DE4204094A1 - Hydrothermal decomposition of polymers - esp. de-vulcanisation of rubber, for reuse of sepd. components - Google Patents
Hydrothermal decomposition of polymers - esp. de-vulcanisation of rubber, for reuse of sepd. componentsInfo
- Publication number
- DE4204094A1 DE4204094A1 DE19924204094 DE4204094A DE4204094A1 DE 4204094 A1 DE4204094 A1 DE 4204094A1 DE 19924204094 DE19924204094 DE 19924204094 DE 4204094 A DE4204094 A DE 4204094A DE 4204094 A1 DE4204094 A1 DE 4204094A1
- Authority
- DE
- Germany
- Prior art keywords
- esp
- polymers
- rubber
- water
- reuse
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
Technische Gummis stellen Vielkomponenten-Werkstoffe dar und sind Träger hochwertiger Rohstoffe. Ein Verwertungsverfahren für Altgummis, das dem Wertstoffgehalt Rechnung trägt, setzt eine Separation der Komponenten voraus. Diese Forderung ist Ausgangspunkt eines von einem der Erfinder entwickelten Verfahrens zur Verwertung von Naturkautschuk-Gummis, das eine Fest-Flüssig-Extraktion der zerkleinerten Gummiprodukte (Weichmacherabtrennung) und einen sauer-oxidativen Abbau des Vulkanisats mit Separation des dabei erhaltenen Naturkautschuk- Derivats vom freigesetzten Ruß beinhaltet.Technical rubbers are multi-component materials and are carriers of high quality raw materials. A recovery process for waste rubber, which takes into account the recyclable content separation of the components beforehand. This requirement is Starting point for one developed by one of the inventors Process for the recovery of natural rubber rubbers, the one Solid-liquid extraction of the shredded rubber products (Plasticizer removal) and an acidic oxidative degradation of the Vulcanizate with separation of the natural rubber Released from released carbon black.
Dieses Verfahren ist mit folgenden Nachteilen behaftet:This method has the following disadvantages:
- - es ist auf Naturkautschuk-Gummis beschränkt. Andere Gummitypen lassen sich damit nicht abbauen.- It is limited to natural rubber rubbers. Other rubber types cannot be dismantled with it.
- - der Naturkautschuk wird zu relativ niedermolekularen hydroxyfunktionellen Polymeren abgebaut, für die noch keine Verwendung gefunden sind.- Natural rubber becomes relatively low molecular weight degraded hydroxy-functional polymers for which none Are used.
- - das sauer-oxidative Abbaureagenz ist eine relativ teure Chemikalie und wird in äquimolarer Menge verbraucht, was die Wirtschaftlichkeit des Verfahrens beeinträchtigt.- The acidic oxidative degradation reagent is a relatively expensive one Chemical and is consumed in an equimolar amount what the Economics of the process affected.
Ein universell anwendbares und zudem wirtschaftlich arbeitendes
Verfahren erfordert ein Abbaureagenz, das diese Nachteile
vermeidet. Die rein thermischen Verfahren
Pyrolyse (Abbau-"Reagenz": Wärme)
Verbrennung (Abbau-"Reagenz": Wärme + Sauerstoff)
ergeben keine chemisch verwertbaren Produkte und werden dem
Wertstoffgehalt der Gummis nicht gerecht. Die Altgummi
verwendungen als Füll- und Dämmstoffe kommen letztlich Edel
deponierungen gleich.A process which can be used universally and which also works economically requires a degradation reagent which avoids these disadvantages. The purely thermal processes
Pyrolysis (degradation "reagent": heat)
Combustion (degradation "reagent": heat + oxygen)
do not produce any chemically usable products and do not do justice to the value of the rubber. The used rubber as filler and insulation material ultimately equates to precious landfills.
Der Erfindung lag die Aufgabe zugrunde, ein wirtschaftlich arbeitendes Verfahren zu schaffen, mit welchem alle Polymere abgebaut oder umgewandelt und der Wiederverwertung zur Verfügung gestellt werden können. Die Erfindung besteht in der Anwendung der im Kennzeichen des Patentanspruches 1 genannten Maßnahme.The invention was based, an economical create working process with which all polymers mined or converted and available for recycling can be put. The invention consists in the application the measure mentioned in the characterizing part of claim 1.
Es wird hier erstmals ein Abbauverfahren mit dem als Abbau reagenz in jeder Hinsicht optimalen Wasser vorgeschlagen und zwar mit Wasser unter erhöhtem Druck und erhöhter Temperatur. Umsetzungen mit Wasser unter solchen Bedingungen sind als "Hydrothermalverfahren" in vielen Technikbereichen, vor allem in anorganischen Technologien z. B. in der Keramik- oder in der Silikattechnologie in Anwendung.For the first time, there will be a mining process with the mining reagent suggested in all respects optimal water and with water under increased pressure and temperature. Reactions with water under such conditions are considered "Hydrothermal process" in many technical areas, especially in inorganic technologies e.g. B. in the ceramic or in the Silicate technology in use.
Eine technische Anwendung zum Abbau organischer Abfallstoffe insbesondere zum Abbau von Gummiwerkstoffen, ist bisher nicht bekannt, während eigene Laborversuche positive Vorergebnisse erbracht haben. In der Literatur sind einige spezielle chemische Reaktionen mit organischen Verbindungen unter hydrothermalen Bedingungen erwähnt, die die hohe Reaktivität des Wassers, inbesondere in Gegenwart entsprechender Katalysatoren belegen.A technical application for the degradation of organic waste in particular for the degradation of rubber materials, is not yet known, while own laboratory tests positive preliminary results have rendered. In the literature there are some special chemical ones Reactions with organic compounds under hydrothermal Conditions mentioned that the high reactivity of water, in particular in the presence of appropriate catalysts.
Erhitzt man Wasser unter Druck, so ändern sich im Temperatur bereich zwischen 150-200°C wichtige physikalische Parameter des Wassers sehr stark, z. B. die Dielektrizitätskonstante Insgesamt bewirken diese Veränderungen, daß sich die Reaktivität des Wassers gravierend vom "normalen" Verhalten bis 100°C unterscheidet. Es finden unerwartete und zunächst kaum vorhersehbare Reaktionen statt, was einerseits auf den ungewöhnlichen chemisch-physikalischen Molekülparametern und andererseits auch auf kinetischen Effekten bei den hohen Temperaturen beruht. Das Wassermolekül mit seiner hohen Polarität (große Dielektrizitätskonstante) entfaltet unter hydrothermalen Bedingungen eine extreme Nukleophilie, die zu Anlagerungs- und Hydratisierungsreaktionen führt, die die übliche Wasserchemie nicht kennt. If you heat water under pressure, the temperature changes range between 150-200 ° C important physical parameters of the water very strong, e.g. B. the dielectric constant Overall, these changes cause reactivity to increase of water seriously from "normal" behavior up to 100 ° C differs. It will find unexpected and initially hardly predictable reactions instead of what on the one hand to the unusual chemical-physical molecular parameters and on the other hand also on kinetic effects at the high ones Temperatures. The water molecule with its high Polarity (large dielectric constant) unfolds below hydrothermal conditions an extreme nucleophilicity leading to Addition and hydration reactions leads to the does not know usual water chemistry.
In Schwefelvulkanisaten stellen die C-S-Bindungen polare Funktionen dar, die einen Wasserangriff am C-Atom erlauben, was zur Spaltung der Schwefelbrücken und damit zum Abbau des Vulkanisats führen sollte. Gleichzeitig werden damit die Füllstoffe, z. B. Ruß, freigesetzt. Inwieweit die Kautschukketten abgebaut werden, bleibt durch Untersuchungen zu klären.In sulfur vulcanizates, the C-S bonds are polar Functions that allow a water attack on the C atom, what to split the sulfur bridges and thus to dismantle the Vulcanizate should lead. At the same time Fillers, e.g. B. Soot released. To what extent the rubber chains to be broken down remains to be clarified by investigations.
Bei der hydrothermalen Arbeitstechnik arbeitet man unterhalb der kritischen Temperatur des Wassers, damit eine echte flüssige Wassererphase und nicht nur Dampfphase vorhanden ist. Damit ergibt sich der variable Temperaturarbeitsbereich von ca. 150-350°C, entsprechend einem Arbeitsdruck von ca. 5-163 bar. Durch Hilfsstoffe bzw. Katalysatoren, vornehmlich Cu- oder Fe-Salze, wird der Abbau offensichtlich gefördert. Der Einfluß des pH-Wertes ist ebenfalls wesentlich. Diese Reaktionsparameter müssen auf eine optimale Reaktionszeit eingestellt werden.With hydrothermal work technology one works below the critical temperature of the water, making it a real liquid Water phase and not only vapor phase is present. So that results the variable temperature working range of approx. 150-350 ° C, corresponding to a working pressure of approx. 5-163 bar. By Auxiliaries or catalysts, primarily Cu or Fe salts, mining is obviously encouraged. The influence of the pH is also essential. These reaction parameters must be set for an optimal response time.
Als interessanter weiterführender Aspekt ergibt sich, daß hydrothermale Abbauverfahren auch auf andere organische Abfallstoffe angewendet werden können, z. B. Thermoplaste, Duromere, halogenierte organische Verbindungen.An interesting further aspect is that hydrothermal degradation processes also to other organic Waste materials can be applied, e.g. B. thermoplastics, Duromeric, halogenated organic compounds.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924204094 DE4204094A1 (en) | 1992-02-12 | 1992-02-12 | Hydrothermal decomposition of polymers - esp. de-vulcanisation of rubber, for reuse of sepd. components |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924204094 DE4204094A1 (en) | 1992-02-12 | 1992-02-12 | Hydrothermal decomposition of polymers - esp. de-vulcanisation of rubber, for reuse of sepd. components |
Publications (1)
Publication Number | Publication Date |
---|---|
DE4204094A1 true DE4204094A1 (en) | 1993-08-19 |
Family
ID=6451502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19924204094 Ceased DE4204094A1 (en) | 1992-02-12 | 1992-02-12 | Hydrothermal decomposition of polymers - esp. de-vulcanisation of rubber, for reuse of sepd. components |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE4204094A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022082163A1 (en) * | 2020-10-16 | 2022-04-21 | The Procter & Gamble Company | Recycling a superabsorbent polymer using hydrothermal treatment |
US11993684B2 (en) | 2021-02-23 | 2024-05-28 | The Procter & Gamble Company | Recycling of superabsorbent polymer with a hybrid oxidative degradation and high shear mixing |
US12036098B2 (en) | 2020-10-16 | 2024-07-16 | The Procter & Gamble Company | Absorbent hygiene product comprising superabsorbent polymer partly derived from a recycled resource and methods of producing said product |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE313554C (en) * | 1900-01-01 | |||
DE9910C (en) * | 1900-01-01 | L. HEYER in Berlin SO., Oranienstrafse 183 | Process for the recovery of rubber from used vulcanized rubber | |
DE910962C (en) * | 1944-07-25 | 1954-05-10 | Bayer Ag | Process for the regeneration of old or waste rubber |
DE918897C (en) * | 1951-07-31 | 1954-10-07 | Pirelli | Process for processing rubber waste |
GB1522992A (en) * | 1974-09-04 | 1978-08-31 | Bayer Ag | Process for the continupus degradation of plastics |
DE2520598C2 (en) * | 1974-05-14 | 1983-04-14 | Piovanelli Macchinari e Impianti S.p.A., S. Ilario d'Enza, Reggio Emilia | Process for the regeneration of old rubber in an autoclave |
-
1992
- 1992-02-12 DE DE19924204094 patent/DE4204094A1/en not_active Ceased
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE313554C (en) * | 1900-01-01 | |||
DE9910C (en) * | 1900-01-01 | L. HEYER in Berlin SO., Oranienstrafse 183 | Process for the recovery of rubber from used vulcanized rubber | |
DE910962C (en) * | 1944-07-25 | 1954-05-10 | Bayer Ag | Process for the regeneration of old or waste rubber |
DE918897C (en) * | 1951-07-31 | 1954-10-07 | Pirelli | Process for processing rubber waste |
DE2520598C2 (en) * | 1974-05-14 | 1983-04-14 | Piovanelli Macchinari e Impianti S.p.A., S. Ilario d'Enza, Reggio Emilia | Process for the regeneration of old rubber in an autoclave |
GB1522992A (en) * | 1974-09-04 | 1978-08-31 | Bayer Ag | Process for the continupus degradation of plastics |
Non-Patent Citations (1)
Title |
---|
DE-Z.: Kunststoffe 68(1978), S. 281-284 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022082163A1 (en) * | 2020-10-16 | 2022-04-21 | The Procter & Gamble Company | Recycling a superabsorbent polymer using hydrothermal treatment |
US12036098B2 (en) | 2020-10-16 | 2024-07-16 | The Procter & Gamble Company | Absorbent hygiene product comprising superabsorbent polymer partly derived from a recycled resource and methods of producing said product |
US11993684B2 (en) | 2021-02-23 | 2024-05-28 | The Procter & Gamble Company | Recycling of superabsorbent polymer with a hybrid oxidative degradation and high shear mixing |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
OP8 | Request for examination as to paragraph 44 patent law | ||
8131 | Rejection |