WO2011018374A1 - Désactiveurs d’oxygène - Google Patents

Désactiveurs d’oxygène Download PDF

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Publication number
WO2011018374A1
WO2011018374A1 PCT/EP2010/061187 EP2010061187W WO2011018374A1 WO 2011018374 A1 WO2011018374 A1 WO 2011018374A1 EP 2010061187 W EP2010061187 W EP 2010061187W WO 2011018374 A1 WO2011018374 A1 WO 2011018374A1
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WO
WIPO (PCT)
Prior art keywords
aluminosilicates
precursor composition
comprised
composition according
scavenger
Prior art date
Application number
PCT/EP2010/061187
Other languages
English (en)
Inventor
Roberto Macchi
Jürgen Sauer
Original Assignee
Saes Getters S.P.A.
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 Saes Getters S.P.A. filed Critical Saes Getters S.P.A.
Publication of WO2011018374A1 publication Critical patent/WO2011018374A1/fr

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Classifications

    • 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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J7/00—Details not provided for in the preceding groups and common to two or more basic types of discharge tubes or lamps
    • H01J7/14—Means for obtaining or maintaining the desired pressure within the vessel
    • H01J7/18—Means for absorbing or adsorbing gas, e.g. by gettering
    • H01J7/183—Composition or manufacture of getters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations

Definitions

  • the present invention refers to a new type of oxygen absorbers, a method for their activation and the use of such absorbers in anaerobic environments.
  • Oxygen absorbers also commonly referred to in the technical field with the term “oxygen scavengers” have a variety of applications. Among the most common ones there are food and medicine preservation. At industrial level there is a wide spectrum of other possible applications, spanning from the use within metallic piping in order to prevent corrosion, such as the ones for oil transportation, to the use within solid state or organic electronic systems, in order to prevent oxidation and degradation of the components installed therein. The most important devices of this latter category are OLED screens (Organic Light Emitting Display) and Organic Solar Cells (OSC). Another field of application of particular relevance is given by chemical syntheses or preparations that in intermediate process phases may be subject to the undesired generation of oxygen, which leads to the needing of its removal.
  • OLED screens Organic Light Emitting Display
  • OSC Organic Solar Cells
  • the oxygen scavenger remains essentially inert to oxygen until it is exposed to a meaningful concentration of humidity, which activates its function of O 2 scavenger.
  • US 5,798,055 discloses a preferred mode of use that provides for heating of the scavenger precursor once installed within the device in order to ease the H 2 O generation in the anaerobic environment and therefore trigger the functionality of the activated scavenger.
  • This type of solution has two different problems, the first one regarding the necessity of the presence of H 2 O in the closed environment for an effective O 2 sorption that is incompatible with many final application.
  • a typical example in this case is provided by the organo-electronic devices, where the presence of H 2 O is detrimental to the features of the device and therefore cannot be guarantee.
  • the second problem is related to the scavenger preservation, that must be made in an anhydrous environment in order to avoid its premature activation and the consequent loss of capacity.
  • This oxygen scavenger precursor composition comprise microporous aluminosilicates exchanged with bivalent metallic ions having a silica to alumina molar ratio comprised between 1.5 and 5 characterized in that said bivalent exchanged aluminosilicates are in their hydrated form.
  • scavenger precursor composition of the invention there is the possibility of storing and shipping them without particularly caring about the exposure to air.
  • These scavengers are inert to air because, being pre-saturated with H 2 O as a consequence of the production process of the exchanged aluminosilicates.
  • H 2 O occupies essentially all the sites active for the removal of O 2 .
  • H 2 O molecules occupy a number of active sites that is consequence of the thermodynamical equilibrium with the environmental humidity (generally equivalent to a water content comprise between 3.2 and 28% respect the total weight of the aluminosilicates) resulting in a limitated reactivity of the composition respect oxygen moleules until its activation treatment.
  • zeolites having a molar ratio silica to alumina lower than 2 require particular solutions in order to be manufactured. For this reason, in a preferred embodiment, such molar ratio is comprised between 2 and 2.5.
  • aluminosilicates also encompasses structures that may optionally comprise other metals/substituents such as e.g. germanium as substituent within the reticular structure of some silicon atoms, or gallium as substituent of some aluminum atoms.
  • Faujasite X Faujasite Y
  • LTA also known with the term Linde type A, X, Y are particularly suitable to carry out the invention.
  • Patent US 3,503,901 describes the catalytic use of aluminosilicates exchanged with divalent ions, preferably in association with a noble metal loading (i.e. Palladium). Differently to the present invention, it describes material suitable for manufacturing catalytic systems useful for organic chemistry reactions, with particular reference to hydrocarbon conversion reaction.
  • a noble metal loading i.e. Palladium
  • the inventors have instead focused their studies on a different application and technical problem, namely the oxygen removal, for which they have found that the use of aluminosilicates having a molar ratio between silica (SiO 2 ) and alumina
  • aluminosilicates exchanged with bivalent ions that are the object of the present invention, are typically used in the form of micrometric powders dispersed in a suitable polymeric matrix.
  • aluminosilicates are used in nanometric form, also in this case dispersed in a suitable polymeric matrix, the single elements of the matrix having a size below 400 nm.
  • the expression "single element” means the single particle of the aluminosilicates.
  • Polymers with thermoplastic or thermosetting characteristics or, more generally, polymers and their precursors that do not interfere with the oxygen absorbing function of the dispersed material can be employed as polymeric matrix.
  • Suitable polymeric materials for carrying out the invention are, as a non- limiting example, vinyl polymers, polyesters, polyethers, polyamides, polymers deriving from condensation of phenolformaldehyde, polysiloxanes, ionic polymers, polyurethanes, epoxy resins, acrylates, styrene block copolymers (SBS or SEBS gums) and natural polymers such as cellulose.
  • SBS or SEBS gums styrene block copolymers
  • Particularly interesting are also polymers chosen from the polyolefm family, also comprising block co-polymers of the same, among which butyl rubber and ethyl-vinyl-acetate copolymers have a particular importance.
  • the invention in a second aspect thereof, relates to an activation process for oxygen scavenger precursor, which can overcome the problems of the prior art.
  • This activation process consist in a thermal heating of the oxygen scavenger precursor composition comprising hydrated aluminosilicates exchanged with bivalent metallic ions having a silica to alumina molar ratio comprised between 1.5 and 5 and characterized in that the water amount removed by said activation process is comprised between 3 and 25 wt % respect to the aluminosilicate weight.
  • the aluminosilicates object of the present invention it has been found that an efficient activation process leads to a weight loss comprised between 5 and 20% after they have been saturated with H 2 O.
  • the estimation of the percentage weight loss shall be made with respect to the whole amount of aluminosilicates.
  • Such weight loss may be achieved by means of a suitable heating, typically carried out in vacuum or inert gas, for example by heating for a time ranging between 5 and 30 minutes and temperatures between 120 0 C and 300 0 C. Obviously, when low activation temperatures are used the corresponding activation times are longer. Atypical example of suitable activation process leading to a 7% weight loss can be achieved by heating at 200 0 C for 10-15 minutes. In alternative, when heating is carried out in no inert conditions, scavenger properties can be substantially preserved simply limiting the exposure to the environment before its complete cooling.
  • the invention in a third aspect thereof relates to the use of aluminosilicates exchanged with bivalent metallic ions having a molar ratio between silica and alumina comprised between 1.5 and 5 for the removal of O 2 from anaerobic environments, characterized in that said aluminosilicates have a water amount comprised between 0.2 and 3 wt% respect the aluminosilicates weight.
  • aluminosilicates are in fact the activated form of the oxygen precursor composition described above by the previous described aspect of the invention.
  • the method provides for the use of aluminosilicates exchanged with bivalent ions of chromium, manganese or combinations of bivalent ions of chromium and manganese.
  • the aluminosilicates are used in the form of powder dispersed in a suitable polymeric matrix, although the aluminosilicates may also possibly be used within suitable permeable containers or in pill form, in which a suitable binder is added to the zeolite in order to grant mechanical integrity.
  • the method may advantageously be applied in the case of food and medicine packaging, or used for oxygen removal from the internal atmosphere of electronic or organo-electronic devices, such as OLED screens and organic solar cells.
  • a batch of oxygen scavenger was prepared by exchanging a Faujasite X with
  • the ion exchange reaction was performed in degassed, oxygen free water under inert atmosphere (Argon) by using Cr(Cl) 2 at a concentration of 1 mol/liter for 10 minutes under stirring.
  • the solid was rinsed with degassed deionized water under inert gas atmosphere using schlenk equipment. It was dried at ambient temperature overnight.
  • the Zeolite changed is color from white to light blue.
  • 500 mg of sample was the heated under dynamic vacuum at 200 0 C for 60 minutes, naturally cooled to room temperature and then exposed to dry air. The sample gained about 3.5 % wt, and turned its color to brown.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

La présente invention concerne une nouvelle composition de précurseur pour des désactiveurs d’oxygène constitués d’aluminosilicates échangés avec des ions métalliques bivalents, un procédé pour leur activation et leur utilisation en tant que sorbant d’oxygène dans des environnements anaérobies.
PCT/EP2010/061187 2009-08-12 2010-08-02 Désactiveurs d’oxygène WO2011018374A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2009A001465 2009-08-12
IT001465A ITMI20091465A1 (it) 2009-08-12 2009-08-12 Assorbitore di ossigeno

Publications (1)

Publication Number Publication Date
WO2011018374A1 true WO2011018374A1 (fr) 2011-02-17

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IT (1) ITMI20091465A1 (fr)
WO (1) WO2011018374A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013982A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Metal loading of molecular sieves
US3503901A (en) 1969-01-13 1970-03-31 Union Carbide Corp Chemical reaction catalyst and its preparation
US5234876A (en) 1992-10-20 1993-08-10 Corning Incorporated Thermally stable chromium-exchanged zeolites and method of making same
WO1997006104A1 (fr) 1995-08-07 1997-02-20 Saes Getters S.P.A. Procede permettant d'extraire de l'oxygene de gaz ammoniac a temperature ambiante
US5798055A (en) 1995-12-15 1998-08-25 Blinka; Thomas Andrew Oxygen scavenging metal-loaded ion-exchange compositions
WO1999047351A1 (fr) 1998-03-19 1999-09-23 W.R. Grace & Co.-Conn. Compositions desoxygenantes et leurs procedes de production
WO2007013118A1 (fr) * 2005-07-29 2007-02-01 Saes Getters S.P.A. Systemes de getter comprenant une phase de sorption de gaz dans les pores d'un materiau poreux distribue dans un moyen permeable

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013982A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Metal loading of molecular sieves
US3503901A (en) 1969-01-13 1970-03-31 Union Carbide Corp Chemical reaction catalyst and its preparation
US5234876A (en) 1992-10-20 1993-08-10 Corning Incorporated Thermally stable chromium-exchanged zeolites and method of making same
WO1997006104A1 (fr) 1995-08-07 1997-02-20 Saes Getters S.P.A. Procede permettant d'extraire de l'oxygene de gaz ammoniac a temperature ambiante
US5798055A (en) 1995-12-15 1998-08-25 Blinka; Thomas Andrew Oxygen scavenging metal-loaded ion-exchange compositions
WO1999047351A1 (fr) 1998-03-19 1999-09-23 W.R. Grace & Co.-Conn. Compositions desoxygenantes et leurs procedes de production
WO2007013118A1 (fr) * 2005-07-29 2007-02-01 Saes Getters S.P.A. Systemes de getter comprenant une phase de sorption de gaz dans les pores d'un materiau poreux distribue dans un moyen permeable

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KELLERMAN R; HUTTA PJ; KLIER K: "Reversible Oxygen Binding by Divalent Chromium(II) Ion Exchanged Molecular Sieve", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 96, no. 18, 4 September 1974 (1974-09-04), pages 5946 - 5947, XP002573247, ISSN: 0002-7863, DOI: 10.1021/ja00825a048 *
QIU L; LAWS PA; BI-ZENG Z; WHITE MA: "Thermodynamic investigations of zeolites NaX and NaY", CANADIAN JOURNAL OF CHEMISTRY, vol. 84, 22 February 2006 (2006-02-22), pages 134 - 139, XP002573246, ISSN: 1480-3291, DOI: 10.1139/V05-244 *
SEBASTIAN J; PILLAI R S; SUNIL AP; JASRA R V: "Sorption of N2, O2, and Ar in Mn(II)-Exchanged Zeolites A and X Using Volumetric Measurements and Grand Canonical Monte Carlo Simulation", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 46, no. 19, 9 August 2007 (2007-08-09), pages 6293 - 6302, XP002573245, ISSN: 0888-5885, DOI: 10.1021/ie070067w *

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