WO2000035304A1 - Procede catalytique - Google Patents

Procede catalytique Download PDF

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Publication number
WO2000035304A1
WO2000035304A1 PCT/GB1999/004100 GB9904100W WO0035304A1 WO 2000035304 A1 WO2000035304 A1 WO 2000035304A1 GB 9904100 W GB9904100 W GB 9904100W WO 0035304 A1 WO0035304 A1 WO 0035304A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
package
catalyst
scavenging composition
oxygen scavenging
Prior art date
Application number
PCT/GB1999/004100
Other languages
English (en)
Inventor
Amanda Maria Elsome
John Malcolm Gascoyne
Hugh Gavin Hamilton
Allin Sidney Pratt
Raj Rao Rajaram
Elizabeth Slade
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Priority to AU15771/00A priority Critical patent/AU1577100A/en
Publication of WO2000035304A1 publication Critical patent/WO2000035304A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23L3/3436—Oxygen absorbent

Definitions

  • This invention relates to a method of removing small quantities of entrained oxygen from closed containers, sealed bags and the like (hereinafter called “sealed packages”) which contain oxidisable products, including perishable foodstuff, by utilisation of catalytic oxygen scavenging composition.
  • oxidisable product includes materials which are damaged by oxygen or spoiled by micro-organisations in the presence of oxygen.
  • the small quantities of entrained oxygen can be eliminated by including hydrogen in the sealed package to react with the entrained oxygen to produce water.
  • a quantity of hydrogen equal to or greater than that stoichiometrically required to combine with the entrained oxygen is introduced into the package along with an inert gas or gases either before or after sealing.
  • Such foodstuff preservation methods utilise catalysts which have high activity for combining hydrogen and oxygen to produce water.
  • Suitable catalysts include platinum group metals which conveniently can be impregnated on a finely divided inert porous support material. Such supported catalysts are commonly contained in sealed pouches or sachets of microporous film which are stuck on to the interior surface of the packaging material. Sealed pouches or sachets, however, suffer from the disadvantage that the sachet is liable to ruption with the catalyst getting onto the foodstuff.
  • An object of the present invention is to provide an improved oxygen scavenging system which obviates or mitigates the problems experienced with systems containing moisture and carbon dioxide.
  • a method of removing entrained oxygen in a sealed package containing an oxidisable product comprising (1) applying to a predetermined area of the intended inside surface of the package an oxygen scavenging composition comprising a mixture of a hydrophobic material and a catalyst which has a high activity for combining hydrogen and oxygen and (2) introducing into the package before or after sealing hydrogen and an inert gas or gases including carbon dioxide; the hydrogen being present in the package in sufficient amount to react with the entrained oxygen to form water.
  • the catalyst comprises a platinum group metal or combinations thereof.
  • the catalyst may be in the form of a finely divided unsupported material or it may be supported on a porous inert carrier.
  • the porous inert carrier is carbon, alumina, zirconia, silica, ceria, titania or an insoluble carbonate.
  • the hydrophobic material is a fluorocarbon polymer.
  • the fluorocarbon polymer is polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, polychlorofiuoroethylene, polyvinylidene fluoride or mixtures thereof.
  • the oxygen scavenging composition contains a water-insoluble adhesive material.
  • the adhesive material is poly(vinylbutyral), nitrocellulose, ethyl cellulose, a polyurethane or a silicone material.
  • the oxygen scavenging composition contains one or more additives commonly used in ink compositions (including UV curable inks) such as one or more of plasticisers, fillers, driers, surfactants and pigments.
  • additives commonly used in ink compositions such as one or more of plasticisers, fillers, driers, surfactants and pigments.
  • the catalyst particles are partially encapsulated on the surface of the oxygen scavenging composition.
  • the oxygen scavenging composition comprises a minor weight amount of the hydrophobic material and a major weight amount of the catalyst.
  • the oxygen scavenging composition is applied to the intended inside surface of the package by printing, brushing, spraying or powder coating.
  • the oxygen scavenging composition comprises a label which is attached to the intended inside surface of the package.
  • the method of the present invention is particularly suitable for the preservation of perishable foodstuffs, especially moist perishable foodstuffs.
  • the present invention is a sealed package containing an oxidisable product from which package oxygen has been removed by the methods specified above.
  • the present invention is the use as an oxygen scavenger of a catalytic/hydrophobic composition as specified above.
  • the hydrophobic polymeric particles and catalyst particles may be blended by any convenient technique that will produce a uniform mixture.
  • an aqueous suspension may be formed by conventional techniques, such as high shear mixing of a mixture of catalyst particles and an aqueous dispersion of hydrophobic polymer particles.
  • the aqueous suspension is then caused to aggregate (floe), such as by heating or adding a floccing agent.
  • aggregate such as by heating or adding a floccing agent.
  • Alternative methods of obtaining the blend of catalyst particles and hydrophobic polymer particles are disclosed in US Patents Nos. 4,185,131; 4,382,875; 4,851,377 and 4,927,514, the disclosures of which are incorporated herein by reference.
  • the sealed packages holding the oxygen scavenging composition and the perishable foodstuff or other oxidisable product may be in the form of plastic bags, metal cans, glass jars and the like or they may be made of plastic film materials, aluminium foil or combinations thereof as well as of paper or cardboard types of materials which in turn may be coated or impregnated with wax or plastic to provide generally air impervious and waterproof materials.
  • the oxygen scavenging composition of the present invention can be applied in a distributed manner on the interior surface of the packaging material thus providing an extended surface area of contact for the entrained oxygen and the hydrogen within the sealed package.
  • Such an extended area of contact is more difficult to achieve with pouches or sachets containing the catalyst due to restricted gas access to the catalyst.
  • the oxygen scavenger can be face down to the packaging material.
  • the oxygen scavengers of the invention can be used in other applications where small quantities of entrained oxygen can have a detrimental effect on oxidisable products.
  • the present invention can be applied usefully to the storage of chemicals, pharmaceuticals, clothes, skins, medical equipment, instruments, electronic components, artefacts, security packages (eg bank notes) and other oxidisable products.
  • the activity of the scavengers tested in the following Examples is expressed as the time (T 50 ) taken for the oxygen content of the test gas to be reduced by 50%.
  • Rh black flocced with 15wt% PTFE (Fluon GP1, Whitford Plastics Ltd) was dispersed in 39ml of a 1% polyurethane solution (lg polyurethane (Estane 5202F, B.F. Goodrich) made up to 1 OOg with methyl ethyl ketone/ethyl acetate (9: 1 )).
  • the suspension was subjected to high shear mixing for a period of 20 minutes. It was then sprayed on to 150 ⁇ m polyurethane film (Tuftane TFL-1EA, Lord Corporation) marked out with insulation tape into 2cm by 2cm squares and then left to air dry.
  • One label was removed from the sheet and tested for oxygen scavenging ability. This had a T 50 of 20 minutes and furthermore reduced the oxygen level to 0.08% in 180 minutes.
  • a further ink composition containing Pd black at an equivalent metal loading to the inks described in Examples 1 & 2 above was prepared.
  • Pd black was flocced with 9wt% PTFE and 0.53g of the catalyst was mixed with 39ml of 1% polyurethane solution (as described in Example 1).
  • the suspension was sprayed on to polyurethane sheet marked out into 2 x 2 cm squares and left to air dry. One of these labels was removed from the sheet and found to have a T 50 of 235 minutes.
  • An ink was prepared using 1.94g Pt:Ru black (50:50) flocced with 10wt% PTFE dispersed in 39ml of 1 % polyurethane solution (described in Example 1 ). The suspension was high shear mixed and subsequently sprayed on to a polyurethane sheet template of 2 x 2 cm squares, then left to air dry. One of the labels was tested and gave a T 50 value of 40 minutes and reduced the oxygen concentration in the test bag to 0.2% in 150 minutes.
  • a further ink was made using the Pt:Ru black catalyst (as detailed in Example 5), flocced with 20wt% PTFE. 1.94g of this catalyst was dispersed in 2% polyurethane solution (lg of polyurethane made up to 50g with methyl ethyl ketone/ethyl acetate (9:1)) and high shear mixed. The ink was sprayed on to a polyurethane sheet template of 2cm by 2cm squares and the labels left to air dry. One label was selected for testing and reduced the oxygen concentration to 0.52% after 270 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Gas Separation By Absorption (AREA)
  • Packages (AREA)

Abstract

L'invention concerne un procédé d'élimination de l'oxygène entraîné dans un conditionnement scellé contenant un produit pouvant s'oxyder, qui comporte les étapes consistant à: (1) appliquer sur une zone prédéterminée de la surface intérieure voulue du conditionnement une composition désoxygénante renfermant un mélange composé d'une matière hydrophobe et d'un catalyseur, ce mélange présentant une forte activité de combinaison d'hydrogène et d'oxygène; et (2) introduire dans le conditionnement avant ou après scellage de l'hydrogène et un ou des gaz inerte(s), y compris du dioxyde de carbone; l'hydrogène est présent dans le conditionnement en quantité suffisante pour réagir avec l'oxygène entraîné et former de l'eau. Le catalyseur comporte un métal de la mine du platine ou des combinaisons de celui-ci. La matière hydrophobe est du polytétrafluoréthylène, un copolymère éthylène-propylène fluoré, du polychlorofluoroéthylène, du fluorure de polyvinylidène ou des mélanges de ceux-ci. La composition désoxygénante peut contenir un adhésif insoluble dans l'eau pouvant être du poly(vinylbutyral), de la nitrocellulose, de l'éthyl cellulose, un polyuréthanne ou une matière de silicone.
PCT/GB1999/004100 1998-12-11 1999-12-10 Procede catalytique WO2000035304A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU15771/00A AU1577100A (en) 1998-12-11 1999-12-10 Catalytic process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9827195.0 1998-12-11
GBGB9827195.0A GB9827195D0 (en) 1998-12-11 1998-12-11 Catalytic process

Publications (1)

Publication Number Publication Date
WO2000035304A1 true WO2000035304A1 (fr) 2000-06-22

Family

ID=10843983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/004100 WO2000035304A1 (fr) 1998-12-11 1999-12-10 Procede catalytique

Country Status (3)

Country Link
AU (1) AU1577100A (fr)
GB (1) GB9827195D0 (fr)
WO (1) WO2000035304A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007059903A1 (fr) * 2005-11-22 2007-05-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Systeme composite, utilisation de celui et procede pour emballer dans une atmosphere exempte d'oxygene des produits a emballer sensibles a l'oxydation
WO2011112696A3 (fr) * 2010-03-12 2011-11-24 Amcor Limited Contenant présentant un système d'activation de piégeage d'oxygène
US9108176B2 (en) 2010-06-25 2015-08-18 Amcor Limited Oxygen scavenging system for a container
US9289938B2 (en) 2010-03-12 2016-03-22 Amcor Limited Container having oxygen scavenging system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927514A (en) * 1988-09-01 1990-05-22 Eltech Systems Corporation Platinum black air cathode, method of operating same, and layered gas diffusion electrode of improved inter-layer bonding
JPH05208473A (ja) * 1992-01-31 1993-08-20 Mishima Seishi Kk 通気性撥油紙及びその製造方法
WO1993019937A1 (fr) * 1990-10-12 1993-10-14 Gelman Sciences, Inc. Emballage pour agent de conservation et son procede de fabrication
WO1996007711A1 (fr) * 1994-09-08 1996-03-14 Multisorb Technologies, Inc. Composition absorbant l'oxygene
EP0861602A1 (fr) * 1997-02-19 1998-09-02 Mitsubishi Gas Chemical Company, Inc. Agent absorbant l'oxygène sous forme d'étiquette
WO1999005922A1 (fr) * 1997-07-30 1999-02-11 Johnson Matthey Public Limited Company Procede catalytique visant a eliminer l'oxygene de contenants hermetiquement fermes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927514A (en) * 1988-09-01 1990-05-22 Eltech Systems Corporation Platinum black air cathode, method of operating same, and layered gas diffusion electrode of improved inter-layer bonding
WO1993019937A1 (fr) * 1990-10-12 1993-10-14 Gelman Sciences, Inc. Emballage pour agent de conservation et son procede de fabrication
JPH05208473A (ja) * 1992-01-31 1993-08-20 Mishima Seishi Kk 通気性撥油紙及びその製造方法
WO1996007711A1 (fr) * 1994-09-08 1996-03-14 Multisorb Technologies, Inc. Composition absorbant l'oxygene
EP0861602A1 (fr) * 1997-02-19 1998-09-02 Mitsubishi Gas Chemical Company, Inc. Agent absorbant l'oxygène sous forme d'étiquette
WO1999005922A1 (fr) * 1997-07-30 1999-02-11 Johnson Matthey Public Limited Company Procede catalytique visant a eliminer l'oxygene de contenants hermetiquement fermes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. O' KEEFFE ET AL.: "Anoxic storage of fresh beef. I: Nitrogen and carbon dioxide storage atmospheres", MEAT SCIENCE., vol. 5, no. 1, 1981, ELSEVIER SCIENCE., GB, pages 27 - 39, XP002079066, ISSN: 0309-1740 *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 648 (M - 1518) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007059903A1 (fr) * 2005-11-22 2007-05-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Systeme composite, utilisation de celui et procede pour emballer dans une atmosphere exempte d'oxygene des produits a emballer sensibles a l'oxydation
JP2009516605A (ja) * 2005-11-22 2009-04-23 フラオンホファー−ゲゼルシャフト・ツア・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファオ 複合システムとその使用、および酸化されやすい包装物品を酸素非含有包装する方法
WO2011112696A3 (fr) * 2010-03-12 2011-11-24 Amcor Limited Contenant présentant un système d'activation de piégeage d'oxygène
US9289938B2 (en) 2010-03-12 2016-03-22 Amcor Limited Container having oxygen scavenging system
US9108176B2 (en) 2010-06-25 2015-08-18 Amcor Limited Oxygen scavenging system for a container
US9662622B2 (en) 2010-06-25 2017-05-30 Amcor Limited Oxygen scavenging system for a container

Also Published As

Publication number Publication date
AU1577100A (en) 2000-07-03
GB9827195D0 (en) 1999-02-03

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