JP3155037B2 - How to keep fruits and vegetables fresh - Google Patents
How to keep fruits and vegetables freshInfo
- Publication number
- JP3155037B2 JP3155037B2 JP26272691A JP26272691A JP3155037B2 JP 3155037 B2 JP3155037 B2 JP 3155037B2 JP 26272691 A JP26272691 A JP 26272691A JP 26272691 A JP26272691 A JP 26272691A JP 3155037 B2 JP3155037 B2 JP 3155037B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- honeycomb
- palladium chloride
- gas
- impregnated
- 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.)
- Expired - Fee Related
Links
- 235000012055 fruits and vegetables Nutrition 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 155
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 239000005977 Ethylene Substances 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000004913 activation Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940062057 nitrogen 80 % Drugs 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BHZSLLSDZFAPFH-UHFFFAOYSA-L palladium(2+);difluoride Chemical compound F[Pd]F BHZSLLSDZFAPFH-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩化パラジウムを添着BACKGROUND OF THE INVENTION 1. Field of the Invention
したハニカム状活性炭及びその活性炭を使用した、青果Fruits and vegetables using dried honeycomb-shaped activated carbon and the activated carbon
物の鮮度保持方法に関するもので、更に詳しく述べるIt relates to the method of maintaining the freshness of an article
と、酸化触媒性を有する塩化パラジウムを添着したハニAnd palladium chloride impregnated with oxidation catalyst
カム状活性炭及び、その活性炭を使用してエチレンを酸Cam-like activated carbon and the use of activated carbon to acidify ethylene
化除去するために使用する方法であり、更に青果物の鮮This method is used to remove
度保持方法である。This is the degree holding method.
【０００２】[0002]
【従来の技術】活性炭に塩化パラジウムを担持したもの
を触媒として使用し、エチレンを酸化する反応はよく知
られているが、それらは粉末状や粒状の活性炭を担体と
する場合が殆どであった（日本化学会誌 1972, p 1092
〜1097、特公昭60- 10776 、特開昭56-55147）。本出願
人は先に塩化パラジウムを添着した活性炭について出願
したが（特公昭60-10776、特開昭56-55147）、これらは
塩化パラジウムを担持する活性炭が粒状であるため、小
袋に入れるかまたはカラムに充填して使用する外はなか
った。この様な方法で使用する場合には圧損失が高くな
ったり、またはガスを高速で通過させることが困難であ
る等の問題があった。2. Description of the Related Art The reaction of oxidizing ethylene by using palladium chloride supported on activated carbon as a catalyst is well known, but most of them use powdered or granular activated carbon as a carrier. (Journal of the Chemical Society of Japan 1972, p 1092
-1097, JP-B-60-10776, JP-A-56-55147). Although applicants filed on activated carbon impregnated with previously palladium chloride (Akira Japanese public 60-10776, JP 56-55147), or they are for activated carbon carrying palladium chloride is a granular, placed in a pouch Or, there was no use out of packing the column. When used in such a method, there have been problems such as a high pressure loss and difficulty in passing gas at high speed.
【０００３】また、従来からあるハニカム状の活性炭に
塩化パラジウムを添着するという方法では、担体となる
ハニカム状活性炭の強度が小さく、比表面積が小さいた
め塩化パラジウムの添着量を多くする事が困難で、高活
性の塩化パラジウム担持活性炭は得られなかった。Further, in the conventional method of impregnating palladium chloride on honeycomb-shaped activated carbon, it is difficult to increase the amount of palladium chloride impregnated because the strength of the honeycomb-shaped activated carbon serving as a carrier is small and the specific surface area is small. No highly active palladium chloride-supported activated carbon was obtained.
【０００４】例えば、室内用の空気清浄器や、鮮度保持
ボックス等においてフィルターとして使用する場合、従
来からある粒状の活性炭に塩化パラジウムを添着したも
のでは不適当であった。それは活性炭をカラムや容器に
充填して使用する方法では、圧損失が高くガスを高速で
通過させることが困難であったからである。For example, when used as a filter in an indoor air purifier, a freshness keeping box, or the like, a conventional granular activated carbon impregnated with palladium chloride is not suitable. This is because, in the method of using activated carbon by filling it in a column or a container, pressure loss is high and it is difficult to pass gas at high speed.
【０００５】従って、この様なフィルターとして使用す[0005] Therefore, such a filter is used.
る場合エチレンを除去するために、酸化触媒として高性High efficiency as an oxidation catalyst to remove ethylene
能で且つ圧損失が低いハニカム状塩化パラジウム添着活Activated Honeycomb with Low Pressure Loss
性炭が求められていた。Sex charcoal was required.
【０００６】[0006]
【発明が解決しようとする課題】本発明は前述の問題点SUMMARY OF THE INVENTION The present invention has the above-mentioned problems.
に鑑み、低温で希薄なエチレンガスを除去するためガスIn order to remove dilute ethylene gas at low temperatures,
を高速で酸化触媒中を通過させても充分に除去出来る様Can be sufficiently removed even when passing through the oxidation catalyst at high speed
な、圧損失が低く、触媒性が高い塩化パラジウム添着活Palladium chloride impregnation with low pressure loss and high catalytic properties
性炭及びそれを使用した、鮮度保持ボックス中の青果物Sexual Charcoal and Fruits and Vegetables in Freshness Preservation Box Using It
の鮮度保持方法を提供しようとするものである。It is an object of the present invention to provide a method for maintaining freshness.
【０００７】[0007]
【課題を解決するための手段】本発明者は低温で希薄なSUMMARY OF THE INVENTION The inventor of the present invention has developed a low-temperature
エチレンガスを除去するため、例えば青果物の鮮度保持To remove ethylene gas, for example, to keep fruits and vegetables fresh
ボックス等において使用出来る、圧損失が低く触媒性がCan be used in boxes, etc., with low pressure loss and low catalytic properties
優れた塩化パラジウムを担持させるハニカム状活性炭にExcellent honeycomb-like activated carbon supporting palladium chloride
ついて、種々検討した。その結果、特定のプロセスを経Various investigations were made. As a result, certain processes
て作られたハニカム状活性炭により、０〜40℃で10ppm 10ppm at 0-40 ° C by honeycomb-shaped activated carbon
程度の低濃度のエチレンが、充分に酸化除去出来る極めExtremely low concentration of ethylene can be sufficiently oxidized and removed
て高活性な塩化パラジウム添着ハニカム状活性炭が得らAnd highly active palladium chloride impregnated honeycomb activated carbon
れることを見出し、これに基づいて本発明に到達した。And found the present invention based on this.
【０００８】すなわち、石炭をタールをバインダーとし
てセル数が 250〜800 セル/ inch2 のハニカム状に成型
して炭化し、水蒸気含有率15容量％以下の雰囲気で賦し
た後、そのままの雰囲気で300 ℃以下まで冷却し、塩化
パラジウムを 0.1〜10重量％（以下、重量％の重量を省
略する）担持せしめた活性炭或いはまた、石炭の炭化物
よりタールをバインダーとして成型されたセル数が 250
〜800 セル/inch2の通常のハニカム状活性炭を、実質的
に酸素または/ 及び水蒸気を含まない窒素ガスまたは/
及び炭酸ガス中で 500℃以上で処理した後、そのままの
雰囲気中で300 ℃以下まで冷却し、更に塩化パラジウム
を 0.1〜10％担持せしめた活性炭を使用することを特徴
とする、青果物の鮮度保持方法である。That is, coal is formed into a honeycomb shape having a cell number of 250 to 800 cells / inch 2 by using tar as a binder and carbonized, and is applied in an atmosphere having a water vapor content of 15% by volume or less. Activated carbon loaded with 0.1 to 10% by weight of palladium chloride (hereinafter, weight% is omitted).
~ 800 cells / inch 2 of ordinary honeycomb activated carbon is converted into nitrogen gas or /
And after treatment with 5 00 ° C. or more carbon gas, and cooled to 300 ° C. or less in as atmosphere, characterized by the use of more active carbon was allowed palladium chloride 0.1 to 10% fruit or vegetable freshness It is a holding method.
【０００９】ここで「通常のハニカム状活性炭」とは常Here, "ordinary honeycomb activated carbon" is always used.
法で得られた、エチレンガスの酸化触媒性が低いハニカHas low oxidation catalytic activity of ethylene gas
ム状活性炭或いは、本発明によって得られたエチレンガActivated carbon or ethylene gas obtained by the present invention
スの酸化触媒性が高いハニカム状活性炭を使用したためUse of honeycomb activated carbon with high oxidation catalytic properties
に触媒性が低下したハニカム状活性炭である。また、This is a honeycomb-shaped activated carbon having reduced catalytic activity. Also,
「実質的に酸素又は／及び水蒸気を含まない」とは、賦"Substantially free of oxygen and / or water vapor" means
活後の活性炭の熱処理において活性炭表面に結合した酸Acids bound to activated carbon surface during heat treatment of activated carbon after activation.
素原子が存在しないような雰囲気の意味で、酸素及び水Oxygen and water in an atmosphere in which elemental atoms do not exist
蒸気が１〜２％以下の状態をいう。It refers to a state in which steam is 1 to 2% or less.
【００１０】以下本発明について詳しく説明する。Hereinafter, the present invention will be described in detail.
【００１１】本発明において用いられるハニカム状活性[0011] Honeycomb-like activity used in the present invention
炭は炭素質原料として石炭を使用する必要がある。まCoal needs to use coal as a carbonaceous raw material. Ma
た、バインダーとしてはタールを使用する必要がある。In addition, it is necessary to use tar as a binder.
通常は粉末状の石炭にタールを加えてハニカム状に成型Usually, tar is added to powdered coal and formed into a honeycomb shape
した後、炭化し、本発明の方法で賦活することにより得And then carbonized and obtained by activating with the method of the present invention.
られる。この様な組成のハニカム状活性炭は硬質で摩擦Can be Honeycomb-like activated carbon with such a composition is hard and frictional
による粉塵が発生しにくいメリットがある。There is a merit that dust is less likely to be generated.
【００１２】この際賦活ガスは水蒸気の他、二酸化炭素
ガスを含むが、水蒸気含有率は15％以下とする必要があ
る。通常使用されている活性炭賦活用ガスの組成は水蒸
気40〜60％で、それより高い場合も多い。水蒸気による
炭素質の賦活速度は二酸化炭素ガスよりかなり速いた
め、賦活ガスの組成は水蒸気分圧がなるべく高くなる様
に設定されている。従って本発明の条件は、常法に較べ
て著しく賦活速度を遅くしたマイルドな条件になってい
る。実施例16及び比較例８〜10、表５に示すように水蒸
気含有率が高い条件下で賦活された場合は、明らかにエ
チレンの酸化触媒性が低下していることが分かる。水蒸
気含有率が低い賦活条件が活性炭の酸化触媒能を向上さ
せる機構の詳細は明らかでないが、かかる条件下で得ら
れたハニカム状活性炭は、その表面に結合した酸素原子
が存在しない状態になっていることが指摘されている。At this time, the activation gas contains carbon dioxide gas in addition to water vapor, and the water vapor content must be 15% or less. The composition of activated carbon utilization gas that is usually used is 40 to 60% of water vapor, and is often higher than that. Since the activation rate of carbonaceous material by steam is considerably higher than that of carbon dioxide gas, the composition of the activation gas is set so that the partial pressure of steam becomes as high as possible. Therefore, the condition of the present invention is a mild condition in which the activation rate is remarkably slowed down as compared with the ordinary method. As shown in Example 16 and Comparative Examples 8 to 10 and Table 5 , when activated under the condition that the water vapor content is high, it is apparent that the oxidation catalytic activity of ethylene is clearly lowered. The details of the mechanism by which the activation condition with a low water vapor content enhances the oxidation catalytic ability of the activated carbon are not clear, but the honeycomb-shaped activated carbon obtained under such conditions is in a state where there is no oxygen atom bonded to its surface. It is pointed out that
【００１３】本発明の活性炭の比表面積は 500m2/g以上
であることが好ましく、800m2/g 以上になればより好ま
しい。ハニカム活性炭の比表面積及びセル数と酸化触媒
性の関係は実施例４〜11及び表２に示す様にエチレンに
対して比表面積が大きい程触媒性が高くなることが分か
る。また、セル数が多い程触媒性が高くなる傾向を示す
がセル数が多くなり過ぎると、充填比重が低下するため
却って触媒性が低下する傾向がある。The specific surface area of the activated carbon of the present invention is preferably at least 500 m 2 / g, more preferably at least 800 m 2 / g. As shown in Examples 4 to 11 and Table 2 , the relationship between the specific surface area and the number of cells of the honeycomb activated carbon and the oxidation catalytic property indicates that the larger the specific surface area with respect to ethylene, the higher the catalytic property. In addition , the larger the number of cells, the higher the catalytic property tends to be. However, if the number of cells is too large, the specific gravity of the packing decreases, so that the catalytic property tends to decrease.
【００１４】通常のハニカム状活性炭は、ハニカム状に
成型した炭素質原料を水蒸気、燃焼ガス等で賦活するこ
とにより製造されているが、かかる活性炭を本発明に使
用しても、充分な酸化触媒性を示さない。本発明の効果
は前述の様な特定の組成のガスで賦活された、ハニカム
状活性炭を用いることによって初めて得られるものであ
る。[0014] Ordinary honeycomb activated carbon is produced by activating a carbonaceous raw material formed into a honeycomb shape with steam, combustion gas or the like. Even if such activated carbon is used in the present invention, a sufficient oxidation catalyst can be obtained. Does not show sex. The effects of the present invention can be obtained for the first time by using a honeycomb activated carbon activated by a gas having a specific composition as described above.
【００１５】この様にして得られた活性炭に塩化パラジThe activated carbon thus obtained is treated with palladium chloride.
ウムを添着すれば、エチレンを速やかに酸化する強い触A strong touch that oxidizes ethylene quickly
媒性を示す。しかし、本発明の賦活されたハニカム状活Shows medium properties. However, the honeycomb-shaped active material of the present invention is activated.
性炭を高温のまま系外へ取り出し、水蒸気、水素ガス、The hot coal is taken out of the system at high temperature, and steam, hydrogen gas,
あるいは酸素ガスを多量に含む雰囲気中に放置すれば、Alternatively, if left in an atmosphere containing a large amount of oxygen gas,
酸化触媒としての能力が著しく低下する。The ability as an oxidation catalyst is significantly reduced.
【００１６】賦活後においても賦活ガスと同様のガスの
もとで活性炭を温度300 ℃以下に冷却し、その後系外に
取り出すことが必要である。冷却時の雰囲気は賦活時に
用いられる窒素ガス、炭酸ガスまたはこれらの混合ガス
（酸素、水素、水蒸気の含有量は規定量以下）の雰囲気
であればよく、賦活に用いるガスと冷却に用いるガスと
は必ずしも同一組成のものでなくてもよい。本発明にお
いて「そのままの雰囲気で冷却」するとは前記の様な意
味である。[0016] Even after activation, it is necessary to cool the activated carbon to a temperature of 300 ° C or lower under the same gas as the activation gas, and then take it out of the system. The atmosphere at the time of cooling may be an atmosphere of nitrogen gas, carbon dioxide gas or a mixed gas thereof (the content of oxygen, hydrogen and water vapor is equal to or less than a prescribed amount) used at the time of activation. Need not necessarily have the same composition. In the present invention, “cooling in the same atmosphere” has the same meaning as described above.
【００１７】賦活後の活性炭を300 ℃以上で空気中に取
り出すと、低温低濃度における酸化触媒としての能力が
著しく低下する。賦活後窒素ガス中で冷却した場合と、
空気中で冷却した場合の触媒性に及ぼす影響を、実施例
12、13、比較例４、５及び表３に示す。また賦活後活性
炭が空気に触れる温度が触媒性に及ぼす影響について
は、実施例14、15、比較例６、７及び表４に示す。When the activated carbon after activation is taken out into the air at 300 ° C. or higher, the ability as an oxidation catalyst at low temperature and low concentration is significantly reduced. When cooled in nitrogen gas after activation,
The effects of cooling in air on the catalytic properties
12, 13, Comparative Examples 4 and 5, and Table 3 . The effects of the temperature at which the activated carbon comes into contact with air after activation on the catalytic properties are shown in Examples 14 and 15 , Comparative Examples 6 and 7, and Table 4 .
【００１８】更に本発明においては、空気などに触れて
表面が酸化され酸化触媒性が低下した廃ハニカム状活性
炭或いは、常法により製造されたセル数 250/inch2のハ
ニカム状活性炭を前述の賦活ガスと同組成のガス中で、
温度500 ℃以上で処理し、該ガス中で温度300 ℃以下に
冷却することにより得られるハニカム状活性炭も、前述
のハニカム状活性炭と同様に、エチレンガスに対する高
い酸化触媒性を示している。換言すれば、この熱処理に
よってハニカム状活性炭に高い酸化触媒能が付与され
る。[0018] In addition, the present invention, the waste honeycomb activated carbon surface touching the like is oxidized oxidizing catalytic decreased air or by a conventional method of cell number 2 50 / inch 2 manufactured honeycomb activated carbon described above In a gas of the same composition as the activation gas,
Honeycomb activated carbon obtained by treating at a temperature of 500 ° C. or higher and cooling to a temperature of 300 ° C. or lower in the gas also exhibits high oxidation catalytic activity against ethylene gas, similarly to the above-mentioned honeycomb activated carbon. In other words, the heat treatment imparts a high oxidation catalytic activity to the honeycomb activated carbon.
【００１９】通常の方法で得られたハニカム状活性炭はThe honeycomb activated carbon obtained by the usual method is
いずれもこの方法で処理することにより、本発明の酸化In any case, the oxidation of the present invention
触媒として適用可能なハニカム状活性炭が得られる。処A honeycomb-like activated carbon applicable as a catalyst is obtained. place
理温度は 500℃以上とする必要がある。処理時間は温度The processing temperature must be 500 ° C or higher. Processing time is temperature
によって変わるが、500 ℃の場合は通常、20〜180 分が20 to 180 minutes at 500 ° C
好ましく、800 ℃では数分の処理によって充分その効果Preferably, at 800 ° C, a few minutes treatment is sufficient
が得られる。Is obtained.
【００２０】本発明のハニカム状活性炭には塩化パラジ
ウムを0.1 〜10％添着させる必要がある。活性炭に塩化
パラジウムを添着するには、塩酸濃度が0.1 〜３規定、
好ましくは0.5 〜１規定の塩酸水溶液に所定量の塩化パ
ラジウムを溶解し、この溶液にハニカム状活性炭を入れ
て攪拌し、塩化パラジウムを充分吸着させた後、液切り
し、200 ℃で乾燥する。塩化パラジウムの担持量は0.1
〜10％とする必要があるが、担持量が0.5 〜２％の場合
がより好ましい。The honeycomb activated carbon of the present invention needs to be impregnated with 0.1 to 10% of palladium chloride. To impregnate palladium chloride on activated carbon, the concentration of hydrochloric acid is 0.1 to 3N,
Preferably, a predetermined amount of palladium chloride is dissolved in a 0.5 to 1N aqueous hydrochloric acid solution, honeycomb activated carbon is added to the solution, and the mixture is stirred. After sufficient adsorption of palladium chloride, the solution is drained and dried at 200 ° C. The loading amount of palladium chloride is 0.1
It is necessary to set the amount to be supported to 0.5 to 2%.
【００２１】塩化パラジウムの担持量が0.1 ％以下の場
合は触媒活性が不充分であり、また10％以上になると添
着量が多いわりに触媒性が向上せず、またパラジウムが
高価であるためその経済性も考慮すれば、添着量は10％
以下とする必要がある。塩化パラジウムの担持量の調節
は、塩酸水溶液中の塩化パラジウムの量とハニカム活性
炭の量との比を変更する事により行われる。通常、溶液
中の塩化パラジウムはほぼ完全に活性炭に吸着される。When the supported amount of palladium chloride is 0.1% or less, the catalytic activity is insufficient, and when it is 10% or more, the catalytic performance is not improved due to the large amount of impregnation, and the cost of palladium is high. Considering the nature, the amount of impregnation is 10%
It is necessary to: Adjustment of the supported amount of palladium chloride is performed by changing the ratio of the amount of palladium chloride in the aqueous hydrochloric acid solution to the amount of honeycomb activated carbon. Usually, the palladium chloride in the solution is almost completely adsorbed on the activated carbon.
【００２２】本発明のハニカム状塩化パラジウム添着活The honeycomb-shaped palladium chloride-impregnated activation of the present invention
性炭は、ハニカム状のため圧損失が極めて低く、また常The pressure loss of charcoal is extremely low due to its honeycomb shape.
温あるいは低温においても酸化触媒として高い機能を有Highly functional as an oxidation catalyst even at high or low temperatures
するため、鮮度保持ボックス中の青果物の鮮度保持用にTo preserve the freshness of fruits and vegetables in the freshness keeping box
優れている。Are better.
【００２３】[0023]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
【００２４】（実施例１〜３、比較例１〜３）実施例１
は、300 メッシュ以下に粉砕した石炭100 重量部に対
し、バインダーとしてタールを30重量部添加し、滑り材
を必要量添加し、250 セル/inch2のハニカム状に成型し
た。この成型品をプロパン燃焼ガス（ガス組成：窒素80
％、酸素0.2 ％、炭酸ガス9.8 ％、水蒸気10％）を用い
て、900 ℃で比表面積900m2/g になるまで賦活した後、
該窒素ガス中で300 ℃以下に冷却して、ハニカム状活性
炭担体を得た。Examples 1 to 3 and Comparative Examples 1 to 3
Was prepared by adding 30 parts by weight of tar as a binder to 100 parts by weight of coal pulverized to a size of 300 mesh or less, adding a necessary amount of a sliding material, and forming a honeycomb shape of 250 cells / inch 2 . This molded product is treated with propane combustion gas (gas composition: nitrogen 80
%, Oxygen 0.2%, carbon dioxide 9.8%, steam 10%) at 900 ° C until the specific surface area becomes 900m 2 / g.
By cooling to 300 ° C. or lower in the nitrogen gas, a honeycomb-shaped activated carbon carrier was obtained.
【００２５】次に比較例１は、実施例１と同様にして比
表面積が900m2/g になるまで賦活した後、活性炭を窒素
中に取り出し、500 ℃になるまで冷却し、更に空気中に
取り出して、放置冷却して活性炭担体を得た。更に、比
較例１の活性炭担体を700 ℃、N250％、CO250 ％、の気
流中で10分間処理した後、窒素中に取り出し、室温まで
冷却して実施例２の活性炭担体を得た。また、比較例１
の活性炭担体を900 ℃窒素中で５分間処理した後、窒素
中で室温まで冷却して実施例３の活性炭担体を得た。Next, in Comparative Example 1, after activating the specific surface area to 900 m 2 / g in the same manner as in Example 1, the activated carbon was taken out into nitrogen, cooled to 500 ° C., and further placed in air. It was taken out and allowed to cool to obtain an activated carbon carrier. Further, the activated carbon carrier of Comparative Example 1 was treated in an air stream of 700 ° C., 50% N 2 and 50% CO 2 for 10 minutes, taken out into nitrogen, and cooled to room temperature to obtain the activated carbon carrier of Example 2. Was. Comparative Example 1
Was treated in nitrogen at 900 ° C. for 5 minutes, and then cooled to room temperature in nitrogen to obtain an activated carbon carrier of Example 3.
【００２６】これらのハニカム状活性炭に次の様にして
塩化パラジウムを添着した。塩化パラジウム50mgを含む
0.5 規定塩酸溶液200mlに活性炭担体50g をいれてよく
攪拌し、３時間放置した後、水を切って純水100ml で洗
浄し、200 ℃で乾燥して塩化パラジウム添着量 1.0wt％
の塩化パラジウム添着活性炭ハニカムを得た。Palladium chloride was impregnated into these honeycomb activated carbons as follows. Contains 50mg of palladium chloride
Add 50 g of activated carbon carrier to 200 ml of 0.5 N hydrochloric acid solution, stir well, leave for 3 hours, drain, wash with 100 ml of pure water, dry at 200 ° C., and add 1.0 wt% of palladium chloride.
Activated carbon honeycomb impregnated with palladium chloride was obtained.
【００２７】このようにして得られた塩化パラジウム添
着ハニカム状活性炭10g を1m×1m×1mの箱に入れ、ファ
ンの上に設置してフィルターとして使用しエチレンの除
去テストを行った。[0027] placed this way palladium chloride-impregnated honeycomb activated carbon 10g obtained in a box of 1m × 1m × 1m, installed on the fan used as a filter was removed tests of ethylene.
【００２８】[0028]
【００２９】[0029]
【００３０】30℃におけるエチレンの除去速度の測定結Measurement results of the ethylene removal rate at 30 ° C.
果を表１に示す。尚、比較例２は実施例１で得られた活The results are shown in Table 1. In addition, Comparative Example 2 is the activity obtained in Example 1.
性炭担体に塩化パラジウムを添着せず、その儘の状態でWithout impregnating palladium chloride on the charcoal carrier,
使用したものであり、比較例３は市販のハニカム状活性Comparative Example 3 is a commercially available honeycomb-like active
炭に塩化パラジウム 1.0wt％を添着して使用したもので1.0% by weight of charcoal impregnated with palladium chloride
ある。is there.
【００３１】[0031]
【表１】 [Table 1]
【００３２】本発明のハニカム状塩化パラジウム添着活The honeycomb-like palladium chloride impregnated activation of the present invention
性炭（実施例１〜３）はいづれもエチレンを短時間に完All of the charcoal (Examples 1 to 3) complete ethylene in a short time.
全に除去し、優れた除去能力を示した。一方比較例（１It was completely removed and showed excellent removal ability. On the other hand, the comparative example (1
〜３）に示す様に、通常のハニカム状活性炭及び本発明As shown in (3) to (3), ordinary honeycomb activated carbon and the present invention
以外の方法により調製されたハニカム状塩化パラジウムPalladium chloride prepared by other methods
添着活性炭はいづれも有害ガス除去速度が遅かった。All of the impregnated activated carbons had low harmful gas removal rates.
【００３３】（実施例４〜11）(Examples 4 to 11)
セル数、比表面積の異なる他は実施例１と同様な方法でExcept that the number of cells and the specific surface area are different, the same method as in Example 1 is used.
得られたハニカム状活性炭（実施例４〜11）に、実施例The obtained honeycomb-shaped activated carbon (Examples 4 to 11)
１と同様の方法で塩化パラジウムを添着して、ハニカムThe palladium chloride is impregnated in the same manner as in 1, and the honeycomb
状塩化パラジウム添着活性炭を得た。これらの活性炭のActivated carbon impregnated with palladium chloride was obtained. Of these activated carbons
エチレン除去速度の測定結果を表２（実施例４〜11）にTable 2 (Examples 4 to 11) shows the measurement results of the ethylene removal rate.
示す。Show.
【００３４】[0034]
【００３５】[0035]
【表２】 [Table 2]
【００３６】表２に示すように、本発明の塩化パラジウAs shown in Table 2, the palladium chloride of the present invention
ム添着ハニカム状活性炭は比表面積が大きいほど有害ガThe more the specific surface area of the honeycomb-like activated carbon impregnated with
ス除去速度が速い。また、またセル数が多い程触媒性がFast removal speed. Also, the more cells, the more catalytic
高くなる傾向を示すがセル数が多くなり過ぎると、充填It tends to be high, but if the number of cells becomes too large,
比重が低下するため触媒性が低下する傾向がみられる。There is a tendency for the catalytic properties to decrease because the specific gravity decreases.
【００３７】[0037]
【００３８】[0038]
【００３９】[0039]
【００４０】（実施例12、13、比較例４、５）(Examples 12 and 13, Comparative Examples 4 and 5)
表３に示した本発明のハニカム状塩化パラジウム添着活Honeycomb-like palladium chloride impregnation activity of the present invention shown in Table 3
性炭及び比較のために調製した塩化パラジウム添着ハニCharcoal and palladium chloride impregnated honey prepared for comparison
カム状活性炭各100gを用いて、実施例１と同様の方法でIn the same manner as in Example 1, using 100 g of cam-shaped activated carbon
低温におけるエチレン除去速度を測定した。The ethylene removal rate at low temperature was measured.
【００４１】その結果及び試料の性状を表３に併せて示The results and properties of the samples are also shown in Table 3.
す。You.
【００４２】[0042]
【表３】 [Table 3]
【００４３】表３に示す様に本発明のハニカム状塩化パAs shown in Table 3, the honeycomb-shaped chloride powder of the present invention
ラジウム添着活性炭は、低温でも極めて速やかにエチレActivated carbon impregnated with radium can be etched very quickly even at low temperatures.
ンを除去出来ることが分かる。It can be seen that the ion can be removed.
【００４４】[0044]
【００４５】[0045]
【００４６】[0046]
【００４７】（実施例14、15、比較例６、７）(Examples 14 and 15, Comparative Examples 6 and 7)
表４に示す様に実施例１において、賦活したハニカム状As shown in Table 4, in Example 1, the activated honeycomb shape was used.
活性炭を取り出す際、NWhen taking out activated carbon, N
2Two
中で冷却後、空気中に取り出すAfter cooling in, take out into the air
ときの温度を変えた活性炭を作り、実施例１と同様の方Activated carbon with a different temperature was made, and the same as in Example 1
法で塩化パラジウムを１％添着して、塩化パラジウム添Impregnated with palladium chloride by 1%
着ハニカム状活性炭を得た。これらの活性炭を使用してA honeycombed activated carbon was obtained. Using these activated carbons
エチレン除去速度を測定した。The ethylene removal rate was measured.
【００４８】その結果及び使用した活性炭の性状を併せTogether with the results and the properties of the activated carbon used
て表４に示す。The results are shown in Table 4.
【００４９】[0049]
【表４】 [Table 4]
【００５０】表４に示す様に本発明のハニカム状塩化パ
ラジウム添着活性炭の性能は、冷却後初めて空気に接触
する温度に依存し、300 ℃以上では除去能が大幅に低下
する特性を有する。また、低温でも極めて速やかにエチ
レンを除去出来ることが分かる。As shown in Table 4, the honeycomb-shaped chloride powder of the present invention
The performance of radium impregnated activated carbon comes into contact with air only after cooling
Temperature above 300 ° C, the removal ability is greatly reduced
Have the property of It can also be seen that ethylene can be removed very quickly even at low temperatures.
【００５１】[0051]
【００５２】[0052]
【００５３】[0053]
【００５４】（実施例16、比較例８〜10）(Example 16, Comparative Examples 8 to 10)
石炭粉末を成型して作成したハニカムを賦活する際、賦When activating a honeycomb made by molding coal powder,
活ガスの水蒸気分圧が異なる条件で 900℃で比表面積10Specific surface area of 10 at 900 ° C under different steam partial pressure of active gas
00m00m
2Two
/gになるまで賦活した後、窒素で置換し 容器内に/ g, then replace with nitrogen and place in container
ハニカム活性炭を取り出し、該窒素中で300 ℃以下に冷Take out the honeycomb activated carbon and cool it to 300 ° C or less in the nitrogen.
却して表５に示すハニカム活性炭を得た。これらに実施Instead, a honeycomb activated carbon shown in Table 5 was obtained. Perform on these
例１と同様の方法で塩化パラジウムを 1.0 wt％添着1.0 wt% of palladium chloride impregnated in the same manner as in Example 1.
し、これらのハニカム状塩化パラジウム添着活性炭を使These honeycomb-shaped palladium chloride-impregnated activated carbons
用して、実施例１と同様な方法でエチレン除去速度を測And the ethylene removal rate was measured in the same manner as in Example 1.
定した。Specified.
【００５５】その結果及び使用した活性炭の性状を表５Table 5 shows the results and the properties of the activated carbon used.
に併せて示す。Are shown together.
【００５６】[0056]
【表５】 [Table 5]
【００５７】表５に示すように、本発明のハニカム状塩As shown in Table 5, the honeycomb-like salt of the present invention
化パラジウム添着活性炭の性能は賦活時の水蒸気濃度にThe performance of activated carbon impregnated with palladium fluoride depends on the steam concentration during activation.
依存し、水蒸気濃度が15％以下の場合に高い触媒性を示High catalytic performance when the water vapor concentration is 15% or less.
すことが認められる。Is allowed.
【００５８】[0058]
【発明の効果】本発明のハニカム状塩化パラジウム添着The honeycomb-like palladium chloride impregnated with the present invention
活性炭は、ハニカム状のため圧損失が極めて低く、またActivated carbon has a very low pressure loss due to its honeycomb shape.
常温或いは低温においても酸化触媒として高い機能を有Has a high function as an oxidation catalyst even at room temperature or low temperature
するため、エチレンの酸化除去能力に優れている。Therefore, it has excellent ability to remove ethylene by oxidation.
【００５９】この特性を利用して鮮度保持ボックス中のUsing this characteristic, the freshness holding box
青果物の鮮度保持剤に適している。Suitable for preserving freshness of fruits and vegetables.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) A23B 7/00 - 9/00 B01D 53/86 B01J 21/00 - 38/74 C01B 31/10 ＪＩＣＳＴファイル（ＪＯＩＳ)────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) A23B 7/ 00-9/00 B01D 53/86 B01J 21/00-38/74 C01B 31/10 JICST file ( JOIS)
Claims (1)
が 250〜800 セル/inch2のハニカム状に成型して炭化
し、水蒸気含有率15容量％以下の雰囲気で賦活した後、
そのままの雰囲気で 300℃以下まで冷却し、塩化パラジ
ウムを 0.1〜10重量％担持せしめた活性炭或いはまた、
石炭の炭化物よりタールをバインダーとして成型された
セル数が 250〜800 セル/inch2の通常のハニカム状活性
炭を、実質的に酸素または/ 及び水蒸気を含まない窒素
ガスまたは/ 及び炭酸ガス中で500℃以上で処理した
後、そのままの雰囲気中で 300℃以下まで冷却し、更に
塩化パラジウムを 0.1〜10重量％担持せしめた活性炭を
使用することを特徴とする、青果物の鮮度保持方法。Claims 1. After coal is formed into a honeycomb shape having a cell number of 250 to 800 cells / inch 2 using tar as a binder and carbonized, and activated in an atmosphere having a water vapor content of 15% by volume or less,
Activated carbon cooled to 300 ° C or less in the same atmosphere and loaded with 0.1 to 10% by weight of palladium chloride or
Normal honeycomb activated carbon number of cells that have been molded tar as a binder than carbide coal 250 to 800 cells / inch 2, with nitrogen and / or carbon dioxide gas containing substantially no oxygen and / or steam 5 A method for preserving the freshness of fruits and vegetables, comprising: treating at a temperature of at least 00 ° C., cooling to 300 ° C. or less in an atmosphere as it is, and using activated carbon loaded with 0.1 to 10% by weight of palladium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26272691A JP3155037B2 (en) | 1991-09-15 | 1991-09-15 | How to keep fruits and vegetables fresh |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26272691A JP3155037B2 (en) | 1991-09-15 | 1991-09-15 | How to keep fruits and vegetables fresh |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05154388A JPH05154388A (en) | 1993-06-22 |
| JP3155037B2 true JP3155037B2 (en) | 2001-04-09 |
Family
ID=17379743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26272691A Expired - Fee Related JP3155037B2 (en) | 1991-09-15 | 1991-09-15 | How to keep fruits and vegetables fresh |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3155037B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436067A (en) * | 1993-11-22 | 1995-07-25 | Kuraray Chemical Co., Ltd. | Freshness keeping sheet |
| CN113828311B (en) * | 2021-10-14 | 2024-03-22 | 西安建筑科技大学 | High sulfur-resistant catalyst for removing CO and preparation method thereof |
-
1991
- 1991-09-15 JP JP26272691A patent/JP3155037B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05154388A (en) | 1993-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4708853A (en) | Mercury adsorbent carbon molecular sieves and process for removing mercury vapor from gas streams | |
| US5536302A (en) | Adsorbent for removal of trace oxygen from inert gases | |
| EP0643014B1 (en) | Deodorant comprising metal oxide-carrying activated carbon | |
| EP0474106A2 (en) | Process for making modified carbon molecular sieves for gas separation | |
| JPS6040893B2 (en) | Ethylene absorbent and its manufacturing method | |
| JP3155037B2 (en) | How to keep fruits and vegetables fresh | |
| WO2001005704A1 (en) | Process for production of carbonaceous chars having catalytic activity | |
| JP3357137B2 (en) | Deodorization method | |
| JP2000511099A (en) | Nonmetal and semimetal hydride removal method | |
| JP2001170482A (en) | Active carbon, its manufacturing method and device for purifying treatment of water using the same | |
| JP2950666B2 (en) | Activated carbon water purifier | |
| US5219819A (en) | Copper crystallite in carbon molecular sieves for selective oxygen removal | |
| JP3098290B2 (en) | Activated carbon impregnated with palladium chloride | |
| JP2901212B2 (en) | Activated carbon for removing organic halogen compounds | |
| JPS6010776B2 (en) | Ethylene removal agent | |
| JPH0653214B2 (en) | Nitrogen oxide removal method | |
| JP2551417B2 (en) | Adsorbent for carbon monoxide separation | |
| JP3068231B2 (en) | NO adsorbent | |
| JPS62193633A (en) | Reducing agent for nitrogen oxide | |
| JPS63139990A (en) | Manufacture of high-calorie gas | |
| JP2947478B2 (en) | Carbon monoxide remover | |
| JPS63190645A (en) | Exhaust gas purification agent | |
| JPH0398642A (en) | Air purifier | |
| JPH02113849A (en) | Freshness-keeping agent | |
| JP3731044B2 (en) | Method for producing highly active methane adsorbent and methane storage method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |