JPH10155418A - Environment control storage method for fruit vegetables - Google Patents
Environment control storage method for fruit vegetablesInfo
- Publication number
- JPH10155418A JPH10155418A JP32038496A JP32038496A JPH10155418A JP H10155418 A JPH10155418 A JP H10155418A JP 32038496 A JP32038496 A JP 32038496A JP 32038496 A JP32038496 A JP 32038496A JP H10155418 A JPH10155418 A JP H10155418A
- Authority
- JP
- Japan
- Prior art keywords
- storage
- high silica
- volatile organic
- silica zeolite
- zeolite
- 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
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
- Storage Of Fruits Or Vegetables (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、貯蔵庫内の雰囲気
を制御して果菜類を長期間貯蔵する果菜類の環境制御貯
蔵方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for controlling and storing fruits and vegetables for a long period of time by controlling the atmosphere in a storage.
【０００２】[0002]
【従来の技術】みかん、かぼす、りんご等の果菜類を長
期に貯蔵することは、流通過程における貯蔵物の劣化に
よる損失の回避、通年に亘る安定した出荷の観点から極
めてニーズが高い。このため、各種鮮度技術が検討され
ているが、基本的には環境調整因子として次の(1) 〜
(5) を調整することにより達成される。2. Description of the Related Art Storing fruits and vegetables such as tangerines, kabosu, apples and the like for a long period of time is extremely demanded from the viewpoint of avoiding loss due to deterioration of stored products in the distribution process and stable shipping throughout the year. For this reason, various freshness technologies are being studied, but basically the following (1)-
This is achieved by adjusting (5).
【０００３】(1) 各果菜の種類に応じた酸素濃度、(2)
各果菜の種類に応じたＣＯ2 濃度、(3) 各果菜の種類に
応じた０〜１５℃の低温、(4) 相対湿度の８０％程度の
調湿、(5) 各果菜の成熟に伴って生成し成長、老化因子
となるエチレン，アルデヒト，テルペン等の揮発性有機
物の除去、このうち低温貯蔵は広く普及しているが、雰
囲気ガスの調整については果菜類を揮発性有機物分解剤
で塗布した包装紙で包んで生成する揮発性有機物質を吸
着分解する方法が用いられている程度である。[0003] (1) oxygen concentration according to the type of each vegetable, (2)
CO 2 concentration according to the type of each vegetable, (3) low temperature of 0 to 15 ° C. according to the type of each vegetable, (4) humidity control of about 80% of relative humidity, (5) with maturity of each vegetable Removal of volatile organic substances such as ethylene, aldechet, and terpene, which form and grow and become aging factors. Of these, low-temperature storage is widely used, but for adjusting atmospheric gas, fruits and vegetables are applied with a volatile organic substance decomposer. To this extent, a method of adsorbing and decomposing volatile organic substances generated by wrapping in wrapping paper is used.
【０００４】[0004]
【発明が解決しようとする課題】ところで、果菜類貯蔵
時の鮮度保持においては、まず貯蔵の初期の貯蔵庫から
の酸素除去（Ｏ2 プルダウン）が行われている。また、
貯蔵が開始されると果菜類の代謝により酸素が消費され
てＣＯ2 が放出される。このため、もはや酸素の除去は
必要がなく、むしろ系外から代謝に見合う酸素の供給が
必要であるが、これは貯蔵庫への空気の供給を行えば良
いので容易に実施できる。この段階ではむしろ代謝によ
り発生するＣＯ2 の連続的な系外への除去が重要とあ
る。この為には現在活性炭吸着塔に貯蔵庫ガスを導いて
ＣＯ2 を吸着除去し、ＣＯ2 で飽和した活性炭を系外か
らの空気によるパージ再生で放出する方法が採られてい
る。ＣＯ2 の系外への除去はほぼ大気圧近傍で行われる
ため、それほど大きな負担とはならない。In order to maintain the freshness of fruits and vegetables during storage, first, oxygen is removed from the storage at the beginning of storage (O 2 pull-down). Also,
When storage is started, oxygen is consumed by metabolism of fruits and vegetables, and CO 2 is released. For this reason, it is no longer necessary to remove oxygen. Rather, it is necessary to supply oxygen suitable for metabolism from outside the system, but this can be easily performed because air only needs to be supplied to the storage. At this stage, it is rather important to continuously remove metabolic CO 2 from the system. Therefore To the CO 2 removed by adsorption currently led reservoir gas into the activated carbon adsorption tower, a method of releasing the saturated activated carbon with CO 2 in air purge regeneration with from outside of the system have been taken. Since the removal of CO 2 out of the system is performed almost at the atmospheric pressure, the burden is not so large.
【０００５】また、活性炭は空気再生時の水分による失
活の回避の観点からは良好な吸着剤ではあるが、ゼオラ
イトに比較してＣＯ2 の吸着量が１／２〜１／３に留ま
り、その分吸着剤の使用量が増大する。また、ＣＯ2 の
発生と同時に発生するエチレン，アセトアルデヒト，テ
ルペンなどの揮発性有機物質は果菜類の成長、老化因子
であり、これら物質の除去が必要であるが、活性炭の吸
着量はそれほど大きくない。このため現在は活性炭に担
持されたハロゲン過酸化物による酸化分解が良く用いら
れる。この方法では相対湿度５０％以上では酸化分解反
応は大幅に低下し、反応の維持のためには相対湿度５０
％以下にする為、前段での水分除去又は処理ガスの３０
℃以上への昇温が必要であり、これ等の前処理はかなり
煩雑である。また、ハロゲン酸化物は極めて高価なこと
も課題となる。[0005] Activated carbon is a good adsorbent from the viewpoint of avoiding deactivation due to moisture during air regeneration, but the amount of adsorbed CO 2 is reduced to 1/2 to 1/3 as compared with zeolite. The amount of adsorbent used increases accordingly. In addition, volatile organic substances such as ethylene, acetoaldehyde and terpene, which are generated simultaneously with the generation of CO 2 , are factors for the growth and aging of fruits and vegetables, and it is necessary to remove these substances. However, the adsorption amount of activated carbon is so large. Absent. Therefore, at present, oxidative decomposition by halogen peroxide supported on activated carbon is often used. In this method, the oxidative decomposition reaction is significantly reduced at a relative humidity of 50% or more.
% Or less of water in the previous stage or 30% of the processing gas.
It is necessary to raise the temperature to at least ° C., and these pretreatments are considerably complicated. Another problem is that halogen oxides are extremely expensive.
【０００６】本発明はこうした事情を考慮してなされた
もので、従来別々の装置で実現していた、1)ＣＯ2 の系
外への放出、2)揮発性有機物質の除去を１種類の高シリ
カゼオライトを充填した１段の吸着塔で実現でき、また
設備費の低減、消費電力の低減，及び操作の単純化と保
守の容易性を確保しうる果菜類の環境制御貯蔵方法を提
供することを目的とする。[0006] The present invention has been made in view of such circumstances, and 1) the release of CO 2 to the outside of the system, and 2) the removal of volatile organic substances, which were conventionally realized by separate apparatuses. Provided is an environmentally controlled storage method for fruits and vegetables that can be realized with a single-stage adsorption tower filled with high silica zeolite and that can reduce equipment costs, reduce power consumption, and simplify operation and maintain ease. The purpose is to:
【０００７】[0007]
【課題を解決するための手段】本発明は、貯蔵庫の農作
物の鮮度保持に必要なＣＯ2 の濃度保持，エチレン，ア
セトアルデヒド，テルペン等の揮発性有機物質の除去を
行う果菜類の環境制御貯蔵方法において、高シリカゼオ
ライトを充填した吸着塔を使用し、貯蔵庫の揮発性有機
物質を含有する貯蔵庫内ガスの濃度が高い条件下では、
ＣＯ2 ，揮発性有機物質を含有する貯蔵庫内ガスを前記
高シリカゼオライトと接触せしめてＣＯ2 ，揮発性有機
物質の吸着を行なった後、高シリカゼオライトに吸着し
たＣＯ２，揮発性有機物質を系外へ放出することを特徴
とする果菜類の環境制御貯蔵方法である。The present invention SUMMARY OF] is the concentration retention CO 2 necessary for keeping the freshness of reservoir crops, ethylene, acetaldehyde, fruit vegetables method of environmental control storage which performs removal of volatile organic substances terpene such In the use of an adsorption tower filled with high silica zeolite, under conditions where the concentration of gas in the storage containing volatile organic substances in the storage is high,
CO 2, CO 2 and reservoir within the gas containing volatile organic substances contacted with the high silica zeolite, after performing the adsorption of volatile organic compounds, CO 2 adsorbed on the high silica zeolite, the volatile organic substances It is an environmentally controlled storage method for fruits and vegetables characterized by being released outside the system.
【０００８】本発明において、高シリカゼオライトに吸
着したＣＯ２ ，揮発性有機物質を系外へ放出する手段
としては、1)高シリカゼオライトに吸着したＣＯ2 ，揮
発性有機物質を空気と接触させて系外に放出する、2)高
シリカゼオライトに吸着したＣＯ2 ，揮発性有機物質を
減圧条件下に導いて系外に放出する、3)高シリカゼオラ
イトに吸着したＣＯ2 ，揮発性有機物質を減圧条件下系
外からの空気と接触させて離脱せしめて系外に放出す
る、３つの方法が挙げられる。In the present invention, the means for releasing the CO 2 and volatile organic substances adsorbed on the high silica zeolite to the outside of the system include: 1) bringing the CO 2 and volatile organic substances adsorbed on the high silica zeolite into contact with air; 2) CO 2 and volatile organic substances adsorbed on high silica zeolite are released out of the system under reduced pressure conditions. 3) CO 2 and volatile organic substances adsorbed on high silica zeolite Are brought into contact with air from the outside of the system under reduced pressure conditions to be released and released outside the system.
【０００９】本発明において、前記高シリカゼオライト
としては、ＳｉＯ2 ／Ａｌ2 Ｏ3 比７０以上のペンタシ
ルゼオライト、ＳｉＯ2 ／Ａｌ2 Ｏ3 比５以上の超安定
Ｙ型ゼオライト、ＳｉＯ2 ／Ａｌ2 Ｏ3 比５以上のメソ
ポーラスシリケートが挙げられる。In the present invention, the high silica zeolite includes a pentasil zeolite having a SiO 2 / Al 2 O 3 ratio of 70 or more, an ultra-stable Y-type zeolite having a SiO 2 / Al 2 O 3 ratio of 5 or more, and SiO 2 / Al Mesoporous silicate having a 2 O 3 ratio of 5 or more can be used.
【００１０】［作用」本発明の作用は次の通りである。
貯蔵開始時の貯蔵庫の酸素の系外への放出（Ｏ2 プルダ
ウン）に続いて貯蔵条件が定常に達すると、貯蔵した果
菜類は代謝機構のため酸素を消費してＣＯ2 を放出し、
またエチレン，テルペン，ホルムアルデヒド等の揮発性
有機物質も放出する。ここで、吸着塔に水分の共存下で
もＣＯ2 、揮発性有機物質の吸着能が維持される高シリ
カゼオライトと接触せしめると、ＣＯ2 、揮発性有機物
質は吸着されて低濃度のＣＯ2 、揮発性有機物質が塔頂
から流過するので、このガスは貯蔵庫に戻してＣＯ2 、
揮発性有機物質の濃度上昇の抑制に使用する。[Operation] The operation of the present invention is as follows.
When the storage conditions reach a steady state following the release of oxygen from the storage at the start of storage (O 2 pull-down), the stored fruits and vegetables consume oxygen to release CO 2 due to the metabolic mechanism,
It also emits volatile organic substances such as ethylene, terpene, and formaldehyde. Here, when the adsorption tower is brought into contact with high silica zeolite, which maintains the ability to adsorb CO 2 and volatile organic substances even in the presence of moisture, the CO 2 and volatile organic substances are adsorbed and low concentration CO 2 , As volatile organics flow from the top of the tower, this gas is returned to the storage and CO 2 ,
Used to control the increase in the concentration of volatile organic substances.
【００１１】そこで、吸着したＣＯ2 、揮発性有機物質
は吸着等を空気と接触せしめるか減圧に導くか、減圧条
件下の空気と接触することにより、吸着剤から離脱する
のでこれは系外に放出する。この方法により、従来は別
々の装置で実現していた、1)ＣＯ2 の系外への放出、2)
揮発性有機物質の除去を１種類の高シリカゼオライトを
充填した１段の吸着塔で実現でき、これは環境調節装置
の合理化による1)設備の低減、2)消費電力の低減、3)操
作，保守の簡略化が達成される。Then, the adsorbed CO 2 and volatile organic substances are separated from the adsorbent by bringing the adsorption or the like into contact with air or leading to reduced pressure, or by contact with air under reduced pressure conditions. discharge. By this method, 1) release of CO 2 to the outside of the system, 2)
The removal of volatile organic substances can be achieved with a single-stage adsorption tower packed with one type of high silica zeolite, which is achieved by rationalizing environmental control equipment, 1) reduction of equipment, 2) reduction of power consumption, 3) operation, Simplification of maintenance is achieved.
【００１２】[0012]
【発明の実施の形態】まず、本発明に係る果菜類の環境
制御貯蔵方法を実現するにあたって必要な装置を図１を
参照して説明する。図中の付番１は、例えば容積約３ｍ
3 の貯蔵庫である。この貯蔵庫１には、果菜類としての
かぼすが１Ｔｏｎ貯蔵されている。前記貯蔵庫１の環境
制御条件としては、温度５℃，相対湿度８０％（温度５
℃では相対湿度８０％になる），雰囲気ガス組成として
酸素５ｖｏｌ％，ＣＯ2 ５ｖｏｌ％，窒素９０ｖｏｌ％
に保つ必要がある。前記貯蔵庫１には、流路２ａを介し
て窒素製造装置３が接続されている。ここで、窒素製造
装置３としては、膜法、酸素吸着剤、窒素吸着剤を使用
した圧力スイッチング法が考えられるが、本実施例では
分子篩い型カーボン３Ａを充填した圧力スイング法によ
る窒素製造装置を採用した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an apparatus necessary for realizing the method for controlling and storing fruits and vegetables according to the present invention will be described with reference to FIG. The number 1 in the figure is, for example, about 3 m in volume.
3 storage. The storage 1 stores 1 ton of kabosu as fruits and vegetables. The environmental control conditions for the storage 1 were as follows: temperature 5 ° C., relative humidity 80% (temperature 5 ° C.).
At 80 ° C., the relative humidity is 80%), the composition of the atmosphere gas is oxygen 5 vol%, CO 2 5 vol%, nitrogen 90 vol%
Need to be kept. A nitrogen production device 3 is connected to the storage 1 via a flow path 2a. Here, as the nitrogen producing apparatus 3, a membrane method, a pressure switching method using an oxygen adsorbent and a nitrogen adsorbent can be considered, but in this embodiment, a nitrogen producing apparatus by a pressure swing method filled with molecular sieve type carbon 3A is used. It was adopted.
【００１３】また、前記貯蔵庫１には、バルブ４ｂを介
装した流路２ｂを介して高シリカゼオライト５を充填し
た吸着塔６が接続されている。ここで、高シリカゼオラ
イトとしては、ＳｉＯ2 ／Ａｌ2 Ｏ3 比が２０以上のペ
ンタシルゼオライト、又はＳｉＯ2 ／Ａｌ2 Ｏ3 比が５
以上の超安定Ｙ型ゼオライト（ＵＳＹ）、あるいはＳｉ
Ｏ2 ／Ａｌ2 Ｏ3 比が５以上のメソポーラスシリケート
が有効である。前記貯蔵庫１には、バルブ４ｃを介装し
た流路２ｃを介してブロワー７が接続されている。この
ブロワー７には、バルブ４ｄを介装した流路２ｄを介し
て前記吸着塔６が接続されている。Further, an adsorption tower 6 filled with high silica zeolite 5 is connected to the storage 1 via a flow path 2b provided with a valve 4b. Here, as the high silica zeolite, a pentasil zeolite having a SiO 2 / Al 2 O 3 ratio of 20 or more, or a SiO 2 / Al 2 O 3 ratio of 5 or more is used.
Ultra-stable Y-type zeolite (USY) or Si
A mesoporous silicate having an O 2 / Al 2 O 3 ratio of 5 or more is effective. A blower 7 is connected to the storage 1 via a flow path 2c provided with a valve 4c. The adsorption tower 6 is connected to the blower 7 via a flow path 2d provided with a valve 4d.
【００１４】前記バルブ４ｃとブロワー７間の流路２ｃ
と、前記バルブ４ｄと吸着塔６間の流路２ｄとは、バル
ブ４ｅを介装したバイパス流路２ｅにより接続されてい
る。前記ブロワー７とバルブ４ｄ間の流路２ｄには、バ
ルブ４ｆを介装した流路２ｆが接続されている。この流
路２ｆより貯蔵庫１内の酸素含有ガスが系外へ放出され
る。前記貯蔵庫１にはバルブ４ｇを介装したバイパス流
路２ｇが接続され、これにより系外の空気が貯蔵庫１内
へ送られる。なお、図中の付番２ｈは吸着塔６の頂部に
接続された、バルブ４ｈを介装した流路である。The flow path 2c between the valve 4c and the blower 7
The flow path 2d between the valve 4d and the adsorption tower 6 is connected by a bypass flow path 2e provided with a valve 4e. A flow path 2d provided with a valve 4f is connected to a flow path 2d between the blower 7 and the valve 4d. The oxygen-containing gas in the storage 1 is discharged out of the system from the flow path 2f. The storage 1 is connected to a bypass flow passage 2g having a valve 4g interposed therebetween, whereby air outside the system is sent into the storage 1. Reference numeral 2h in the figure is a flow path connected to the top of the adsorption tower 6 and provided with a valve 4h.
【００１５】次に、こうした構成の装置を用いた果菜類
の環境制御貯蔵方法について説明する。 i)まず、貯蔵庫１内にかぼす１トンを貯蔵した直後、貯
蔵庫１内の温度を冷凍機（図示せず）等を使用して室温
から５℃に冷却するとともに、系統内からの酸素除去
（Ｏ2 プルダウン）を行う。前記窒素製造装置、流路２
ａから９５ｖｏｌ％以上の窒素が０．５ｍ3 Ｎ／ｈの流
量で供給されて開状態のバルブ４ｃ、ブロワー７、バル
ブ４ｆ、流路２ｆから貯蔵庫１内の酸素含有ガスが系外
へ放出され、４０時間のパージで９４ｖｏｌ％の窒素濃
度に到達した。Next, a description will be given of a method for environmentally controlled storage of fruits and vegetables using the apparatus having such a configuration. i) First, immediately after storing 1 ton of spill in storage 1, the temperature in storage 1 is cooled from room temperature to 5 ° C. using a refrigerator (not shown) or the like, and oxygen is removed from the system ( O 2 pull-down) is performed. The nitrogen production apparatus, flow path 2
95% by volume or more of nitrogen is supplied from a at a flow rate of 0.5 m 3 N / h, and the oxygen-containing gas in the storage 1 is discharged out of the system from the open valve 4c, the blower 7, the valve 4f, and the flow path 2f. After a 40 hour purge, a nitrogen concentration of 94 vol% was reached.
【００１６】ii) この後、かぼすの環境調節条件での呼
吸代謝により貯蔵庫１の酸素が消費されてＣＯ2 が放出
される。同時に、エチレン、アセトアルデヒド、テルペ
ン等の揮発性有機物質が各々１μｇ／ｈ程度放出され
る。これらの成長、老化因子としての感受性は０．１ｐ
ｐｍと言われているので、前記吸着塔６で各々０．１ｐ
ｐｍ以下まで吸着除去する。酸素消費分の補充について
は、貯蔵庫１の酸素濃度を監視して不足分として系外の
空気を流路２ｇよりバルブ４ｇを開にして貯蔵庫１内へ
供給すればよいのでそれほど難しくない。ＣＯ2 の除去
についてはＣＯ2の選択的分離除去が必要である。Ii) After that, oxygen in the storage 1 is consumed by respiratory metabolism under the environment control condition of kabosu, and CO 2 is released. At the same time, about 1 μg / h of volatile organic substances such as ethylene, acetaldehyde and terpene are released. Their sensitivity as growth and aging factors is 0.1 p
pm, so that 0.1 p
pm or less. The replenishment of the oxygen consumption is not so difficult, since the oxygen concentration in the storage 1 is monitored and the air outside the system is supplied to the storage 1 by opening the valve 4g from the flow path 2g as a shortage. The removal of CO 2 is required selective separation and removal of CO 2.
【００１７】iii)本発明では３Ｋｇの高シリカゼオライ
トが充填された１塔式のＣＯ2 吸着塔でＣＯ2 の系外へ
の排除を行う。かぼすの代謝機構が定常状態になり貯蔵
庫１内のＣＯ2 が設定ＣＯ2 濃度５ｖｏｌ％を越えた場
合、開状態のバルブ４ｃ、ブロワー７、バルブ４ｄから
貯蔵庫１の雰囲気ガスを循環して吸着塔６に導くと、吸
着塔６の前方からＣＯ2 とエチレン、アセトアルデヒ
ド、テルペン等の揮発性有機物質が高シリカゼオライト
に吸着され、塔頂からはこれらガスを含有しないガスが
流過してバルブ４ｂを通じて貯蔵庫１に戻りＣＯ2 濃度
の維持と揮発性有機物質の除去が行われる。この後、操
作は再びＣＯ2 、揮発性有機物質の吸着工程に戻る。Iii) In the present invention, CO 2 is removed from the system by a single-column type CO 2 adsorption tower filled with 3 kg of high silica zeolite. When the metabolic mechanism of kabosu becomes a steady state and the CO 2 in the storage 1 exceeds the set CO 2 concentration of 5 vol%, the atmospheric gas in the storage 1 is circulated from the open valve 4c, the blower 7 and the valve 4d to adsorb the column. 6, CO 2 and volatile organic substances such as ethylene, acetaldehyde, and terpene are adsorbed to the high silica zeolite from the front of the adsorption tower 6, and a gas not containing these gases flows from the top of the adsorption tower 6 and the valve 4 b Then, the CO 2 is returned to the storage 1 to maintain the CO 2 concentration and remove the volatile organic substances. After this, the operation returns to the step of adsorbing CO 2 and volatile organic substances again.
【００１８】図２は、吸着時間５分、再生時間５分、循
環ガス量５０ｌＮ／分、空気パージガス量７５ｌＮ／
分、空気パージ圧力−大気圧、循環ガス中の水分濃度
０．５ｖｏｌ％の条件で、吸着剤としてペンタシルゼオ
ライトを使用し、ペンタシルゼオライトのＳｉＯ2 ／Ａ
ｌ2 Ｏ3 比を変更した時のＣＯ2 、エチレン、テルペ
ン、アセトアルデヒドの除去率（各々曲線（イ）〜
（ニ））を示したものである。FIG. 2 shows an adsorption time of 5 minutes, a regeneration time of 5 minutes, a circulating gas amount of 50 lN / min, and an air purge gas amount of 75 lN / min.
Pentasil zeolite as an adsorbent under the conditions of air purge pressure-atmospheric pressure, water concentration of 0.5 vol% in circulating gas, and SiO 2 / A of pentasil zeolite.
Removal rate of CO 2 , ethylene, terpene, and acetaldehyde when the l 2 O 3 ratio was changed (each curve (a) ~
(D)).
【００１９】ペンタシルゼオライトとしては、ＵＰＯ社
のＳｉＯ2 ／Ａｌ2 Ｏ3 比の違うサンプルを使用した。
ＳｉＯ2 ／Ａｌ2 Ｏ3 比７０未満では、ＣＯ2 、エチレ
ン、テルペン、アセトアルデヒドとも除去率が大幅に低
下しているが、これは水分の共吸着による失活が生じた
ためと思われる。As the pentasil zeolite, UPO samples having different SiO 2 / Al 2 O 3 ratios were used.
If the SiO 2 / Al 2 O 3 ratio is less than 70, the removal rates of CO 2 , ethylene, terpene, and acetaldehyde are all significantly reduced, but this is probably due to deactivation caused by co-adsorption of water.
【００２０】図３は、吸着時間５分、再生時間５分、循
環ガス量５０ｌＮ／分、空気パージガス量７５ｌＮ／
分、空気パージ圧力−大気圧、循環ガス中の水分濃度
０．５ｖｏｌ％の条件で、吸着剤として超安定Ｙ型ゼオ
ライトを含むＸ，Ｙ型ゼオライトを使用し、そのＳｉＯ
2 ／Ａｌ2 Ｏ3 比を変更した時のＣＯ2 、エチレン、テ
ルペン、アセトアルデヒドの除去率（各々曲線（イ）〜
（ニ））を示したものである。FIG. 3 shows an adsorption time of 5 minutes, a regeneration time of 5 minutes, a circulating gas amount of 50 lN / min, and an air purge gas amount of 75 lN / min.
X, Y-type zeolite containing ultra-stable Y-type zeolite is used as an adsorbent under the conditions of air purge pressure-atmospheric pressure, water concentration of 0.5 vol% in circulating gas,
Removal rate of CO 2 , ethylene, terpene, and acetaldehyde when the 2 / Al 2 O 3 ratio was changed (each curve (a) to
(D)).
【００２１】Ｘ，Ｙ超安定型ゼオライトとしては、ＵＰ
Ｏ社のＳｉＯ2 ／Ａｌ2 Ｏ3 比の違うサンプルを使用し
た。ＳｉＯ2 ／Ａｌ2 Ｏ3 比５未満では、ＣＯ2 、エチ
レン、テルペン、アセトアルデヒドとも除去率が大幅に
低下しているが、これは他のゼオライトと同様に低Ｓｉ
Ｏ2 ／Ａｌ2 Ｏ3 比側で親水性が増大し、水分の共吸着
による失活が生じたためと思われる。X and Y ultrastable zeolites include UP
Samples of Company O having different SiO 2 / Al 2 O 3 ratios were used. When the SiO 2 / Al 2 O 3 ratio is less than 5, the removal rates of CO 2 , ethylene, terpene, and acetaldehyde are greatly reduced.
It is considered that hydrophilicity was increased on the O 2 / Al 2 O 3 ratio side, and deactivation was caused by co-adsorption of water.
【００２２】図４は、吸着時間５分、再生時間５分、循
環ガス量５０ｌＮ／分、空気パージガス量７５ｌＮ／
分、空気パージ圧力−大気圧、循環ガス中の水分濃度
０．５ｖｏｌ％の条件で、吸着剤としてメソポーラスシ
リケートを使用し、そのＳｉＯ2/Al2 Ｏ3 比を変更した
時のＣＯ2 、エチレン、テルペン、アセトアルデヒドの
除去率（各々曲線（イ）〜（ニ））を示したものであ
る。FIG. 4 shows an adsorption time of 5 minutes, a regeneration time of 5 minutes, a circulating gas amount of 50 lN / min, and an air purge gas amount of 75 lN / min.
Min, air purge pressure-atmospheric pressure, water concentration in circulating gas 0.5 vol%, mesoporous silicate as adsorbent, CO 2 and ethylene when SiO 2 / Al 2 O 3 ratio was changed. , Terpene, and acetaldehyde removal rates (curves (a) to (d), respectively).
【００２３】メソポーラスシリケートは、ケイ酸ナトリ
ウムと硝酸アルミニウムを所定のＳｉＯ2 ／Ａｌ2 Ｏ3
比になるように混合した溶液（これをＡ液とする）をド
デシルトリメチルアンモニウムクロライドを塩酸に溶解
した溶液（これをＢ液とする）にテンプレート／（Ｓｉ
＋Ａｌ）比が０．１２になるように加えてえられた沈殿
を３時間熟成しこれを乾燥、焼成（テンプレート除
去）、ペレット成形（１．６ｍｍφ）したＳｉＯ2 ／Ａ
ｌ2 Ｏ3 比の違うサンプルを使用した。ＳｉＯ2 ／Ａｌ
2 Ｏ3 比５未満では、ＣＯ2 、エチレン、テルペン、ア
セトアルデヒドとも除去率が大幅に低下しているが、こ
れは他のゼオライトと同様に低ＳｉＯ2 ／Ａｌ2 Ｏ3 比
側で親水性が増大し、水分の共吸着による失活が生じた
ためと思われる。The mesoporous silicate is prepared by adding sodium silicate and aluminum nitrate to a predetermined SiO 2 / Al 2 O 3
A solution (this is referred to as solution A) obtained by mixing so as to obtain a template / (Si solution) was prepared by dissolving dodecyltrimethylammonium chloride in hydrochloric acid (referred to as solution B).
+ Al) The precipitate obtained by adding the mixture to have a ratio of 0.12 was aged for 3 hours, dried, calcined (removing the template), and pelletized (1.6 mmφ) SiO 2 / A.
Samples with different l 2 O 3 ratios were used. SiO 2 / Al
When the 2 O 3 ratio is less than 5, the removal rates of CO 2 , ethylene, terpene, and acetaldehyde are greatly reduced. However, as with other zeolites, hydrophilicity is low on the low SiO 2 / Al 2 O 3 ratio side. This is probably because the water content increased and deactivation occurred due to co-adsorption of water.
【００２４】これら高シリカゼオライトが疎水性を示す
ことは知られているたが、本実験により水分の共存下で
も安定してＣＯ2 を吸着し、ＣＯ2 の吸着とともにエチ
レン、テルペン、アセトアルデヒド等の有機物を吸着す
ることが確認された。塔後方から上記有機物が出る前に
バルブ４ｂ，４ｃ，４ｄを閉じてバルブ４ｅ，４ｆ，４
ｈを開いて流路２ｈから系外の空気を吸着塔６に導く
と、空気と吸着剤の向流接触により吸着されたＣＯ2 、
エチレン、テルペン、アセトアルデヒド等が離脱して流
路２ｆから系外に放出され再生が終了する。Although it is known that these high silica zeolites exhibit hydrophobicity, in this experiment, they stably adsorb CO 2 even in the presence of water, and together with the adsorption of CO 2 , ethylene, terpene, acetaldehyde, etc. It was confirmed that organic matter was adsorbed. Before the organic matter exits from the rear of the tower, the valves 4b, 4c, 4d are closed and the valves 4e, 4f, 4
h, the air outside the system is introduced from the flow path 2h to the adsorption tower 6, and CO 2 adsorbed by the countercurrent contact between the air and the adsorbent,
Ethylene, terpene, acetaldehyde and the like are released and released out of the system from the flow path 2f, and the regeneration is completed.
【００２５】吸着されたＣＯ2 、揮発性有機物質の除去
として、1)大気圧での空気による向流パージ、2)減圧条
件下での空気による向流パージを試みたが、いずれの方
法でも吸着剤からスカルストロームにより提案されたパ
ージガス量の算出方法の１．２倍以上を使用すれば、除
去は達成されることが確認された。本実施例では、Ｐａ
＝Ｐｄ＝１，Ｋ＝１．５を採用している。下記式（１）
にスカルストローム則によるパージガス量算出式を示
す。In order to remove adsorbed CO 2 and volatile organic substances, 1) countercurrent purging with air at atmospheric pressure and 2) countercurrent purging with air under reduced pressure were attempted. It has been confirmed that removal can be achieved by using at least 1.2 times the method of calculating the amount of purge gas proposed by Skullstrom from the adsorbent. In this embodiment, Pa
= Pd = 1 and K = 1.5. The following equation (1)
The equation for calculating the purge gas amount according to the Skullstrom rule is shown in FIG.
【００２６】 Ｇｐ＝Ｋ＊Ｇ0 ＊Ｐｄ／Ｐａ …（１） 但し、式（１）において、Ｐａは吸着圧力、Ｐｄは再生
圧力、Ｇｐは向流パージガス量、Ｇ0 は吸着工程の入り
口ガス量である。また、Ｋは実験定数であり、１．２以
上が推奨されており、１以下では再生は成立しない。Gp = K * G0 * Pd / Pa (1) In the equation (1), Pa is an adsorption pressure, Pd is a regeneration pressure, Gp is a countercurrent purge gas amount, and G0 is an inlet gas amount in the adsorption step. is there. K is an experimental constant, and 1.2 or more is recommended. If it is 1 or less, regeneration is not established.
【００２７】上述したように、本発明方法では、高シリ
カゼオライトの充填された吸着塔６により環境調節に必
要な1)ＣＯ2 除去、2)エチレン、テルペン、アセトアル
デヒド等の揮発性有機物質の除去が実施されることにな
る。上記実施例における窒素製造では１ｍ3 Ｎの窒素製
造に関わる消費電力は０．２ないし０．８ＫｗＨであ
る。また、ＣＯ2 、エチレン等の揮発性有機物質の除去
に要する消費電力は０．０１ないし０．０５Ｋｗｈ程度
であり、非常にわずかな消費電力でＣＯ2 、揮発性有機
物質の系外への放出が実施されているのが判る。As described above, in the method of the present invention, the adsorption tower 6 filled with high silica zeolite 1) removes CO 2 necessary for environmental control, and 2) removes volatile organic substances such as ethylene, terpene and acetaldehyde. Will be implemented. In the nitrogen production in the above embodiment, the power consumption for producing 1 m 3 N of nitrogen is 0.2 to 0.8 KwH. Further, the power consumption required for removing volatile organic substances such as CO 2 and ethylene is about 0.01 to 0.05 Kwh, and the emission of CO 2 and volatile organic substances to the outside of the system is extremely small. It can be seen that is implemented.
【００２８】[0028]
【発明の効果】以上詳述した如く本発明によれば、従来
別々の装置で実現していた、1)ＣＯ2の系外への放出、
2)揮発性有機物質の除去を１種類の高シリカゼオライト
を充填した１段の吸着塔で実現でき、また設備費の低
減、消費電力の低減，及び操作の単純化と保守の容易性
を確保しうる果菜類の環境制御貯蔵方法を提供できる。As described above in detail, according to the present invention, 1) release of CO 2 to the outside of the system, which has conventionally been realized by separate devices,
2) The removal of volatile organic substances can be realized with a single-stage adsorption tower filled with one kind of high silica zeolite, and the reduction of equipment cost, power consumption, and simplification of operation and ease of maintenance are ensured. It is possible to provide a method for environmentally controlled storage of possible fruits and vegetables.
【図１】本発明の一実施例に係る果菜類の環境制御貯蔵
方法の説明図。FIG. 1 is an explanatory diagram of a method for environmentally controlled storage of fruits and vegetables according to one embodiment of the present invention.
【図２】ペンタシルゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3
比とＣＯ2 、エチレン、テルペン、アセトアルデヒドの
除去率の関係を示す特性図。FIG. 2: SiO 2 / Al 2 O 3 of pentasil zeolite
FIG. 4 is a characteristic diagram showing a relationship between a ratio and a removal rate of CO 2 , ethylene, terpene, and acetaldehyde.
【図３】超安定Ｙ型ゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3
比とＣＯ2 、エチレン、テルペン、アセトアルデヒドの
除去率の関係を示す特性図。FIG. 3 SiO 2 / Al 2 O 3 of ultra-stable Y-type zeolite
FIG. 4 is a characteristic diagram showing a relationship between a ratio and a removal rate of CO 2 , ethylene, terpene, and acetaldehyde.
【図４】メソポーラスシリケートのＳｉＯ2 ／Ａｌ2 Ｏ
3 比とＣＯ2 、エチレン、テルペン、アセトアルデヒド
の除去率の関係を示す特性図。FIG. 4 SiO 2 / Al 2 O of mesoporous silicate
FIG. 3 is a characteristic diagram showing a relationship between the 3 ratio and the removal rates of CO 2 , ethylene, terpene, and acetaldehyde.
１…貯蔵庫、 ２ａ，２ｂ，２ｃ，２ｄ，２ｅ，２ｆ，２ｇ，２ｈ…流
路、 ３…窒素製造装置、 ４ｂ，４ｃ，４ｄ，４ｅ，４ｆ，４ｇ，４ｆ…バルブ、 ６…吸着塔、 ７…高シリカゼオライト。DESCRIPTION OF SYMBOLS 1 ... Storage, 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h ... Flow path, 3 ... Nitrogen production apparatus, 4b, 4c, 4d, 4e, 4f, 4g, 4f ... Valve, 6 ... Adsorption tower, 7 ... High silica zeolite.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 北田 卓也 愛知県名古屋市中村区岩塚町字高道１番地 三菱重工業株式会社名古屋研究所内 (72)発明者 矢頭 義信 愛知県西春日井郡西枇杷島町字旭町３丁目 １番地 三菱重工業株式会社エアコン製作 所内 (72)発明者 須藤 光敏 愛知県西春日井郡西枇杷島町字旭町３丁目 １番地 三菱重工業株式会社エアコン製作 所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takuya Kitada 1 Nagoya Research Laboratory, Mitsubishi Heavy Industries, Ltd. 3-chome, Mitsubishi Heavy Industries, Ltd. Air Conditioner Works (72) Inventor Mitsutoshi Sudo 3-chome, Asahimachi, Nishibiwajima-cho, Nishi-Kasugai-gun, Aichi Prefecture Air Conditioner Works, Mitsubishi Heavy Industries, Ltd.
Claims (7)
2 の濃度保持，エチレン，アセトアルデヒド，テルペン
等の揮発性有機物質の除去を行う果菜類の環境制御貯蔵
方法において、 高シリカゼオライトを充填した吸着塔を使用し、貯蔵庫
の揮発性有機物質を含有する貯蔵庫内ガスの濃度が高い
条件下では、ＣＯ2 ，揮発性有機物質を含有する貯蔵庫
内ガスを前記高シリカゼオライトと接触せしめてＣＯ
2 ，揮発性有機物質の吸着を行なった後、高シリカゼオ
ライトに吸着したＣＯ2 ，揮発性有機物質を系外へ放出
することを特徴とする果菜類の環境制御貯蔵方法。1. CO required for maintaining freshness of agricultural products in a storage
An environmentally controlled storage method for fruits and vegetables that maintains the concentration of 2 and removes volatile organic substances such as ethylene, acetaldehyde, and terpenes. It uses an adsorption tower filled with high silica zeolite and contains volatile organic substances in the storage. Under conditions where the concentration of the gas in the storage is high, the gas in the storage containing CO 2 and volatile organic substances is brought into contact with the high silica zeolite to reduce CO 2.
2. A method for environmentally controlled storage of fruits and vegetables, characterized by releasing CO 2 and volatile organic substances adsorbed on high silica zeolite after absorbing volatile organic substances.
揮発性有機物質を空気と接触させて系外に放出すること
を特徴とする請求項１記載の果菜類の環境制御貯蔵方
法。2. The method according to claim 1, wherein the CO 2 adsorbed on the high silica zeolite,
The environmentally controlled storage method for fruits and vegetables according to claim 1, wherein the volatile organic substance is released from the system when brought into contact with air.
揮発性有機物質を減圧条件下に導いて系外に放出するこ
とを特徴とする請求項１記載の果菜類の環境制御貯蔵方
法。3. The method of claim 2 , wherein the CO 2 adsorbed on the high silica zeolite,
The environmentally controlled storage method for fruits and vegetables according to claim 1, wherein the volatile organic substance is guided under reduced pressure conditions and released outside the system.
揮発性有機物質を減圧条件下系外からの空気と接触させ
て離脱せしめて系外に放出することを特徴とする請求項
１記載の果菜類の環境制御貯蔵方法。4. The method of claim 2 , wherein CO 2 adsorbed on the high silica zeolite,
2. The method for controlling and storing fruits and vegetables according to claim 1, wherein the volatile organic substance is brought into contact with air from outside the system under reduced pressure to release the organic compound from the system.
Ｏ3 比７０以上のペンタシルゼオライトであることを特
徴とする請求項１記載の果菜類の環境制御貯蔵方法。5. The high silica zeolite is SiO 2 / Al 2
Fruit vegetables environmental control storage method of claim 1, wherein the O is 3 ratio of 70 or more pentasil zeolite.
Ｏ3 比５以上の超安定Ｙ型ゼオライトであることを特徴
とする請求項１記載の果菜類の環境制御貯蔵方法。6. The high silica zeolite is SiO 2 / Al 2
2. The method according to claim 1, wherein the zeolite is an ultra-stable Y-type zeolite having an O 3 ratio of 5 or more.
Ｏ3 比５以上のメソポーラスシリケートであることを特
徴とする請求項１記載の果菜類の環境制御貯蔵方法。7. The high silica zeolite is SiO 2 / Al 2
Fruit vegetables environmental control storage method of claim 1, wherein the O is 3 ratio of 5 or more mesoporous silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32038496A JP3349375B2 (en) | 1996-11-29 | 1996-11-29 | Environmentally controlled storage of fruits and vegetables |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32038496A JP3349375B2 (en) | 1996-11-29 | 1996-11-29 | Environmentally controlled storage of fruits and vegetables |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10155418A true JPH10155418A (en) | 1998-06-16 |
| JP3349375B2 JP3349375B2 (en) | 2002-11-25 |
Family
ID=18120878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32038496A Expired - Fee Related JP3349375B2 (en) | 1996-11-29 | 1996-11-29 | Environmentally controlled storage of fruits and vegetables |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3349375B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009214101A (en) * | 2008-02-14 | 2009-09-24 | Research Institute Of Innovative Technology For The Earth | Carbon dioxide separating agent and method for selectively separating carbon dioxide |
| JP2010042331A (en) * | 2008-08-11 | 2010-02-25 | Kyuchaku Gijutsu Kogyo Kk | Ballast water treatment apparatus loaded with an ozone producing device using pressure swing adsorption method |
| JP2018169124A (en) * | 2017-03-30 | 2018-11-01 | 宮崎県 | Vegetables and fruits storage device and vegetables and fruits storage method |
| JP2019034302A (en) * | 2017-08-10 | 2019-03-07 | エア プロダクツ アンド ケミカルズ インコーポレイテッドＡｉｒ Ｐｒｏｄｕｃｔｓ Ａｎｄ Ｃｈｅｍｉｃａｌｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | Rapid cycle pressure swing adsorption step and adsorptive laminate for use in the same |
-
1996
- 1996-11-29 JP JP32038496A patent/JP3349375B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009214101A (en) * | 2008-02-14 | 2009-09-24 | Research Institute Of Innovative Technology For The Earth | Carbon dioxide separating agent and method for selectively separating carbon dioxide |
| JP2010042331A (en) * | 2008-08-11 | 2010-02-25 | Kyuchaku Gijutsu Kogyo Kk | Ballast water treatment apparatus loaded with an ozone producing device using pressure swing adsorption method |
| JP2018169124A (en) * | 2017-03-30 | 2018-11-01 | 宮崎県 | Vegetables and fruits storage device and vegetables and fruits storage method |
| JP2019034302A (en) * | 2017-08-10 | 2019-03-07 | エア プロダクツ アンド ケミカルズ インコーポレイテッドＡｉｒ Ｐｒｏｄｕｃｔｓ Ａｎｄ Ｃｈｅｍｉｃａｌｓ Ｉｎｃｏｒｐｏｒａｔｅｄ | Rapid cycle pressure swing adsorption step and adsorptive laminate for use in the same |
| US10765991B2 (en) | 2017-08-10 | 2020-09-08 | Air Products And Chemicals, Inc. | Rapid cycle pressure swing adsorption process and adsorbent laminates for use therein |
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| Publication number | Publication date |
|---|---|
| JP3349375B2 (en) | 2002-11-25 |
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