WO2008110020A1 - Feuilles catalytiquement actives pour l'absorption d'éthylène - Google Patents

Feuilles catalytiquement actives pour l'absorption d'éthylène Download PDF

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Publication number
WO2008110020A1
WO2008110020A1 PCT/CH2007/000141 CH2007000141W WO2008110020A1 WO 2008110020 A1 WO2008110020 A1 WO 2008110020A1 CH 2007000141 W CH2007000141 W CH 2007000141W WO 2008110020 A1 WO2008110020 A1 WO 2008110020A1
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Prior art keywords
catalyst
catalytic
foil
ethene
poly
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PCT/CH2007/000141
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English (en)
Inventor
Stefan Loher
Wendelin Jan Stark
Original Assignee
Perlen Converting Ag
Eth Zurich
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Publication date
Application filed by Perlen Converting Ag, Eth Zurich filed Critical Perlen Converting Ag
Priority to PCT/CH2007/000141 priority Critical patent/WO2008110020A1/fr
Publication of WO2008110020A1 publication Critical patent/WO2008110020A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups 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 groups 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/11—Air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating

Definitions

  • the present invention concerns the production of a coating and a packaging material with catalytic gas absorption capacity, in particular catalytic ethene (eth- ylene) absorption capacity at low temperatures. More specifically, the present invention concerns a packaging material for the storage of ethene sensitive produce such as fruits, vegetables and cut flowers and the use of a catalytic coating in catalytic oxidation of ethene.
  • Another approach is to avoid accumulation of plant-released ethene by either passive or active methods, where "passive" means that no chemical reaction is involved in the ethene removing process. All passive solutions once in use are limited in terms of ethene adsorbing capacity and hence are inactive after a certain time period or an unusual burst of ethene until desorp- tion that is mostly done by heating.
  • Passive methods Passive removal can be achieved either simply by sufficient ventilation or by introducing an adsorbing material. Latter might be in the form of sachets or in- corporated into the packaging material. Most of the patent applications filed imply zeolites either of hydrophobic (EP0417811, JP0527326, NL1000595-6) or hydrophilic ([H] EP1106233) character. Incorporation of the zeolites and other inorganic materials (e.g.
  • ethene concentrations e.g. 100 ppm
  • packaging materials containing zeolites have a hazy appearance attributed to scattering of the micrometer particles, which negatively affects consumer acceptance.
  • earth-type scavengers such as grinded coral (US5084337) , crysburite ceramic [13], Japanese Oya stone (Evert-Fresh bags, Evert-Fresh Corporation) or mixtures of minerals (US4847145) .
  • the claimed ethene adsorption capacity generally relies on shelf-life experiments and often lacks relevant experimental data. It is believed that the putative ad- sorption is in facts the result of an enhanced permeability of the mineral containing plastics . 2. Active methods
  • Active removal of ethene implies a chemical reaction and can be subdivided into two processes.
  • the first method describing a non-catalytic reaction is inac- tive after the reagent is consumed whereas the second process involves a catalytic absorption of ethene.
  • oxidizing agents e.g. potassium permanganate KMnC>4.
  • the permanganate is generally immobilized on any of several minerals (e.g. zeolites, silica, titania, meerschaum, etc.) having a high surface area ([14], US5314852, WO0154496, WO0130658, US5955004, WO9523517, US5075117).
  • the products are available in the form of sachets for packages, blankets that can be placed in produce-holding rooms, and polymeric films or paper board with incorporated or ' entrapped activated minerals all showing an extension of shelf-life for different fresh produce [15] .
  • a further consumptive approach uses a compound having a hydrosilyl group and a hydrosilylation catalyst selected from group VIII metals which is carried on a pdurous inorganic material (EP0635219) .
  • a hydrosilylation catalyst selected from group VIII metals which is carried on a pdurous inorganic material (EP0635219) .
  • ethene reacts with the hy- drosilyl group via hydrosilylation and therefore the removal is limited to the amount of hydrosilyl groups present.
  • Another solution for non-catalytic absorptions is composed of electron-deficient dienes or trienes (e.g. tetrazine) in an ethene-permeable, hydrophobic, polymeric substrate in the form of a film ([16], WO9104292, WO2004076545, US5334623) .
  • ethene scrubbers are available for fruit cool stores which transport the ethene containing air from the storage room to a heated reaction zone (-27O 0 C) using a supported platinum catalyst for the oxi- dation [ISOCELL ITALIA SPA.39055 Laives (BZ)- Zona Indus- triale- Via Meucci 7] .
  • Another possibility might be the sorption of ethene at room temperature (or at lower temperatures) followed by desorption and catalytic oxidation at higher temperatures.
  • indirect oxidation processes include transportation of contaminated air or sorption material and a separated heating step, which is energy consuming.
  • a preferred packaging form for ethene removal should be active at 25 0 C or below and at low ethene concentrations of ⁇ 200 ppm, preferably ⁇ IOO ppm. It is also desired that such packaging form is based on a catalytic process which keeps activity for 1 day up to 6 weeks starting from its application.
  • the material preferably should also be transparent, e.g. have a transmission (T) at ⁇ 500 nm of >50%.
  • T transmission
  • the system preferably works at an ambient pressure of about 1 atm.
  • a catalytic foil provided with a catalytic system able to remove olefins, especially ethene, at temperatures of 25°C and below.
  • the catalytic system is already active at 20 D C or below.
  • a catalytic foil that is effective at low ethene concentrations of ⁇ 200 ppm, preferably ⁇ IOO ppm and is active for about 3 weeks or more, has good transparency, and is active at ambient pressure.
  • the catalytic foil is manifested by the features that it comprises a catalytic system consisting of a combination of a noble metal catalyst and a co-catalyst system, wherein the noble metal catalyst is selected from the group, consisting of palladium (II) salts, platinum (II) salts, ruthenium (III) salts, rhodium(III) salts and mixtures thereof, and the co-catalyst system consists of or contains a co-catalyst that is a water soluble Mo and/or V and/or W comprising substance, in particular a hetero- polyanion (HPA) of structure [HyPMo (12- ⁇ ) M X O4Q] ( 3 +z ⁇ y) ⁇ or a mixture of such heteropolyanions, and wherein the catalyst and the co-catalyst system are selected such that the reoxidation of the Pd
  • HPA hetero- polyanion
  • a much preferred catalytic system comprises vanadium.
  • the catalyst is selected from the group consisiting of PdCl2, palladium diacetate, Na2PdCl4, palladium sulfate, palladium hydroxide, and mixtures thereof, preferably PdCl2 ⁇
  • mixed co-catalysts of heteropoly- anion type are preferred over exclusively Mo comprising co-catalysts, and Mo 4- V comprising co-catalysts are preferred over Mo + W comprising co-catalysts.
  • Preferred co-catalysts are selected from
  • An especially preferred co-catalyst is
  • the co- catalyst system may contain further compounds with acceptable solubility and redox potential to allow reoxida- tion of the noble metal.
  • the catalytic system and its amount in gen- eral is chosen with regard to the costs, the desired transparency, and the solubility.
  • a minimal amount of catalyst is about 1 mg Pd/m2, or about 10 ⁇ mole noble metal cata- lyst/m.2, preferably 5 to 10 mg Pd/m2, or about 45 to 95 ⁇ mole noble metal catalyst/m2, much preferred about 5 mg Pd/m ⁇ , or about 45 ⁇ mole noble metal catalyst/m2.
  • ⁇ he upper value of about 10 mg Pd/m2, or about 95 ⁇ mole noble metal catalyst/m.2 is an estimate for an optimization in view of efficiency, transparency and costs, however for applications, where the costs, the transparency etc. are of less importance than e.g. in the packaging of produce, higher amounts can be advantageous .
  • the molar ratio of co-catalyst to catalyst in the case of the co-catalyst being a heteropolyanion as defined above is ⁇ 10:l, preferably about 20:1 to 40:1, or, referred to the metals of the HPA, i.e. Mo+W+V, >120:l, preferably about 240:1 to 480:1.
  • a catalytic foil of the present invention is either made of a catalyst system comprising polymer or by applying a polymer coating comprising a catalyst system on at least one, preferably both surfaces of a carrier film.
  • a suitable polymer is a polymer with free acid groups (e.g polymers containing sulphonic acid groups, phosphonic acid groups and mixtures thereof) that is soluble in water or lower alcohols, in particular Cl- C3 alcohols, and that has a solubility sufficient to give a 10wt% aqueous solution at pH ⁇ 2.
  • free acid groups e.g polymers containing sulphonic acid groups, phosphonic acid groups and mixtures thereof
  • polystyrenesulfonic acid poly(styrene phosphonic acid), poly (2-acrylar ⁇ ido- 2-methyl-l-propanesulfonic acid), poly (vinyl sulfonic acid), poly (styrene-ran-ethylene) sulfonated solution, i.e. [CH 2 CH(C 6 H 4 SO 3 H) ] x (CH 2 CH 2 ) y solution.
  • the stability of the polymer can be improved, i.e. its water solubility reduced, by a cross-linking step during curing of the coating.
  • a cross-linking step can be achieved e.g. by replacing some of the ,,acidic" groups, e.g. the solfonic and/or phosphonic acid groups by cross-linkable groups such as vinly groups.
  • Another way of cross-linkage is the use of conventional cross- linkable agents such as vinyl silane cross-linking agent.
  • polystyrene-Mocic-poly (ethylene-ran- butylene) -jblocic-polystyrene, sulfonated, cross-linkable solution [CH 2 CH(C 6 H 4 SO 3 H) ] w (CH 2 CH 2 ) x [CH 2 CH (C 2 H 5 ) ] y _ [CH 2 CH(CgH 4 SO 3 H)I 2 and vinyl silane cross-linking agent, ⁇ 0.5%.
  • the carrier films are uncritical, provided that the catalytic system comprising polymer sufficiently adheres to their surface either directly or after application of an adhesion improving surface treatment such as an adhesion improving primer coating. If both surfaces are coated with the catalytic system comprising polymer, an ethene permeable carrier film is preferred.
  • Suitable carrier films are selected from the group consisting of polyesters, in particular poly (ethylene terephtalate) (PET) , polyolefins (HDPE, LDPE, polypropylene) , poly (vinyl chloride) or mixtures thereof, and presently preferred is amorphous poly (ethylene terephtalate).
  • a method for preparing a homogeneous catalytic coating comprises the steps of: i) Preparing (a) an aqueous catalytic solution or a solid catalyst system and (b) an aqueous polymer solution, ii) adding the aqueous catalytic solution or the solid catalyst system to the aqueous polymer solution, iii) forming a polymeric, solid film material or a coating with the mixture by applying conventional film forming or coating processes such as roll coating, spray coating, gap coating, air knife coating, immersion (dip) coating, curtain coating, or slot die coating, iv) thermally removing at least part, preferably all solvent, and optionally cross-linking the applied polymer by heat or UV radiation, v) optionally applying a protective polymeric cover coating either in liquid form (molten or dissolved or dispersed) or as a solid film laminate .
  • Protective polymeric cover coatings applica- ble either in liquid form or as a solid film must be sufficiently, preferably highly permeable to ethene to ensure its getting into contact with the catalytic system. High ethene permeability is found with a high variety of foils. However, the cover coatings should not comprise water or humidity, respectively, in order to avoid interference with the catalytic foil or coating. Preferred coatings therefore are those comprising
  • Suitable protective materials are e.g. poly- styrene, silicones, polyethylene, polypropylene, poly (vinyl chloride) .
  • Figure 1 shows the ethene concentration as a function of time for different aqueous catalytic solutions .
  • the palladium chloride concentration has been varied from 0 to 2.5 mM.
  • Figure 2 is a logarithmic plot of the normalized ethene concentration versus time. Linear regression was used for data fitting assuming first order kinetics. The reaction rate constant is given as the corresponding slope of the linear fitting line.
  • Figure 3 shows the ethene content as a function of time for a first loading of the reaction flask with 100 ppm ethene and for poly (styrenesulfonic acid) (PSSA) films containing catalytic solutions with 5 mg Pd/m2 and different heteropolyanion (HPA; specifically Na3H3PM ⁇ 9V3 ⁇ 4o) concentrations.
  • PSSA poly (styrenesulfonic acid)
  • Figure 4 shows the third loading of the reaction flask with 100 ppm ethene after 4 days of first experiment.
  • the catalytic activity of the films decreased and concentrations below 10 ppm are observed after 45 hours .
  • Figure 5 shows the sixth loading of the reaction flask with 100 ppm ethene after 3 weeks. Approximately 100 hours are needed to reach ethene concentra- tions below 10 ppm confirming a further decrease of activity compared to the previous cycles.
  • Figure 6 is a comparison of a catalytic film with and without a lO ⁇ m polystyrene (PS) cover coating. Weight ratio of heteropolyanion (HPA) to polymer is held at 0.25. The observed activity of the PS covered film is decreased.
  • HPA heteropolyanion
  • Catalytic solutions with different Pd concen- trations were obtained by dissolving corresponding amounts of PdCl2 (99.9%, ABCR Chemicals) in a 0.3 M Na3H3PMogV3 ⁇ 40 aqueous solution prepared following the procedure outlined in patent application WO 91/13681.
  • the palladium content was chosen constant such that a palladium to dry polymer weight ratio of 2.5 * 10 ⁇ 4 W as obtained.
  • Corresponding amounts of catalytic solution were added to 5.0 g of poly (styrene- sulfonic acid) solution (PSSA, 18wt% in H2O, Sigma- Aldrich) and mixed thoroughly.
  • the weight ratio of the heteropolyanion to dry PSSA was 0 for the reference sample, 0.12, 0.25, and 0.49, respectively.
  • the resulting mixture was coated using an automatic film applicatior (ZAA 2300, Zehntner GmbH) equipped with a 50 ⁇ m doctor roller and dried at room temperature.
  • An amorphous PET film (40 ⁇ m) was used as a substrate.
  • a film containing no catalytic solution was prepared from the PSSA solution.
  • the PSSA film was subsequently coated with a 10 ⁇ m polystyrene (BASF) film from a 20wt% solution in toluene.
  • BASF polystyrene
  • Na3H3PMogV3 ⁇ 40 were tested for the conversion of 1000 ppm ethene (>99%, Fluka) in synthetic air.
  • the solution was stirred at 1000 rpm with a magnetic stirrer to maximize mass transfer.
  • the coated films (0.9 g PSSA, ca . 400 cm 2 ) were put in 500 ml Erlen- meyer flasks, sealed with a septum and flushed for 4 minutes at a flow of 5000 ml/min with 100 ppm ethene in synthetic air (PanGas) .
  • PanGas synthetic air
  • a set of catalytic films were tested together with a polymer reference.
  • gas samples were withdrawn at specific time points with a gas-tight 500 ⁇ l syringe.
  • the reference sample still contained about 60 ppm ethene.
  • the steady ethene decrease might be attributed to diffusion through the septum or minute activity of the PSSA.
  • the similar performance of the different films indicates that the limiting step is the oxidation of ethene by Pd ⁇ + which is then reduced to Pd*- 1 . Reoxidation by the HPA seems to proceed fast as an increase in HPA concentration had no significant influence on the reaction kinetics .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention porte sur une feuille catalytique, en particulier pour l'élimination d'éthylène, qui comprend un système catalytique consistant en une combinaison d'un catalyseur et d'un système de co-catalyseur dans un polymère ayant des groupes acides libres qui est soluble dans l'eau ou dans les alcools inférieurs. Le catalyseur est choisi parmi les sels de palladium (II), par exemple PdCl2, de platine (II), de ruthénium (III) et/ou de rhodium (III), et le système de co-catalyseur contient ou de préférence consiste en un hétéropolyanion (HPA) de structure [HyPMo(12-x)MxO40](3+z-y)-, dans laquelle les variables M, x, y et z sont choisies parmi: - M = W, V, en particulier V; x, y et z : dans le cas de M=W : 0≤x≤12, 0≤y≤3, et z=0, et dans le cas de M=V : 0≤x≤12, 0≤y≤(3+x) et z=x, par exemple Na3H3PMo9V3O40.
PCT/CH2007/000141 2007-03-15 2007-03-15 Feuilles catalytiquement actives pour l'absorption d'éthylène WO2008110020A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10021545B2 (en) 2008-09-29 2018-07-10 Electronics And Telecommunications Research Apparatus and method for transmitting and receiving data in wireless communication system using relay
CN109364750A (zh) * 2018-12-10 2019-02-22 中石化上海工程有限公司 乙二醇生产装置中含氧尾气的处理方法
US10994508B2 (en) 2015-05-12 2021-05-04 Innovia Films Limited Film
EP4215269A1 (fr) * 2022-01-19 2023-07-26 BASF Corporation Catalyseur d'hydrogénation emballé

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DD123085A1 (fr) * 1971-12-15 1976-11-20
JPS59163335A (ja) * 1983-03-09 1984-09-14 Tokuyama Soda Co Ltd オレフイン類の気相酸化方法
JPH02119938A (ja) * 1988-10-31 1990-05-08 Chisso Corp エチレン除去剤、その製造方法およびエチレン除去用合成樹脂フィルム
JPH02222725A (ja) * 1989-02-27 1990-09-05 Chisso Corp エチレン除去剤、その製造法およびエチレン除去用合成樹脂フィルム
US5436067A (en) * 1993-11-22 1995-07-25 Kuraray Chemical Co., Ltd. Freshness keeping sheet

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DATABASE WPI Week 199529, Derwent World Patents Index; AN 1995-222707, XP002458530 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10021545B2 (en) 2008-09-29 2018-07-10 Electronics And Telecommunications Research Apparatus and method for transmitting and receiving data in wireless communication system using relay
US10994508B2 (en) 2015-05-12 2021-05-04 Innovia Films Limited Film
CN109364750A (zh) * 2018-12-10 2019-02-22 中石化上海工程有限公司 乙二醇生产装置中含氧尾气的处理方法
EP4215269A1 (fr) * 2022-01-19 2023-07-26 BASF Corporation Catalyseur d'hydrogénation emballé
WO2023139109A1 (fr) 2022-01-19 2023-07-27 Basf Corporation Catalyseur d'hydrogénation encapsulé

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