JP4436625B2 - Dark current generator, ethylene gas reforming apparatus and reforming method using OH radicals using the apparatus - Google Patents

Description

【００３９】
この化学式にあるように、酢酸に加速電子ｅを衝突させると、ＯＨラジカルが生成される。
【００４０】
そのように、酢酸に加速電子を衝突させて、ＯＨラジカルが生成されると、次に（２）段階として、エチレンとの反応が起きる。
そのときのＯＨラジカルとＣ₂Ｈ₄が反応する仕組を次の化学式２で示す。
【００４１】
【化２】

【００４２】
この化学式２に示されるように、エチレン（Ｃ₂Ｈ₄）にＯＨラジカルが反応して、エタンと水に改質される。即ち、ＯＨラジカルによってエチレンが減少することになる。
上記（１）段階と（２）段階の反応は瞬間的に起きているので、実験的には、反応前と反応後のエチレンの濃度で確かめられる。
【００４３】
次にバナナとりんごの例に説明する。
バナナやりんごからはエチレンを放出するが、次のようなものも一緒に放出している。
【００４４】
＜バナナからの放出物質＞
果実様香り成分のアミルエステル（分極性が強い）
酢酸 ＣＨ₃ＣＯＯＣ₅Ｈ₁₁
酪酸 Ｃ₃Ｈ₇ＣＯＯＣ₅Ｈ₁₁
プロピオン酸 Ｃ₂Ｈ₅ＣＯＯＣ₅Ｈ₁₁
完熟度様香り成分のフェノールエーテル
オイゲノール
オイゲノールメチルエーテル
エレミシン
【００４５】
＜りんごからの放出物質＞
香りの中心：新鮮な青さと甘さ
ヘキサノール Ｃ₆Ｈ₁₃ＯＨ
ヘキサナール
トランス−２−ヘキサナール
甘さと完熟度（エステル類）
エチルブチレート Ｃ₂Ｈ₅ＣＯＯＣ₃Ｈ₅
ブチルアセテート
ブチルブチレート
【００４６】
これらは、次のような方法でＯＨラジカルを生成すると考えられる。
（Ａ）バナナの場合は次の化３、化４、化５となる。
【００４７】
【化３】

【００４８】
【化４】

【００４９】
【化５】

【００５０】
（Ｂ）リンゴの場合では次の化６となる。
【００５１】
【化６】

【００５２】
この化６ではエチルブチレート（Ｃ₂Ｈ₅ＣＯＯＣ₃Ｈ）と水から酢酸（ＣＨ₃ＣＯＯＣ₅Ｈ₁₁）が作られ、その酢酸からＯＨラジカルを生成して、含まれるエチレン（Ｃ₂Ｈ₄）にそのＯＨラジカルが反応しエタンと水に改質される。
しかし、その量はエチレンの発生量に比べて少ないので、本発明では確実に効果を得るために庫内に別途に酢酸などを注入する。
【００５３】
【試験例１】
酢酸を用いて、暗流発生装置を備えた容器中におけるエチレンの濃度とエタンの濃度を測定した実験をした。
その結果を表したものが図１３である。
この実験では、その容器中に連続的にエチレン（Ｃ₂Ｈ₄）を注入している。また、加湿器で容器内の湿度を上げた。
そして、
t＝１０分に電界用の電源を入れる。
t＝６０分に酢酸を水蒸気中に混ぜる。
t＝８５分に電界用の電源を切る。
【００５４】
この実験結果をまとめた図１３に示されているように、水蒸気中に電界を作用させる（１０＜t＜６０）と、ＯＨラジカルがわずかに生成されるために、エチレンの増加量が減少する。
酸を水蒸気に混ぜて電界を作用させる（６０＜t＜８５）と、ＯＨラジカルが大量に生成されるために、エチレンが減少する。
そして電界を「０」にする（t＞８５）と、再び、エチレンは増加量を始めることがわかる。
【００５５】
【発明の効果】
従来、大気圧下で暗流を多量に得ることは極めて困難であったが、本発明の暗流発生装置においては、通電する電極間に通電しない中継電極群を等間隔に配してコンパクト化が実現し、上記各試験の結果に示されるように、大気圧下でも低電圧で効果的に多量の暗流を発生させることが可能になった。
【００５６】
そして、その暗流発生装置を用いたエチレンガスの改質方法とその装置によって、暗流とカルボン酸から多量のＯＨラジカルを生成することにより、そのＯＨラジカルでエチレンガスをエタンと水に効率良く改質できるようになった。
【００５７】
これにより、庫内に保存される生鮮農産物から放出される鮮度保持に害のあるエチレンガスを暗流の作用で無害なエタンと水に効果的に改質して除去するための装置がコンパクト且つ低電圧にできるようになり、電力消費を少なく済ませられるとともに小型化が可能となった。
【００５８】
また、本発明ではオゾンを全く発生しないので当然独特のオゾン臭はなく、一般家庭用にも適した極めてコンパクトで、安全且つ経済的な生鮮農産物の鮮度保持用の保存庫としても利用できるようになった。
【図面の簡単な説明】
【図１】本発明の同心円配置方式の暗流発生装置の斜視図。
【図２】並列配置方式の暗流発生装置の斜視図。
【図３】電極体の形状と配置を示す要部の斜視図。
【図４】電極体が配置された電極配置板の表面の平面図。
【図５】電極体が配置された電極配置板の表面の間隔幅を示す平面図。
【図６】エチレンガスの改質装置の模式的縦断側面。
【図７】エチレンガスの改質装置の要部の模式的縦断側面。
【図８】電極配置板を多数設けた効率的暗流発生装置の斜視図。
【図９】図８の電極配置板面の電極の配置の状態を示す平面図。
【図１０】湿度とＯＨラジカルの発生の関係を示すグラフ図。
【図１１】周波数５００Ｈｚの電圧の変化によるエチレンガスの減少率を示すグラフ図。
【図１２】一定電圧での周波数によるエチレンガスの減少率を示すグラフ図。
【図１３】放電時と放電停止時のエチレンガスの減少率を示すグラフ図。
【符号の説明】
１ 電極配置板
１ａ 電極配置板の表面
１ｂ 電極配置板の裏面
２ 通電した電極
３ 通電した電極
４ 通電しない中継電極
５ 電源
６ 庫
７ 暗流発生装置
８ 送風手段
９ 注入手段
１０ 送風路
１１ 送風機
１１ａ ファン
１２ 通風路壁
１３ 通風孔
１４ 通気孔
１５ 放出ノズル
１６ 通電体
１６ａ 通電体
１６ｂ 通電体
１７ 同電極連接通電体
１８ タンク
１９ 通風路壁
２０ 暗流発生装置の箱
Ａ 電極体
ａ 電極体の極部
ｂ 電極体の脚部
Ｅ エチレンガス
Ｃ カルボン酸
ｅ エタン
ｗ 水[0001]
[Technical field to which the invention belongs]
The present invention relates to a dark current generator that efficiently generates a dark current under atmospheric pressure, and ethylene gas that is harmful to maintaining the freshness of fresh agricultural products released from the fresh agricultural products into the warehouse using the dark current generator. The present invention relates to a device for reforming water and a method for reforming ethylene gas using the dark current generator.
[0002]
[Prior art]
If fresh produce is left untreated, its freshness will decrease or it will rot.
In order to prevent this, fresh produce is put in a refrigerator and stored at a low temperature. However, even if the inside of the warehouse is cooled, the agricultural product releases ethylene gas that is harmful to the agricultural product, and the deterioration of freshness due to the gas cannot be prevented.
Therefore, in order to maintain the freshness of fresh produce over a long period of time, it is necessary to reduce the released ethylene gas from the inside as quickly as possible.
Therefore, for example, when trying to reduce the ethylene gas by discharging the generated ethylene gas to the outside of the warehouse, the air that has been cooled and cooled to a low temperature is also discharged to the outside of the warehouse and the temperature inside the warehouse rises. In order to return it to a low temperature again, it has to be cooled again, and there is a problem that power is consumed more by that amount.
[0003]
Therefore, in order to avoid such extra power consumption, the use of a gas adsorbent such as activated carbon capable of adsorbing and removing ethylene gas in the warehouse is often used.
However, if the gas adsorbent such as activated carbon continues to be used, the adsorption performance deteriorates and must be replaced with a new one as appropriate. This management is very troublesome.
Moreover, since activated carbon is sold as a product in a plastic container or the like, disposal of the used container for disposal may cause a secondary environmental problem.
[0004]
On the other hand, apart from such countermeasures against ethylene gas, arc discharge or spark discharge plasma is generated by applying a high voltage to the electrode, ozone is generated by the plasma, and the fresh food stored by the sterilizing power of the ozone is stored. There have been proposed methods and devices for eliminating the cause of corruption by killing various bacteria attached to agricultural products.
The freshness maintaining device for fresh produce by such a method is easy to use in that it can be easily carried out under atmospheric pressure, but on the other hand, it is a large-scale device because it generates ozone and uses a high voltage current. A lot of power consumption is required, and the maintenance cost of the apparatus becomes high. Furthermore, plasma emission and heat generation are caused by application of a high-voltage current, and the temperature inside the freezer or refrigerator to be cooled also rises.
[0005]
Furthermore, the generated ozone has the effect of disinfecting spoilage bacteria, but it causes a decoloration change of the food and makes the food look bad, and if it is generated in a large amount, it has an adverse effect on the human body. It is not preferable to use a simple ozone apparatus as it is as a storage for fresh produce for household use.
[0006]
Therefore, the inventor of the present application paid attention to the dark current generated at a relatively low voltage rather than the high voltage at which plasma for generating harmful ozone is generated.
It is known that the dark current that does not emit light is usually generated by applying a voltage that is considerably lower than the voltage that generates a spark discharge. The amount to be generated is extremely small, and it has been very difficult to generate efficiently, particularly under atmospheric pressure, which is a human sphere.
[0007]
[Problems to be solved by the invention]
The present invention has been made in order to solve the conventional difficulties, and provides a compact dark current generator capable of efficiently generating a large amount of dark current under atmospheric pressure. Provide a small, low-power, safe ethylene gas reforming device for maintaining the freshness of fresh produce in the plant over a long period of time, and from the fresh produce accumulated in the fresh food storage using the dark current generator Provided a method for reforming ethylene gas, which is harmful to maintaining freshness, to harmless ethane and water without generating ozone harmful to human body by OH radicals generated by dark current generated between electrodes It is.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the dark current generating apparatus of the present invention includes (a) a center electrode disposed at the center position of the circle, and (b) opposite to the center electrode on the outer circumference of the circle at a certain distance from the center electrode. An electrode group including a plurality of peripheral electrodes at the poles and (c) a plurality of relay electrodes insulated from the power source is formed between the central electrode and the peripheral electrodes.
And each electrode body of this electrode group is formed in a perfect circular cylinder shape, and it arranges so that the mutual interval of each electrode body may become equal intervals keeping the short distance between the electrode bodies which oppose To do.
Then, by applying a voltage having a value that can produce a dark current in an amount capable of generating OH radicals from carboxylic acid between the electrode groups, ethylene existing between the electrode groups by OH radicals generated from the injected carboxylic acid. It is set as the structure characterized by enabling it to decompose | disassemble.
[0009]
The invention described in claim 2 includes: (a) a plurality of positive electrodes disposed on one side; (b) a plurality of negative electrodes at a certain distance from the electrodes; and (c) the positive electrodes. An electrode group including a plurality of relay electrodes insulated from the power source is formed between the negative electrode and the negative electrode.
And like the invention of the said Claim 1, while forming each electrode body of this electrode group in a perfect circular cylinder shape, a spark discharge does not arise between the electrode bodies which mutually oppose the space | interval of each electrode body. It arrange | positions so that it may become equal intervals keeping a short distance.
Then, by applying a voltage having a value that can produce a dark current in an amount capable of generating OH radicals from carboxylic acid between the electrode groups, ethylene existing between the electrode groups by OH radicals generated from the injected carboxylic acid. It is set as the structure characterized by enabling it to decompose | disassemble.
[0010]
Further, according to a third aspect of the present invention, in the configuration of each of the above inventions, the electrode body used for the electrode is integrally formed with the small diameter leg portion on the large diameter electrode portion.
Then, the electrode body is placed on the electrode arrangement plate surface, the distance between the surfaces of the electrode portions facing each other is 0.3 mm or more, and the distance between the electrode arrangement plate surfaces of the leg portions is 3 mm or more. It arrange | positions so that it may become.
[0011]
Furthermore, the invention described in claim 4 uses a pulse voltage as a voltage applied between the electrodes in the configuration of each invention described above.
[0012]
An ethylene gas reforming device according to claim 5 is (A) a dark current generator according to any one of claims 1 to 4 installed in a warehouse and (B) a container. An injection means for injecting the carboxylic acid into the warehouse; and (C) a mixed gas of ethylene gas discharged from fresh produce stored in the warehouse and the injected carboxylic acid into the dark current generator. It is comprised with the ventilation means for spraying between each electrode body.
The ethylene gas contained therein can be reformed into ethane and water by OH radicals generated by spraying a carboxylic acid mixed gas onto the dark flow generator.
[0013]
The ethylene gas reforming method according to claim 5 includes: (A) a step of generating a dark current in the cabinet using the dark current generating device according to any one of claims 1 to 4; B) Injecting carboxylic acid into the warehouse and mixing it with ethylene gas released from fresh produce stored in the warehouse, and (C) blowing the mixed gas against the dark current to cause the A large amount of OH radicals are generated from an acid, and the ethylene gas is reformed into ethane and water by the OH radicals.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The inventor has repeated research and experiments so that dark current can be used even under atmospheric pressure, and has been able to create a compact device capable of effectively generating dark current.
And, by using the dark current generator, reforming of ethylene gas that can treat harmful ethylene gas released by fresh produce stored in the warehouse as harmless as possible with OH radicals A method and an ethylene gas reformer for carrying out the method were completed.
[0015]
Of these, a dark current generator capable of effectively generating dark current will be described in detail.
Regarding the arrangement of the electrodes using the electrode body, two different arrangement methods, concentric arrangement and parallel arrangement, are possible.
[0016]
First, the form of the concentric arrangement method will be described.
In this method, as shown in FIG. 1, (a) one positive or negative center electrode 2 disposed at the center position of a circle is disposed on the surface 1 a of the insulating circular electrode arrangement plate 1.
Then, (b) a plurality of peripheral electrodes 3 are disposed on the outer circumference of the circle at a certain distance from the center electrode 2 with the opposite poles to the center electrode 2.
Further, (c) a plurality of relay electrodes 4 that are insulated from the power source without being connected to the current-carrying member are disposed between the center electrode 2 and the peripheral electrode 3.
As an electrode used for these electrodes, an electrode body A in which a perfect circular cylindrical electrode part a is integrally formed on the leg part b is optimal.
Then, the leg portions b are fixed on the electrode arrangement plate 1 by making the intervals between the adjacent electrode bodies stand upright so that the distance between the surfaces of the electrode bodies facing each other is equal, keeping a short distance so that plasma is not induced.
And the voltage of the value which can obtain the dark current of the quantity which can produce | generate OH radical from carboxylic acid between this electrode group is applied.
[0017]
The arrangement of the electrode body A is generally such that when the surfaces of the opposing electrode portions are closer, a larger amount of dark current can be obtained with a lower voltage. When the distance between the surfaces is closer than 0.3 mm, spark discharge is likely to occur in the atmosphere and the generation of dark current is hindered.
Further, when the distance between the plate surfaces on the surface between the legs b is closer than 3 mm, creeping discharge is generated on the surface 1a even if the electrode arrangement plate is an insulator, and dark current is generated from the electrode portion a. Be inhibited.
Furthermore, if there is a place where the distance between the electrode parts a is closer than the others, concentrated discharge occurs there and the generation of dark current is inhibited, so that the electrode bodies are all equidistant.
In order to make them equidistant in this way, it is preferable that the pole center positions of the electrode bodies A are mutually apexes of equilateral triangles.
[0018]
Therefore, as shown in FIG. 5, the center positions of the polar parts of the electrode bodies A are the vertices of equilateral triangles, and the surfaces of the electrode parts a are equidistant from each other by 0.3 mm or more. The configuration according to claim 3, wherein the distance between the plate surfaces on the surface of b is 3 mm or more, and the opposing surfaces of the electrode portions a are upright so as to be equidistant in parallel.
Further, if there is a peripheral electrode 3 close to the center electrode 2, concentrated discharge to the electrode occurs, and in order to avoid this, the outer peripheral electrode 3 centering on the center electrode 2 should be arranged on the circle as much as possible. Should be placed.
[0019]
Then, the intensity of voltage spark discharge does not occur, i.e., possible voltage value amount of dark current is obtained which can produce OH radicals from the carboxylic acid between the center electrode 2 and the peripheral electrode 3 at the applied power 5 is installed and connected to the two electrodes 2 and 3 of the electrode body A to be energized through current-carrying bodies 16a and 16b such as electric wires.
[0020]
With respect to the voltage having a value capable of producing an amount of dark current capable of generating OH radicals from the carboxylic acid, for example, by a device that generates a pulse voltage having a frequency of about 500 Hz and a frequency of about 250 V, as described in claim 4. A dark current can be efficiently obtained with a low-voltage power supply.
Then, when such a low voltage is applied to the electrodes 2 and 3, as shown in FIG. 3, the relay electrodes 4 are relayed independently from each other without being connected to the current conductors 16a and 16b. As shown in FIG. 5, the dark current is dispersed throughout without being shifted to one place, and a large amount of dark current is generated.
[0021]
Next, a parallel arrangement system according to the second aspect of the present invention will be described.
As shown in FIG. 2, this method uses an electrode body A in which a perfect circular columnar electrode part a is integrally formed on a leg part b, on the surface 1 a of the insulating rectangular electrode arrangement plate 1. (A) A plurality of positive electrodes 2 disposed on one side is disposed.
Also, (b) a plurality of negative electrodes 3 arranged in parallel at a certain distance from the electrode 2 are provided.
(C) A plurality of relay electrodes 4 insulated from the power source are arranged between the positive electrode 2 and the negative electrode 3 columns.
[0022]
Then, the interval between adjacent electrode bodies is set upright so that the distance between adjacent surfaces of the electrode bodies 2, 3, and 4 is kept at an equal interval maintaining a short distance so that plasma is not generated. Secure on top.
And the voltage of the value which can obtain the dark current of the quantity which can produce | generate OH radical from carboxylic acid between this electrode group is applied.
[0023]
In the case of this form, for the same reason as the above form, the center positions of the respective electrode bodies A become the vertices of equilateral triangles, and the surfaces of the electrode parts a are equidistant from each other by 0.3 mm or more. A power supply that is arranged so that the distance between the plate surfaces of the part b is 3 mm or more, and can be applied with a voltage having a value that can generate a dark current in an amount capable of generating OH radicals from carboxylic acid between the opposing electrodes 2 and 3. 5 is installed and connected to both poles 2 and 3 through current-carrying bodies 16a and 16b such as electric wires.
[0024]
The electrode body A used for each of the electrodes 2, 3, 4 will be described in more detail. For example, as shown in FIG. 1, a columnar leg b having a small diameter for standing on the electrode arrangement plate 1 is provided. It is effective to use a rod-shaped electrode body A integrally formed with a cylindrical electrode portion a having a large diameter in order to increase the discharge capacity and effectively obtain a dark current.
[0025]
The electrode body A needs to be a perfect circular cylinder. The reason is that the dark current generated in the electrode is generated perpendicular to the smooth surface. However, a prism or a perfect sphere has a protruding portion close to the adjacent portion, and discharge is concentrated on that portion. If the partial concentrated discharge occurs, it becomes a spark discharge instead of a dark current, and the generation of the dark current is hindered.
In the electrode body of the present invention, since the circular cylindrical side surfaces are parallel to each other at equal distances, there is no concentrated discharge portion, and the dark current can be efficiently generated by being dispersed above and below the cylindrical side surfaces.
[0026]
The rod-shaped electrode body A is made of stainless steel that does not rust. The size of the rod-shaped electrode body A is, for example, as shown in FIG. 1, a total length of 20 mm, about 1/2 of which is a small-diameter leg b having a diameter of 3 mm. A large-diameter electrode portion a having a shape in which bars having different diameters of 5 mm are integrated is suitable for use.
And among such electrode bodies A erected on the electrode arrangement plate 1, the current bodies 16 a and 16 b are welded to the legs b of the electrode bodies A which are the electrodes 2 and 3 to be energized and connected to the power source 5. Let
[0027]
Next, an ethylene gas reforming apparatus using the dark current generating apparatus according to the invention described in claim 5 will be described.
In this apparatus, as shown in FIG. 6, the dark current generating device 7 is installed in a cabinet 6.
An injection means 9 having a discharge nozzle 15 for discharging the carboxylic acid C contained in the container into the storage 6 is provided.
As the injection means 9, an ultrasonic humidifier can be used, and the carboxylic acid C is put in supplementary water to be put in the tank 18 of the humidifier.
The carboxylic acid C is specifically acetic acid, formic acid, oxalic acid, propionic acid, etc., and among them, the most suitable one is acetic acid.
Then, when carboxylic acid C such as acetic acid is injected into the storage 6 by the injection means 9, it is mixed with ethylene gas E released from the fresh agricultural products stored in the storage 6.
[0028]
Further, a blowing means 8 for blowing gas toward the groups 2, 3 and 4 of the dark current generating device 7 is provided.
For example, as shown in FIG. 6, the air blowing means 8 is suitably equipped with a blower 11 so that the fan 11 a can be directed between the electrodes 2, 3, and 4 groups on the surface 1 a of the electrode arrangement plate 1. ing.
By this blowing means 8, a mixed gas of ethylene gas E and carboxylic acid C is blown into the cabinet 6.
[0029]
When an upper limit voltage that does not generate spark discharge under atmospheric pressure is applied to the electrodes 2 and 3 of the dark current generator 7, a large amount of dark current is generated between the relay electrodes 4 that are not energized.
Further, depending on the scale of the dark current generating device 7, as shown in FIGS. 8 and 9, a plurality of electrode arrangement plates 1 arranged in a box 20 to increase the dark current generating ability can be used.
In addition, the optimum voltage applied between the energized electrodes 2 and 3 for generating a dark current at atmospheric pressure by this method varies depending on the scale, and in order to save power consumption, the application is continuously performed by a pulse voltage or the like. Or it is good to continue intermittently.
[0030]
As shown in FIGS. 6 and 7, in order to obtain a gas flow from the front surface 1 a to the back surface 1 b of the electrode arrangement plate 1, a ventilation hole penetrating the electrode arrangement plate 1 between the electrodes 2, 3, 4. If 14 is provided, the flow of gas can be made smooth.
The reformed gas that has escaped from the vent hole 14 passes through the vent path surrounded by the vent path walls 12 and 19 and circulates again into the cabinet from the vent hole 13 provided on the side surface.
Thereby, a large amount of OH radicals are generated from the carboxylic acid C blown from the blower 11 against the dark current generated in the electrode group by voltage application, and from fresh agricultural products such as ethylene, ammonia, and methane blown by the OH radicals. The generated harmful organic gas is effectively reformed into ethane e and water w.
[0031]
Next, an ethylene gas reforming method using the above dark current generator according to the invention described in claim 6 will be described.
In this reforming method, first, a large amount of dark current is generated in the warehouse using the dark current generator.
And carboxylic acid is inject | poured in a warehouse and it is made to mix with the ethylene gas discharge | released from the fresh agricultural product preserve | saved in the warehouse.
Further, when the mixed gas is blown against the dark current, a large amount of OH radicals are generated from the carboxylic acid by the dark current.
The ethylene gas is instantly reformed into ethane and water by the action of the generated OH radicals.
[0032]
[Action]
When a low voltage that causes dark current to be applied to the electrodes 2 and 3 that are energized to the power source 5 is applied to the dark current generator, OH radicals are generated from carboxylic acid such as acetic acid by the generated dark current. Ethylene is modified by OH radicals.
This principle will be described below.
This reaction is considered to be due to the reactions in the following stages (1) and (2).
[0033]
First, in step (1), in order to generate OH radicals, it is necessary to give energy to acetic acid and separate the OH part of the molecule.
[0034]
Therefore, OH is separated by colliding high energy electrons with a gas (acetic acid) containing an OH component.
As a feature of this device, high-energy electrons accelerate low-energy electrons that form a dark current with a strong electric field between the electrodes (the distance between the electrodes is very short, for example, 0.3 mm to make a strong electric field at a low voltage), It is generated by storing energy by elastic collision with many nitrogen molecules in the gas in the chamber, and the high energy electrons collide with acetic acid, and radicals are generated by dissociating OH.
[0035]
If the acceleration electric field is too strong, the collision effect between electrons and nitrogen molecules decreases, and the generation rate of electrons decreases, so that OH radicals decrease.
Further, the generation rate of OH radicals is proportional to humidity. This is shown in the graph of FIG. 10 which shows experimental data with the apparatus of FIG. FIG. 10 shows a state in which OH radicals increase to the peak point as the humidity increases and decrease thereafter.
Also, the generation of OH radicals is proportional to the frequency of the electric field (applied voltage), but if the frequency is too high, current tends to flow and conducts between the electrodes, leading to a reduction in gas dissociation efficiency.
[0036]
This is shown in FIG. 11 of experimental data in which the reduction rate of C ₂ H _{4 in} the apparatus of FIG. 6 was examined. FIG. 11 shows a state in which C ₂ H ₄ decreases to the peak point as the humidity increases, and no longer decreases after that.
When the applied voltage is 125 V at a humidity of 85%, the reduction rate of C ₂ H ₄ increases as the frequency increases up to a certain point, and the reduction rate does not change beyond that (FIG. 12). To show).
[0037]
On the other hand, if the humidity is too high, the insulation between the electrodes decreases, the electric field strength decreases, and the acceleration energy of electrons decreases.
Therefore, the following can be considered.
The following chemical formula 1 is a process in which accelerating electrons collide with acetic acid to generate OH radicals.
[0038]
[Chemical 1]

[0039]
As shown in this chemical formula, when accelerated electrons e collide with acetic acid, OH radicals are generated.
[0040]
As described above, when accelerating electrons collide with acetic acid to generate OH radicals, a reaction with ethylene occurs next as step (2).
The mechanism by which the OH radical and C ₂ H ₄ react at that time is represented by the following chemical formula 2.
[0041]
[Chemical formula 2]

[0042]
As shown in this chemical formula 2, OH radicals react with ethylene (C ₂ H ₄ ) to be reformed into ethane and water. That is, ethylene is reduced by OH radicals.
Since the reaction in the above steps (1) and (2) occurs instantaneously, it can be experimentally confirmed by the ethylene concentration before and after the reaction.
[0043]
Next, an example of banana and apple will be explained.
It releases ethylene from bananas and apples, but also releases the following:
[0044]
<Substances released from bananas>
An amyl ester with a fruity fragrance (highly polarizable)
Acetic acid CH ₃ COOC ₅ H ₁₁
Butyric acid C ₃ H ₇ COOC ₅ H ₁₁
Propionic acid C ₂ H ₅ COOC ₅ H ₁₁
Ripeness-like scented component phenol ether eugenol eugenol methyl ether elemicin [0045]
<Materials released from apples>
The center of fragrance: fresh blue and sweetness hexanol C ₆ H ₁₃ OH
Hexanal trans-2-hexanal sweetness and maturity (esters)
Ethyl butyrate C ₂ H ₅ COOC ₃ H ₅
Butyl acetate butyl butyrate [0046]
These are considered to generate OH radicals by the following method.
(A) In the case of a banana, the following chemical formula 3, chemical formula 4, and chemical formula 5 are obtained.
[0047]
[Chemical 3]

[0048]
[Formula 4]

[0049]
[Chemical formula 5]

[0050]
(B) In the case of an apple, the following chemical formula 6 is obtained.
[0051]
[Chemical 6]

[0052]
In this chemical formula 6, acetic acid (CH ₃ COOC ₅ H ₁₁ ) is made from ethyl butyrate (C ₂ H ₅ COOC ₃ H) and water, OH radicals are generated from the acetic acid, and the contained ethylene (C ₂ H ₄ ) Reacts with the OH radical to be modified into ethane and water.
However, since the amount thereof is smaller than the amount of ethylene generated, acetic acid or the like is separately injected into the chamber in order to obtain the effect with certainty in the present invention.
[0053]
[Test Example 1]
An experiment was conducted in which acetic acid was used to measure the ethylene and ethane concentrations in a vessel equipped with a dark current generator.
FIG. 13 shows the result.
In this experiment, ethylene (C ₂ H ₄ ) is continuously injected into the container. Moreover, the humidity in the container was raised with a humidifier.
And
Turn on the power for the electric field at t = 10 minutes.
At t = 60 minutes, acetic acid is mixed into the steam.
Turn off the electric field power at t = 85 minutes.
[0054]
As shown in FIG. 13 that summarizes the results of this experiment, when an electric field is applied in water vapor (10 <t <60), the amount of increase in ethylene decreases because OH radicals are slightly generated. .
When an electric field is applied by mixing an acid with water vapor (60 <t <85), a large amount of OH radicals are generated, and ethylene is reduced.
When the electric field is set to “0” (t> 85), it can be seen that ethylene starts increasing again.
[0055]
【The invention's effect】
Conventionally, it has been extremely difficult to obtain a large amount of dark current under atmospheric pressure, but the dark current generator of the present invention realizes compactness by arranging relay electrodes that are not energized between energized electrodes at equal intervals. As shown in the results of the above tests, a large amount of dark current can be effectively generated at a low voltage even under atmospheric pressure.
[0056]
And by the ethylene gas reforming method using the dark flow generator and the device, a large amount of OH radicals are generated from the dark flow and carboxylic acid, and the ethylene gas is efficiently reformed into ethane and water by the OH radicals. I can do it now.
[0057]
As a result, the apparatus for effectively modifying and removing ethylene gas, which is harmful to the preservation of freshness released from fresh produce stored in the warehouse, into harmless ethane and water by the action of dark current, is compact and low. It has become possible to use a voltage, which can reduce power consumption and reduce the size.
[0058]
Further, in the present invention, since ozone is not generated at all, there is naturally no unique ozone odor, so that it can be used as a storage container for keeping freshness of fresh produce that is extremely compact and safe and suitable for general household use. became.
[Brief description of the drawings]
FIG. 1 is a perspective view of a concentric arrangement type dark current generator of the present invention.
FIG. 2 is a perspective view of a parallel flow type dark current generator.
FIG. 3 is a perspective view of a main part showing the shape and arrangement of an electrode body.
FIG. 4 is a plan view of the surface of an electrode arrangement plate on which electrode bodies are arranged.
FIG. 5 is a plan view showing the interval width of the surface of the electrode arrangement plate on which the electrode body is arranged.
FIG. 6 is a schematic longitudinal side view of an ethylene gas reformer.
FIG. 7 is a schematic vertical side view of the main part of an ethylene gas reforming apparatus.
FIG. 8 is a perspective view of an efficient dark current generator provided with a large number of electrode arrangement plates.
9 is a plan view showing a state of electrode arrangement on the electrode arrangement plate surface of FIG. 8. FIG.
FIG. 10 is a graph showing the relationship between humidity and generation of OH radicals.
FIG. 11 is a graph showing a decrease rate of ethylene gas due to a change in voltage at a frequency of 500 Hz.
FIG. 12 is a graph showing a decrease rate of ethylene gas with a frequency at a constant voltage.
FIG. 13 is a graph showing a reduction rate of ethylene gas when discharging and when discharging is stopped.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Electrode arrangement | positioning board 1a The surface 1b of an electrode arrangement | positioning board 2 The back surface of an electrode arrangement board 2 The energized electrode 3 The energized electrode 4 The non-energized relay electrode 5 Power supply 6 Warehouse 7 Dark flow generator 8 Blowing means 9 Injecting means 10 Blower path 11 Blower 11a Fan 12 Ventilation channel wall 13 Ventilation hole 14 Ventilation hole 15 Discharge nozzle 16 Electric conduction body 16a Electric conduction body 16b Electric conduction body 17 Same electrode connection electric conduction body 18 Tank 19 Ventilation passage wall 20 Dark flow generator box A Electrode body a Electrode part b of electrode body Electrode leg E Ethylene gas C Carboxylic acid e Ethane w Water

Claims (6)

(A) a central electrode disposed at a circular center position, (b) a plurality of peripheral electrodes on the outer periphery of the circle at a certain distance from the central electrode and opposite to the central electrode, and (c) the central electrode and the peripheral edge An electrode group consisting of a plurality of relay electrodes insulated from the power source is formed between the electrodes,
Each electrode body of the electrode group is formed in a perfect circular cylindrical shape, and the mutual distance between the electrode bodies is arranged at equal intervals keeping a short distance between the opposing electrode bodies,
By applying a voltage having a value that can generate a dark current in an amount capable of generating OH radicals from carboxylic acid between the electrode groups, ethylene existing between the electrode groups is decomposed by OH radicals generated from the injected carboxylic acid. A dark current generator characterized in that it can be used. (A) a plurality of positive electrodes disposed on one side; (b) a plurality of negative electrodes at a certain distance from the electrodes; and (c) a power source insulated between the positive electrodes and the negative electrodes. Forming an electrode group consisting of a plurality of relay electrodes,
Each electrode body of the electrode group is formed in a perfect circular cylindrical shape, and the mutual distance between the electrode bodies is arranged at equal intervals keeping a short distance between the opposing electrode bodies,
By applying a voltage having a value that can generate a dark current in an amount capable of generating OH radicals from carboxylic acid between the electrode groups, ethylene existing between the electrode groups is decomposed by OH radicals generated from the injected carboxylic acid. A dark current generator characterized in that it can be used. The electrode body used for the electrode is formed by integrally forming a small-diameter leg portion on a large-diameter electrode portion, and the distance between the surfaces of the electrode portions facing each other adjacent to each other on the electrode arrangement plate surface is 0. The dark current generator according to claim 1 or 2, wherein the electrode body is arranged so that the distance between the electrode arrangement plate surfaces of the legs is 3 mm or more at 3 mm or more. The dark current generator according to any one of claims 1 to 3, wherein the voltage to be applied is a pulse voltage. (A) The dark current generator according to any one of claims 1 to 4 installed in a warehouse;
(B) injection means for injecting the carboxylic acid contained in the container into the chamber;
(C) It comprises air blowing means for blowing a mixed gas of ethylene gas released from the fresh produce stored in the warehouse and the injected carboxylic acid between each electrode body of the dark current generator,
An ethylene gas reforming apparatus characterized in that the ethylene gas contained therein can be reformed into ethane and water by OH radicals generated by spraying a carboxylic acid mixed gas onto the dark flow generator. (A) a step of generating a dark current in the warehouse using the dark current generating device according to any one of claims 1 to 4, and
(B) a step of injecting carboxylic acid into the warehouse and mixing it with ethylene gas released from fresh produce stored in the warehouse;
(C) blowing the mixed gas against a dark stream to generate a large amount of OH radicals from the carboxylic acid by the dark stream, and reforming ethylene gas to ethane and water by the OH radicals;
A method for reforming ethylene gas with OH radicals.

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