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WO2024176483A1 - Matériau solide libérant de manière prolongée de l'éthylène gazeux - Google Patents

Matériau solide libérant de manière prolongée de l'éthylène gazeux Download PDF

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Publication number
WO2024176483A1
WO2024176483A1 PCT/JP2023/026838 JP2023026838W WO2024176483A1 WO 2024176483 A1 WO2024176483 A1 WO 2024176483A1 JP 2023026838 W JP2023026838 W JP 2023026838W WO 2024176483 A1 WO2024176483 A1 WO 2024176483A1
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WIPO (PCT)
Prior art keywords
ethylene gas
zeolite
solid material
silver
dehydrating agent
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Ceased
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PCT/JP2023/026838
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English (en)
Japanese (ja)
Inventor
真一郎 野呂
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Hokkaido University NUC
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Hokkaido University NUC
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Publication of WO2024176483A1 publication Critical patent/WO2024176483A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L19/00—Products from fruits or vegetables; Preparation or treatment thereof
    • A23L19/10—Products from fruits or vegetables; Preparation or treatment thereof of tuberous or like starch containing root crops
    • A23L19/12—Products from fruits or vegetables; Preparation or treatment thereof of tuberous or like starch containing root crops of potatoes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/22—Type X
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a solid material that slowly releases ethylene gas.
  • Ethylene gas is a type of plant hormone that is known to affect the freshness and ripeness of fruits, vegetables, and flowers. For example, if the concentration of ethylene gas around fruits, vegetables, and flowers becomes high, the fruit, vegetables, and flowers will begin to rot and lose their freshness. Therefore, in order to prevent the rot of such fruit, vegetables, and flowers and to maintain their freshness, a method is known in which ethylene gas around the fruit, vegetables, and flowers is adsorbed and removed using an ethylene adsorbent.
  • Ethylene gas is also known to have the function of promoting the ripening of fruits, vegetables, and flowers, and inhibiting germination and germination.
  • Such functions of ethylene gas are realized by maintaining the ethylene gas concentration around the fruits, vegetables, and flowers within an appropriate range, but in order to maintain the ethylene gas concentration around the fruits, vegetables, and flowers within an appropriate range, it is necessary to have the fruits, vegetables, and flowers coexist with a material that can gradually release ethylene gas (ethylene gas sustained release material).
  • Ethephon liquid which contains 2-chloroethylphosphonic acid as an active ingredient, has been commonly used as such an ethylene gas sustained-release material.
  • liquid ethylene gas sustained-release materials are not suitable for use in transporting fruits, vegetables, or flowers.
  • 2-chloroethylphosphonic acid in ethephon liquid generates ethylene gas through the decomposition of the acid, and the above-mentioned functions are realized.
  • chlorine and surfactants are also generated at the same time, so it is necessary to prevent the release of these.
  • 2-chloroethylphosphonic acid decomposes within 1-2 days, it is necessary to frequently replenish or spray ethephon liquid in order to maintain the ethylene gas concentration within an appropriate range for a long period of time.
  • JP 2010-94059 A describes a method for inhibiting potato germination in which potatoes are stored in a breathable container together with an ethylene adsorbent such as zeolite, silica gel, or activated carbon, and the ethylene concentration in the container is kept within a predetermined range to preserve the potatoes.
  • an ethylene adsorbent such as zeolite, silica gel, or activated carbon
  • JP 2016-160383 A (Patent Document 2) describes, as an organic solid ethylene gas slow-release material, a slow-release material for slowly releasing volatile substances such as ethylene gas, which comprises polymer particles having structural units derived from (meth)acrylic acid ester and a coating portion that coats at least a portion of the polymer particles.
  • the present invention was made in consideration of the problems with the conventional technology described above, and aims to provide a solid material for the sustained release of ethylene gas that is capable of sustained release of ethylene gas over a long period of time.
  • silver-containing zeolite which is zeolite into which silver has been introduced, has superior performance in slowing down the rate at which ethylene gas is released, i.e., superior sustained release performance, compared to zeolite alone, and further discovered that by combining this silver-containing zeolite with a dehydrating agent, it becomes possible to sustainably release ethylene gas over an extended period of time, which led to the completion of the present invention.
  • the present invention provides the following aspects:
  • a solid material for sustained release of ethylene gas comprising a silver-containing zeolite and a dehydrating agent.
  • the present invention makes it possible to slowly release ethylene gas over a long period of time.
  • 1 is a graph showing the results of an ethylene gas sustained release test under dry conditions for Ag-containing Na-A type zeolite and Na-A type zeolite alone.
  • 1 is a graph showing the results of an ethylene gas sustained release test of Ag-containing Na-A type zeolite under dry and humid conditions, and the results of an ethylene gas sustained release test of Na-A type zeolite alone under dry conditions.
  • 1 is a photograph showing the state of potato sprouts at the start of a sprout inhibition test conducted using the samples prepared in Examples A1 to A3 and a control test sample, and the state after 31 days.
  • 1 is a graph showing the relative sprout amount of the samples prepared in Examples A1 to A3 to the sprout amount of the control test sample (sprout amount of the control test sample: 100) for potatoes 31 days after the sprout inhibition test conducted using the samples prepared in Examples A1 to A3 and the control test sample.
  • 1 is a graph showing the ethylene gas concentration in fruit and vegetable freshness-preserving packs during a sprout inhibition test conducted using the samples prepared in Examples A1 to A3 and the control test sample.
  • 1 is a graph showing the relative sprout amount of the samples prepared in Example B1 and Comparative Examples B1 and B2 to the sprout amount of the control test sample (sprout amount of the control test sample: 100) for potatoes 29 days after the sprout inhibition test conducted using the samples prepared in Example B1 and Comparative Examples B1 and B2 and the control test sample.
  • 1 is a graph showing the ethylene gas concentration in fruit and vegetable freshness-preserving packs during a sprout inhibition test conducted using the samples prepared in Example B1 and Comparative Examples B1 to B2 and the control test samples.
  • 1 is a graph showing the ethylene gas concentration in fruit and vegetable freshness-preserving packs during a sprout inhibition test period conducted in a reference test.
  • the ethylene gas sustained-release solid material of the present invention contains a silver-containing zeolite (hereinafter also referred to as "silver-containing zeolite”) and a dehydrating agent.
  • a silver-containing zeolite hereinafter also referred to as "silver-containing zeolite”
  • dehydrating agent hereinafter also referred to as "silver-containing zeolite”
  • the zeolites used in the present invention include, for example, A-type zeolite, ferrierite, MCM-22 zeolite, ZSM-5 zeolite, mordenite, L-type zeolite, Y-type zeolite, X-type zeolite, and beta-type zeolite. These zeolites may be used alone or in combination of two or more types.
  • the molar ratio of Si to Al (Si/Al) in the zeolite is preferably 30 or less, more preferably 20 or less, even more preferably 12 or less, and particularly preferably 5 or less. If the Si/Al ratio exceeds the upper limit, the amount of ethylene gas adsorbed tends to be too low, and a sufficient amount of ethylene gas tends not to be released.
  • the lower limit of Si/Al is preferably 1 or more.
  • the BET specific surface area of the zeolite is preferably 10 m2/g or more, more preferably 20 m2/g or more, particularly preferably 50 m2/g or more, and is preferably 1000 m2 /g or less, more preferably 700 m2 /g or less, particularly preferably 500 m2 /g or less. If the BET specific surface area of the zeolite is less than the lower limit, the amount of ethylene gas adsorbed tends to be small, and the amount of ethylene gas gradually released tends to be small. On the other hand, if the BET specific surface area of the zeolite exceeds the upper limit, the hydrophilicity of the zeolite is excessively improved, and handling in the air tends to be difficult.
  • the average pore diameter of the zeolite is preferably 0.2 nm or more, more preferably 0.3 nm or more, particularly preferably 0.35 nm or more, and is preferably 1.2 nm or less, more preferably 0.8 nm or less, particularly preferably 0.5 nm or less. If the average pore diameter of the zeolite is less than the lower limit, ethylene gas is less likely to be adsorbed, and the amount of ethylene gas released gradually tends to be reduced. On the other hand, if the average pore diameter of the zeolite exceeds the upper limit, molecules with a molecular weight larger than ethylene are adsorbed, and the amount of ethylene adsorbed tends to be relatively reduced.
  • ethylene gas sustained-release solid material of the present invention it is necessary that silver is introduced into the zeolite in order to achieve excellent ethylene gas sustained-release performance.
  • Zeolite containing silver hereinafter abbreviated as "silver-containing zeolite"
  • the silver content in the silver-containing zeolite is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 25% by mass or less, based on the total amount of the silver-containing zeolite. If the silver content is less than the lower limit, the ethylene gas sustained release performance tends to be less likely to be exhibited. On the other hand, even if silver is introduced in an amount exceeding the upper limit, the ethylene gas sustained release performance tends to saturate, and therefore the effect of introducing silver tends to be less likely to be obtained.
  • Such silver-containing zeolites can be prepared, for example, by an ion exchange reaction. Specifically, they can be obtained by mixing zeolite with a water-soluble silver compound (e.g., silver nitrate, silver sulfate, silver acetate) and water, and then carrying out an ion exchange reaction between the cations in the zeolite and the silver ions.
  • a water-soluble silver compound e.g., silver nitrate, silver sulfate, silver acetate
  • the dehydrating agent used in the present invention is used to remove the effects of moisture contained in the atmosphere from the sustained-release material. More specifically, it is used to prevent the release rate of ethylene from increasing due to the presence of moisture.
  • dehydrating agent there are no particular limitations on the type of dehydrating agent that can be used, and any type can be used, such as a physical adsorption type, a chemical reaction type, a water of crystallization type, or a composite type in which a number of these types act in parallel.
  • the dehydrating agent it is preferable for the dehydrating agent to be in the form of a solid.
  • Physical adsorption dehydrating agents remove moisture from the atmosphere mainly through physical adsorption resulting from intermolecular forces.
  • Specific examples include mainly porous materials such as silica gel, molecular sieves, natural zeolites, activated alumina, diatomaceous earth, and metal organic frameworks.
  • Chemical reaction type dehydrating agents remove moisture from the atmosphere by chemically reacting with water.
  • Specific examples include oxides of alkali metals or alkaline earth metals, such as calcium oxide and magnesium oxide, and phosphorus oxide.
  • Crystal water-type dehydrating agents remove moisture from the atmosphere by retaining the moisture as crystal water.
  • Specific examples include compounds that can contain crystal water, such as calcium chloride, zinc chloride, calcium sulfate, magnesium sulfate, potassium hydroxide, potassium carbonate, and other alkali metals, alkaline earth metals, and halogen salts, sulfates, carbonates, and the like of other metals.
  • dehydrating agents physical adsorption type dehydrating agents are preferred because they are small and highly safe as they do not undergo chemical reactions. In addition, they can be regenerated and reused by adding a dehydration process to the desiccant after use.
  • crystal water type dehydrating agents have the advantage that they can be made compact overall because they can adsorb a large amount of water. This makes them ideal when compactness and weight reduction are required.
  • the ethylene gas sustained-release solid material of the present invention contains such a silver-containing zeolite and a dehydrating agent.
  • the amount of water that can be adsorbed by the dehydrating agent is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more, relative to 100 parts by mass of the silver-containing zeolite, and is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 500 parts by mass or less, and particularly preferably 300 parts by mass or less.
  • the amount of water that can be adsorbed by the dehydrating agent is less than the lower limit, the water may easily pass through the dehydrating agent, and the effect of combining the dehydrating agent may not be exerted.
  • the amount of water that can be adsorbed by the dehydrating agent exceeds the upper limit, the dehydrating agent tends to be larger or heavier than necessary.
  • the amount of water that can be adsorbed by the dehydrating agent can be appropriately adjusted by changing the compounding ratio of the silver-containing zeolite and the dehydrating agent.
  • a layer made of the silver-containing zeolite and a layer made of the dehydrating agent are arranged so that the ethylene gas released from the silver-containing zeolite passes through the layer made of the dehydrating agent.
  • a container with a bottom such as a sample tube or test tube, is filled with the silver-containing zeolite, and the dehydrating agent is filled on top of that. This forms a dehydrating agent layer on top of the silver-containing zeolite layer, and the ethylene gas released from the silver-containing zeolite passes through the dehydrating agent layer and is dried, making it possible to sustainably release ethylene gas under dry conditions.
  • the ethylene gas sustained-release solid material of the present invention can be used by adsorbing ethylene gas to the silver-containing zeolite.
  • adsorbing ethylene gas to the silver-containing zeolite it is preferable to remove moisture from the ethylene gas sustained-release solid material beforehand. This allows for the sustained release of a large amount of ethylene gas.
  • the solid component was collected by suction filtration to obtain Na-A type zeolite containing Ag (hereinafter abbreviated as "Ag-containing Na-A type zeolite").
  • the Ag content in the obtained Ag-containing Na-A type zeolite was calculated to be 20 mass% by ICP emission analysis.
  • Figure 1 is a graph showing the results of an ethylene gas release test under dry conditions for Ag-containing Na-A type zeolite and Na-A type zeolite alone
  • Figure 2 is a graph showing the results of an ethylene gas release test under dry and humid conditions for Ag-containing Na-A type zeolite, as well as the results of an ethylene gas release test under dry conditions for Na-A type zeolite alone.
  • Figure 1 it was confirmed that Ag-containing zeolite has superior ethylene gas release performance compared to zeolite alone.
  • Figure 2 it was found that Ag-containing zeolite can release ethylene gas for a longer period of time when used under dry conditions compared to when used under humid conditions, improving ethylene gas release performance.
  • Example A1 Preparation of ethylene gas sustained release solid material> A 25 ml glass sample tube was filled with 1 g of Ag-containing Na-X type zeolite obtained in Synthesis Example 2 to form an Ag-containing zeolite layer, then filled with glass wool, and filled with 1 g of anhydrous calcium chloride as a dehydrating agent to form a dehydrating agent layer, and then filled with glass wool. A three-way cock was attached to the opening of the sample tube to prepare an ethylene gas sustained release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent. Note that anhydrous calcium chloride becomes calcium chloride hexahydrate at the maximum, so the theoretical water absorption per 1 g of anhydrous calcium chloride is 0.97 g.
  • Example A2 An ethylene gas controlled-release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent was prepared in the same manner as in Example A1, except that the amount of Ag-containing Na-X type zeolite was changed to 2 g. Ethylene gas was then encapsulated in this ethylene gas controlled-release solid material, and a test sample for inhibiting sprouting of fruits and vegetables was prepared using this ethylene gas encapsulated solid material.
  • Example A3 An ethylene gas controlled-release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent was prepared in the same manner as in Example A1, except that the amount of Ag-containing Na-X type zeolite was changed to 3 g. Ethylene gas was then encapsulated in this ethylene gas controlled-release solid material, and a test sample for inhibiting sprouting of fruits and vegetables was prepared using this ethylene gas encapsulated solid material.
  • Figure 3 is a photograph showing the state of sprouting of potatoes at the start of the test and after 31 days in a sprouting inhibition test conducted using the samples prepared in Examples A1 to A3 and target test sample A.
  • Figure 4 is a graph showing the relative value of the amount of sprouting of the samples prepared in Examples A1 to A3 to the amount of sprouting of target test sample A (amount of sprouting of target test sample A: 100) for potatoes after 31 days in a sprouting inhibition test conducted using the samples prepared in Examples A1 to A3 and target test sample A.
  • Figure 5 is a graph showing the ethylene gas concentration in fruit and vegetable freshness-preserving packs during the period of the sprouting inhibition test conducted using the samples prepared in Examples A1 to A3 and target test sample A.
  • Example B1 An ethylene gas controlled-release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent was prepared in the same manner as in Example A1, except that the amount of Ag-containing Na-X type zeolite was changed to 2 g. Ethylene gas was then encapsulated in this ethylene gas controlled-release solid material, and a test sample for inhibiting sprouting of fruits and vegetables was prepared using this ethylene gas encapsulated solid material.
  • Figure 6 is a graph showing the relative sprout amount for the samples prepared in Example B1 and Comparative Examples B1-B2 to the amount for the target test sample B (sprout amount for the target test sample B: 100) for potatoes 29 days after the sprout inhibition test conducted using the samples prepared in Example B1 and Comparative Examples B1-B2 and the target test sample B.
  • Figure 7 is a graph showing the ethylene gas concentration in fruit and vegetable freshness-preserving packs during the sprout inhibition test conducted using the samples prepared in Example B1 and Comparative Examples B1-B2 and the target test sample B.
  • Example B1 As shown in Figure 6, it was confirmed that the coexistence of an ethylene gas slow-release solid material containing (or containing) ethylene gas suppresses sprouting of fruits and vegetables (Example B1 and Comparative Examples B1-B2).
  • Example B1 when an ethylene gas slow-release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent was used (Example B1), sprouting of fruits and vegetables was further suppressed compared to when an ethylene gas slow-release solid material containing a commercially available fruit ripening agent (containing zeolite and ethylene) and a dehydrating agent was used (Comparative Example B1), and when an ethylene gas slow-release solid material containing Ag-containing Na-X type zeolite but no dehydrating agent was used (Comparative Example B2).
  • ethylene gas sustained-release solid material containing a commercially available fruit ripening agent (containing zeolite and ethylene) and a dehydrating agent (Comparative Example B1)
  • ethylene gas sustained-release solid material containing Ag-containing Na-X type zeolite but no dehydrating agent (Comparative Example B2)
  • ethylene gas sustained-release solid material containing Ag-containing Na-X type zeolite and a dehydrating agent (Example B1).
  • the present invention it is possible to slowly release ethylene gas over a long period of time. Therefore, by allowing the ethylene gas slow-release solid material of the present invention to coexist with fruits, vegetables, or flowers, the ethylene gas concentration around the fruits, vegetables, or flowers can be maintained within an appropriate range for a long period of time, making it possible to promote the ripening of the fruits, vegetables, or flowers and to inhibit germination and sprouting.
  • the ethylene gas slow-release solid material of the present invention is easy to handle, it is also useful as an ethylene gas slow-release material during the transportation of fruits, vegetables, vegetables, or flowers.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Storage Of Fruits Or Vegetables (AREA)

Abstract

L'invention concerne un matériau solide libérant de manière prolongée de l'éthylène gazeux, le matériau solide comprenant une zéolite contenant de l'argent et comprenant également un agent de déshydratation, une couche comprenant la zéolite contenant de l'argent et une couche comprenant l'agent de déshydratation étant de préférence agencées de sorte que l'éthylène gazeux libéré de la zéolite contenant de l'argent traverse la couche comprenant l'agent de déshydratation.
PCT/JP2023/026838 2023-02-24 2023-07-21 Matériau solide libérant de manière prolongée de l'éthylène gazeux Ceased WO2024176483A1 (fr)

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JP2023027529 2023-02-24

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011129402A1 (fr) * 2010-04-16 2011-10-20 三菱瓦斯化学株式会社 Procédé pour le contrôle de pousses de pomme de terre
CN113441171A (zh) * 2021-05-12 2021-09-28 中新国际联合研究院 一种载体改性的银基乙烯脱除剂及其制备方法和应用
CN114682295A (zh) * 2022-03-30 2022-07-01 宁波锋成先进能源材料研究院有限公司 一种催化型乙烯脱除剂的制备方法及应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011129402A1 (fr) * 2010-04-16 2011-10-20 三菱瓦斯化学株式会社 Procédé pour le contrôle de pousses de pomme de terre
CN113441171A (zh) * 2021-05-12 2021-09-28 中新国际联合研究院 一种载体改性的银基乙烯脱除剂及其制备方法和应用
CN114682295A (zh) * 2022-03-30 2022-07-01 宁波锋成先进能源材料研究院有限公司 一种催化型乙烯脱除剂的制备方法及应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CISNEROS LARISHA, GAO FEI, CORMA AVELINO: "Silver nanocluster in zeolites. ADSORPTION of ETHYLENE traces for fruit preservation", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 283, 1 July 2019 (2019-07-01), Amsterdam ,NL , pages 25 - 30, XP055885747, ISSN: 1387-1811, DOI: 10.1016/j.micromeso.2019.03.032 *
SHENOY SPOORTHY; PATHAK NAMRATA; MOLINS ADRIANA; TONCHEVA ANTONIYA; SCHOUW TIM; HEMBERG AXEL; LAOUTID FOUAD; MAHAJAN PRAMOD V.: "Impact of relative humidity on ethylene removal kinetics of different scavenging materials for fresh produce industry", POSTHARVEST BIOLOGY AND TECHNOLOGY, vol. 188, 4 March 2022 (2022-03-04), AMSTERDAM, NL , pages 1 - 11, XP087008400, ISSN: 0925-5214, DOI: 10.1016/j.postharvbio.2022.111881 *
VAN ZANDVOORT ILONA; VAN KLINK GERARD P.M.; DE JONG ED; VAN DER WAAL JAN C.: "Selectivity and stability of zeolites [Ca]A and [Ag]A towards ethylene adsorption and desorption from complex gas mixtures", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 263, 8 December 2017 (2017-12-08), Amsterdam ,NL , pages 142 - 149, XP085366379, ISSN: 1387-1811, DOI: 10.1016/j.micromeso.2017.12.004 *

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