー内に水５０ｒａ １２を入れない
で各種ゼオライト５ｇのみを入れたものを用いて、同じ
操作を行いエチレン吸着作用を測定した。このときの容
器内の相対湿度は３０〜４０％であった。Next, the ethylene adsorption effect was measured by carrying out the same operation using a beaker in which only 5 g of each type of zeolite was added without adding 50 ra 12 of water. The relative humidity inside the container at this time was 30 to 40%.
なお、この実施例で用いた結晶性高シリカゼオライトは
常法にしたがって合成し、各種ゼオライトの乾燥品５０
ｇに０．０８モル硝酸銀水溶液２５００＋ ４１！を加
えて得られた混合物を、室温にて３０分間撹拌しながら
イオン交換を行った。得られたＡｇ−ゼオライトを濾過
、水洗し、過剰の銀イオンを除去した後、１１０°Ｃで
２時間乾燥してへｇ−ゼオライトの粉末を得た。また、
比較例に用いたゼオライトは市販の試薬を用い、前述と
同様のイオン交換操作を行い、Ａｇ−ゼオライトの粉末
を得た。The crystalline high-silica zeolite used in this example was synthesized according to a conventional method, and 50% of dried products of various zeolites were synthesized.
0.08M silver nitrate aqueous solution 2500+ 41! The resulting mixture was subjected to ion exchange while stirring at room temperature for 30 minutes. The obtained Ag-zeolite was filtered and washed with water to remove excess silver ions, and then dried at 110°C for 2 hours to obtain a heg-zeolite powder. Also,
The zeolite used in the comparative example was subjected to the same ion exchange operation as described above using a commercially available reagent to obtain Ag-zeolite powder.
第１表 この試験結果は、第２表に示す通りであった。Table 1 The test results were as shown in Table 2.
水分濃度が低い場合には、実施例及び比較例ともにエチ
レンをよく吸着している。ところが、水分濃度が高い場
合、ＳｉＯ□／Ａｈ０３のモル比が約２５以下である比
較例１〜３のものは、はとんどエチレン吸着していない
。一方、ＳｉＯ２／Ａｌ２Ｏ３のモル比が約２５以上で
ある実施例１〜５のものは、水分濃度が高い場合でもエ
チレンをよく吸着していることがわかる。When the water concentration is low, both the examples and comparative examples adsorb ethylene well. However, when the water concentration is high, ethylene is hardly adsorbed in Comparative Examples 1 to 3 in which the SiO□/Ah03 molar ratio is about 25 or less. On the other hand, it can be seen that Examples 1 to 5 in which the SiO2/Al2O3 molar ratio is about 25 or more adsorb ethylene well even when the water concentration is high.
第２表 ＊数値はエチレンガス濃度（ＰＰｎ＋）を示す。Table 2 *Numbers indicate ethylene gas concentration (PPn+).
＊ブランクはゼオライトを入れない状態を示す。*Blank indicates the state without zeolite.
実施例６
すだち約２００ｇを２０ｃｍ Ｘ ３０ｃ＋ａ Ｘ Ｏ
，０３順のポリエチレン袋に密閉包装し、実施例１，４
及び比較例１で用いた試料１ｇを通気性不織布袋に入れ
て同封し、２０°Ｃの温度で保存して鮮度及び袋内のエ
チレンガス濃度を経時的に測定した。この試験結果は第
３表に示す通りであった。Example 6 Approximately 200g of sudachi 20cm x 30c+a x O
,03 sealed in polyethylene bags, Examples 1 and 4
1 g of the sample used in Comparative Example 1 was placed in a breathable non-woven bag and sealed, and stored at a temperature of 20°C, and the freshness and ethylene gas concentration in the bag were measured over time. The test results are shown in Table 3.
この試験結果から、ＳｉＯ２／Ａｌ２Ｏ３のモル比が約
２５以上のＡｇ−結晶性高シリカゼオライトを用いた場
合には、他のものに比べてよくエチレンを吸着し、また
はるかに優れた鮮度保持効果が認められた。From this test result, when Ag-crystalline high silica zeolite with a SiO2/Al2O3 molar ratio of about 25 or more is used, it adsorbs ethylene better than other zeolites and has a far superior freshness retention effect. was recognized.
第３表
＊上段は鮮度の外観を示し、下段はエチレンガス濃度（
ＰＰｍ）を示す。Table 3 *The upper row shows the appearance of freshness, and the lower row shows the ethylene gas concentration (
PPm).
実施例７
トマト約３００ｇを２０ｃｍ Ｘ ３０ｃｍ Ｘ Ｏ，
０３ｍｍのポリエチレン袋に密閉包装し、実施例１．
４及び比較例１で用いた試料２ｇを通気性不織布袋に入
れて同封し、２０°Ｃの温度で保存して、鮮度及び袋内
のエチレンガス濃度を経時的に測定した。その試験結果
は、第４表に示すとおりであった。Example 7 Approximately 300g of tomatoes in 20cm x 30cm x O,
Example 1 was sealed and packaged in a 03 mm polyethylene bag.
4 and Comparative Example 1, 2 g of the samples used in Comparative Example 1 were placed in a breathable nonwoven fabric bag and sealed together, and stored at a temperature of 20° C., and the freshness and ethylene gas concentration in the bag were measured over time. The test results were as shown in Table 4.
この試験結果から、ＳｉＯ２／Ａｌ２Ｏ３のモル比が約
２５以上のへｇ＝結晶性高シリカゼオライトを用いた場
合には、他のものに比べてよくエチレンを吸着し、また
、はるかに優れた鮮度保持効果が認められ第４表
＊上段は鮮度の外観を示し、下段はエチレンガス濃度（
ＰＰｗ＋）を示す。From this test result, when using Heg = crystalline high silica zeolite with a SiO2/Al2O3 molar ratio of about 25 or more, it adsorbs ethylene better than other zeolites, and also has much better freshness. The retention effect was observed in Table 4 *The upper row shows the appearance of freshness, and the lower row shows the ethylene gas concentration (
PPw+).
実施例８
実施例１及び比較例１で用いた試料を１０重量％程度に
なるように混入させて、ポリエチレンフィルムを作製し
た。このフィルムを用いた２０ＣＩＸ３０ｃｍＸ０．０
３Ｍの袋と、ブランクとして試料を混入９さセていない
同一サイズのポリエチレン袋を用いて、すだち約２００
ｇを密閉包装し、２０°Ｃの温度で保存して鮮度及び袋
内のエチレンガス濃度を経時的に測定した。Example 8 A polyethylene film was prepared by mixing the samples used in Example 1 and Comparative Example 1 to about 10% by weight. 20CIX30cmX0.0 using this film
Using a 3M bag and a polyethylene bag of the same size containing the sample as a blank, approximately 200
g was sealed and stored at a temperature of 20°C, and the freshness and ethylene gas concentration inside the bag were measured over time.
この試験結果は、第５表に示す通りであった。The test results were as shown in Table 5.
この試験結果から、ＳｉＯ□／ＡｈＯ＋のモル比が約２
５以上のＡｇ−結晶性高シリカゼオライトを樹脂に混練
させた後フィルム化した場合においても、他のものと比
べてよくエチレンを吸着し、またはるかに優れた鮮度保
持効果が認められた。From this test result, the molar ratio of SiO□/AhO+ is approximately 2.
Even when a Ag-crystalline high silica zeolite of 5 or more was kneaded into a resin and then formed into a film, it adsorbed ethylene better than other zeolites, and a far superior freshness retention effect was observed.
第５表
＊上段は鮮度の外観を示し、下段はエチレンガス濃度（
ＰＰｍ）を示す。Table 5 *The upper row shows the appearance of freshness, and the lower row shows the ethylene gas concentration (
PPm).
発明の効果
本発明によれば、水分濃度が高い場合においても、水分
よりエチレンを選択的によく吸着しうるので、青果物類
の鮮度を長期間保持できる効果が得られる。Effects of the Invention According to the present invention, even when the water concentration is high, ethylene can be selectively adsorbed better than water, so that the freshness of fruits and vegetables can be maintained for a long period of time.
Claims (1)
＿２Ｏ＿３のモル比が約２５以上である結晶性高シリカ
ゼオライトを必須成分とするエチレン吸着剤。The cationic species is silver ion, and SiO_2/Al
An ethylene adsorbent containing crystalline high silica zeolite having a molar ratio of _2O_3 of about 25 or more as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62306758A JPH01148341A (en) | 1987-12-02 | 1987-12-02 | Ethylene adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62306758A JPH01148341A (en) | 1987-12-02 | 1987-12-02 | Ethylene adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01148341A true JPH01148341A (en) | 1989-06-09 |
Family
ID=17960949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62306758A Pending JPH01148341A (en) | 1987-12-02 | 1987-12-02 | Ethylene adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01148341A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2735992A1 (en) * | 1995-06-29 | 1997-01-03 | Inst Francais Du Petrole | ADSORBENTS USEFUL IN PROCESSES FOR PURIFYING ETHYLENE POLLUTED ATMOSPHERES |
| EP0775518A3 (en) * | 1995-11-22 | 1997-08-06 | Degussa | Silicon rich zeolite |
| EP0888815A2 (en) * | 1997-07-02 | 1999-01-07 | Tosoh Corporation | Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas |
| EP1134022A1 (en) * | 2000-03-15 | 2001-09-19 | Degussa AG | Adsorbent |
| KR100426957B1 (en) * | 2001-12-31 | 2004-04-14 | 한국에너지기술연구원 | Adsorbent Preparations and Applications for C4 Olefin Separation from Mixtures |
| KR100787210B1 (en) * | 2006-06-30 | 2007-12-21 | 한국에너지기술연구원 | Silver nitrate impregnated aluminosilica gel adsorbent for separation of olefin/parafin |
| JP2010042381A (en) * | 2008-08-18 | 2010-02-25 | Taiyo Nippon Sanso Corp | Xenon sorbent, method for enriching xenon, xenon concentrator, and air liquefaction separation apparatus |
-
1987
- 1987-12-02 JP JP62306758A patent/JPH01148341A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2735992A1 (en) * | 1995-06-29 | 1997-01-03 | Inst Francais Du Petrole | ADSORBENTS USEFUL IN PROCESSES FOR PURIFYING ETHYLENE POLLUTED ATMOSPHERES |
| GB2302824A (en) * | 1995-06-29 | 1997-02-05 | Inst Francais Du Petrole | Adsorbents for use in processes for purifying gases |
| BE1010560A5 (en) * | 1995-06-29 | 1998-10-06 | Inst Francais Du Petrole | Adsorbents methods of use in treatment of polluted atmospheres by ethylene. |
| GB2302824B (en) * | 1995-06-29 | 1999-09-15 | Inst Francais Du Petrole | Adsorbents for use in processes for purifying atmospheres polluted with ethylene |
| EP0775518A3 (en) * | 1995-11-22 | 1997-08-06 | Degussa | Silicon rich zeolite |
| EP0888815A2 (en) * | 1997-07-02 | 1999-01-07 | Tosoh Corporation | Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas |
| EP0888815A3 (en) * | 1997-07-02 | 1999-01-20 | Tosoh Corporation | Adsorbent for ethylene, method for adsorbing and removing ethylene and method for purifying an exhaust gas |
| EP1134022A1 (en) * | 2000-03-15 | 2001-09-19 | Degussa AG | Adsorbent |
| KR100426957B1 (en) * | 2001-12-31 | 2004-04-14 | 한국에너지기술연구원 | Adsorbent Preparations and Applications for C4 Olefin Separation from Mixtures |
| KR100787210B1 (en) * | 2006-06-30 | 2007-12-21 | 한국에너지기술연구원 | Silver nitrate impregnated aluminosilica gel adsorbent for separation of olefin/parafin |
| JP2010042381A (en) * | 2008-08-18 | 2010-02-25 | Taiyo Nippon Sanso Corp | Xenon sorbent, method for enriching xenon, xenon concentrator, and air liquefaction separation apparatus |
| WO2010021127A1 (en) * | 2008-08-18 | 2010-02-25 | 国立大学法人岡山大学 | Xenon adsorbent, xenon enrichment method, xenon enrichment device, and air liquefaction and separation device |
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