FR2693118A1 - Plastic waste degradation by chemical reaction - induced by external radiation, e.g. UV, ionising radiation, ultrasonic or heat generating free radicals causing degradation - Google Patents

Plastic waste degradation by chemical reaction - induced by external radiation, e.g. UV, ionising radiation, ultrasonic or heat generating free radicals causing degradation Download PDF

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FR2693118A1
FR2693118A1 FR9208559A FR9208559A FR2693118A1 FR 2693118 A1 FR2693118 A1 FR 2693118A1 FR 9208559 A FR9208559 A FR 9208559A FR 9208559 A FR9208559 A FR 9208559A FR 2693118 A1 FR2693118 A1 FR 2693118A1
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radiation
degradation
ultrasonic
free radicals
plastic waste
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Mezza Michel
Berthomieu Brigitte
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    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/13Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to sonic energy
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • A62D3/176Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

Plastic waste material partic. household waste is treated prior to disposed by exposure to radiation able to induce free radical functions that cause photodegradation in the plastic. The externally applied radiation is UV, ionising radiation, ultrasonic or heat. Prior to exposure metal oxides or metal salts or colourants are added to the compsn. USE/ADVANTAGE - To render all plastic prods. degradable. Produces no air pollutants compared to incineration and is an alternative to biodegradable prods.

Description

Mise en application de reactions chimiques afin de dégrader des produits en matières plastiques diverses.Application of chemical reactions to degrade products made of various plastics.

La présente invention concerne la mise en application de réactions chimiques afin de fragmenter tous produits en matière plastique.The present invention relates to the application of chemical reactions to fragment any plastic products.

Les ordures ménagères a base de plastique sont a l'heure actuelle considérées comme une nuisance à réduire.Plastic-based household garbage is currently considered a nuisance to be reduced.

Les modes de traitements d'aujourd'hui sont:
-I'incinération
- la décharge dite contrôlée
- le recyclage
- la biodégrabilité
L'incinération.
Today's treatment modes are:
-I'incinération
- the so-called controlled discharge
- the recycling
- the biodegradability
Incineration.

Elle traite 12% des déchets plastiques ménagères. L'incinération reste difficile à mettre en oeuvre car elle nécessite un tri spécifique (Ex: Pour un même polymère, il existe des dizaines de grades différents). D'une manière générale, les déchets plastiques sont trop disparatres pour pouvoir être traités de la même façon car ceux-ci polluent l'atmosphère comme le PVC qui dégage des émanations d'acide chlorhydrique.It processes 12% of household plastic waste. Incineration remains difficult to implement because it requires specific sorting (Ex: For the same polymer, there are dozens of different grades). In general, plastic waste is too disparate to be treated in the same way because they pollute the atmosphere such as PVC which emits hydrochloric acid fumes.

La décharge dite contrôlée.The so-called controlled discharge.

Elle doit en effet répondre à des critères stricts concernant le choix du site d'enfouissement.Celui-ci est déterminé en fonction d'études géologiques et hydrogéologiques sur l'environnement.It must meet strict criteria concerning the choice of the landfill site. This is determined by geological and hydrogeological studies on the environment.

Son exploitation est très suivie notamment au point de vue de l'étanchéité et des risques d'incendie qui sont accrus par les matières plastiques. Les sites d'enfouissement sont peu à peu menacés d'engorgement et ceci est surtout attribuable aux plastiques. En outre, le patrimoine des sites d'enfouissement n'est pas illimité et déjà son érosion se fait sentir. Le tri des différents matériaux valorisables sur le volume global des ordures ménagères est quelquefois réalisé; il est cependant très difficileet côuteux. Celà représente 43% des plastiques de consommation ménagère.Its operation is very popular especially in terms of watertightness and fire risks which are increased by plastics. Landfill sites are slowly becoming waterlogged and this is mostly due to plastics. In addition, the heritage of landfills is not unlimited and already its erosion is felt. The sorting of the different recyclable materials on the overall volume of household refuse is sometimes realized; however, it is very difficult and expensive. This represents 43% of household plastics.

Le recyclage. The recycling.

Les déchets plastiques recyclables sont souvent souillés par les phases organiques des ordures ménagères dont ils sont issus.Recyclable plastic waste is often contaminated by the organic phases of household waste from which it is derived.

Leur recyclage devient plus délicat et coûteux car il implique un lavage préalable. La collecte séléctive est une autre solution qui pourrait être employée surtout pour le PVC. De telles collectes demandent des efforts aux consommateurs qui doivent porter leurs déchets dans différents containers spéciaux disséminés un peu partout dans leurs villes. L'effort demandé au public devient alors trop important.Their recycling becomes more delicate and expensive because it involves a preliminary washing. Selective collection is another solution that could be used especially for PVC. Such collections require efforts from consumers who must carry their waste in different special containers scattered throughout their cities. The effort required from the public becomes too important.

Le recyclage énergétique traite 27% des déchets plastiques et le recyclage matière traite de 1 à 2%.Energy recycling processes 27% of plastic waste and material recycling processes 1% to 2%.

La biodégrabilité.Biodegradability

Elle suppose la destruction complète du contenant par des microorganismes vivants, dont le démarrage du processus n'est pas prévisible ce qui peut survenir lors du stockage, du transport où de la distribution.It assumes the complete destruction of the container by live microorganisms, whose start of the process is not predictable which can occur during storage, transport or distribution.

Les plastiques biodégradables sont issus de l'Agro-chimie. Ils sont composés de glucose et d'amidon de maïs. Ceux-ci ne peuvent prétendre à des applications en milieu aqueux car en contact avec de l'eau, ils perdent leur tenue. Ces propriétés sont incompatibles avec la fonction Emballage.Biodegradable plastics are from Agro-chemistry. They are composed of glucose and corn starch. These can not claim applications in an aqueous environment because in contact with water, they lose their behavior. These properties are incompatible with the Packaging function.

II n'existe donc pas de solution pouvant résoudre globalement le problème des déchets plastiques au niveau des emballages. There is therefore no solution that can globally solve the problem of plastic waste packaging.

Le procédé de l'invention que nous avons retenu comme moyen de dégradation est l'application d'une réaction chimique engendrée par une source extérieure d'énergie.The process of the invention that we have chosen as degradation means is the application of a chemical reaction generated by an external source of energy.

Celle-ci pourra être:
- la chaleur provenant de rayons solaires.
This one can be:
- heat from solar rays.

- I'ionisation de rayonnements divers. The ionization of various radiations.

- les rayons ultra-violets solaires
les ultra-sons de provenances diverses.
- solar ultra-violet rays
ultrasounds of various origins.

La dégradation dans le cas de polyolefines consiste en une phase d'initiation durant laquelle l'hydrogène est soustrait de la molécule du polymère conduisant a un radical libre. Cette apparition de radicaux libres pourra avoir lieu par des rayons ultra-violets, des rayons ionisants, de la chaleur, des ultra-sons. Une fois l'initiation établie et de petites fractions de radicaux libres formés, la propagation se produit. La première réaction étant la formation rapide d'un radical peroxy résultant de la réaction d'addition du radical avec l'oxygène. La vitesse de réaction de l'oxygène sur un radical de bas poids moléculaire depend de sa structure. Le radical peroxy peut arracher un atome d'hydrogène d'une molécule du polymère pour former un hydroperoxyde avec libération simultanée d'un nouveau radical libre.The degradation in the case of polyolefins consists of an initiation phase during which hydrogen is removed from the polymer molecule leading to a free radical. This appearance of free radicals may take place by ultraviolet rays, ionizing rays, heat, ultrasounds. Once established initiation and small fractions of free radicals formed, the spread occurs. The first reaction is the rapid formation of a peroxy radical resulting from the addition reaction of the radical with oxygen. The rate of reaction of oxygen on a radical of low molecular weight depends on its structure. The peroxy radical can scavenge a hydrogen atom from one molecule of the polymer to form a hydroperoxide with simultaneous release of a new free radical.

Exemple: Propagation.

Figure img00030001
Example: Propagation.
Figure img00030001

Le processus de propagation dépend de la facilité d'enlèvement de l'hydrogène des différentes structures présentés dans les polymères. Les groupes carbonyl, les points d'insaturation ethyleniques existant dans les polyoléfines facilitent cette abstraction de l'hydrogène. En fonction de la réaction, chaque étape de la propagation conduit a un radical identique au radical formé dans la réaction d'initiation. Ce radical pouvant donc réagir avec l'oxygène d'une façon similaire, avec formation d'un radical polymère. II en résultera l'initiation de nouvelles chaines d'oxydation par accumulation des hydroperoxydes et de leur décomposition en radicaux, la vitesse d'oxydation s'accélère. La terminaison est due à la réaction des radicaux libres par des combinaisons conduisant à la formation de produits inactifs.The propagation process depends on the ease of removal of hydrogen from the different structures presented in the polymers. The carbonyl groups, the ethylenic unsaturation points existing in the polyolefins facilitate this abstraction of hydrogen. Depending on the reaction, each stage of the propagation leads to a radical identical to the radical formed in the initiation reaction. This radical can therefore react with oxygen in a similar manner, with formation of a polymer radical. This will result in the initiation of new oxidation chains by accumulation of hydroperoxides and their decomposition into radicals, the rate of oxidation accelerates. The termination is due to the reaction of free radicals by combinations leading to the formation of inactive products.

Exemple:

Figure img00030002
Example:
Figure img00030002

<tb> ROO <SEP> + <SEP> ROO <SEP> --------- > <SEP> ROOR <SEP> <SEP> + <SEP> R00R+02 <SEP>
<tb> ROO+R <SEP> --------- > <SEP> > <SEP> ROOR <SEP> Produits <SEP> inactifs
<tb> R <SEP> +R <SEP> --------- > <SEP> R-R
<tb>
Mais avant que ce stade ne soit atteint, une sévère dégradation s'est produite amenant la chute des caractéristiques électriques et mécaniques quand la décomposition des hydropéroxydes formés commence à se produire à une vitesse rapide, l'oxydation devient alors autocatalytique.
<tb> ROO <SEP> + <SEP> ROO <SEP>---------><SEP> ROOR <SEP><SEP> + <SEP> R00R + 02 <SEP>
<tb> ROO + R <SEP>---------><SEP>><SEP> ROOR <SEP> Inactive <SEP> Products
<tb> R <SEP> + R <SEP>---------><SEP> RR
<Tb>
But before this stage is reached, a severe degradation has occurred bringing about the fall of electrical and mechanical characteristics when the decomposition of hydroperoxides formed begins to occur at a fast speed, the oxidation then becomes autocatalytic.

Cette invention est la mise en application d'une réaction chimique conduisant toute matière plastique à la perte de ses caracté ristiques mécaniques afin d'accélérer cette dégradation qui sera due à une source d'énergie extérieure (rayonnements ultraviolets, rayonnements ionisants, chaleur, ultra-sons), nous incorporerons des adjuvants accélérants l'oxydation des polymères. Ces adjuvants seront donc tous les produits succeptibles de dégager des ions métalliques (oxydes métalliques, sels, colorants) afin de rendre dans un délai variable tout produit plastique dégradable. Nous prendrons comme norme de fragmentation la densité optique à 1715 cm-4 mesurée à l'aide d'un spectrophotomètre à infra-rouge. S i cette densité optique est égale à 1,0 pour une épaisseur de 100 microns, il y a donc fragmentation et perte des caractéristiques mécaniques. This invention is the implementation of a chemical reaction leading all plastic material to the loss of its mechanical characteristics in order to accelerate this degradation which will be due to an external energy source (ultraviolet radiation, ionizing radiation, heat, ultra -sons), we will incorporate adjuvants accelerating the oxidation of polymers. These adjuvants will therefore all products likely to release metal ions (metal oxides, salts, dyes) to make in a variable time any degradable plastic product. As a fragmentation standard, we will take the optical density at 1715 cm-4 measured using an infra-red spectrophotometer. If this optical density is 1.0 for a thickness of 100 microns, there is fragmentation and loss of mechanical characteristics.

Claims (3)

REVENDICATIONS i) Procédé de traitement des ordures ménagères comprenant des(i) Domestic waste treatment process including matières plastiques caractérisé en ce que préalablement à plastics characterized in that prior to leur dépôt dans un site, on les expose à un rayonnement their deposit in a site, they are exposed to radiation succeptible d'induire la fonction de radicaux libres, d'où likely to induce the function of free radicals, hence il semble une photodégrabilité avenue des matières plastiques it seems a photodegradability avenue of plastics constitutives. constituent. de la chaleur. heat. rayons ionisants, des rayons ultra-violets, des ultra-sons,  ionizing radiation, ultraviolet rays, ultrasound, l'un au moins des rayonnements du groupe comprendra des at least one of the group's radiations will include dication 1 caractérisé en ce que le dit rayonnement, soit cation 1 characterized in that the said radiation, 2) Procédé de traitement des ordures ménagères selon la reven2) Method of treatment of garbage according to the revenge liques et des sels métalliques.  and metal salts. un composé métallique du groupe comprenant des oxydes métal a metal compound of the group comprising metal oxides tion aux rayonnements, on incorpore aux matières plastiques radiation is incorporated into plastics dication 2 caractérisé en ce que, préalablement à l'exposi 2, characterized in that prior to the exposure 3) Procédé de traitement des ordures ménagères selon la reven3) Method of treatment of garbage according to the revenge
FR9208559A 1992-07-03 1992-07-03 Plastic waste degradation by chemical reaction - induced by external radiation, e.g. UV, ionising radiation, ultrasonic or heat generating free radicals causing degradation Withdrawn FR2693118A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5515716A (en) * 1994-08-22 1996-05-14 University Of Nevada-Las Vegas Method of detecting pollution in water using sonication

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916766A (en) * 1972-06-02 1974-02-14
FR2233353A1 (en) * 1973-06-14 1975-01-10 Tsutomu Kagiya Breakdown of polymer waste - by photo-oxidation in presence of chlorinated carbonyl cpds
WO1988008871A1 (en) * 1987-05-13 1988-11-17 Kenneth Michael Holland Destruction of plastics waste
WO1989008079A1 (en) * 1988-03-02 1989-09-08 Trustees Of Boston University Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products
US5069885A (en) * 1990-04-23 1991-12-03 Ritchie David G Photocatalytic fluid purification apparatus having helical nontransparent substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916766A (en) * 1972-06-02 1974-02-14
FR2233353A1 (en) * 1973-06-14 1975-01-10 Tsutomu Kagiya Breakdown of polymer waste - by photo-oxidation in presence of chlorinated carbonyl cpds
WO1988008871A1 (en) * 1987-05-13 1988-11-17 Kenneth Michael Holland Destruction of plastics waste
WO1989008079A1 (en) * 1988-03-02 1989-09-08 Trustees Of Boston University Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products
US5069885A (en) * 1990-04-23 1991-12-03 Ritchie David G Photocatalytic fluid purification apparatus having helical nontransparent substrate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7443, Derwent Publications Ltd., London, GB; AN 74-74848 & JP-A-49 016 766 (CANON) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5515716A (en) * 1994-08-22 1996-05-14 University Of Nevada-Las Vegas Method of detecting pollution in water using sonication

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