EP0732154A1 - Cleaning with liquid gases - Google Patents

Cleaning with liquid gases Download PDF

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Publication number
EP0732154A1
EP0732154A1 EP96103894A EP96103894A EP0732154A1 EP 0732154 A1 EP0732154 A1 EP 0732154A1 EP 96103894 A EP96103894 A EP 96103894A EP 96103894 A EP96103894 A EP 96103894A EP 0732154 A1 EP0732154 A1 EP 0732154A1
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Prior art keywords
pressure
cleaning
gas
liquefied
pressure vessel
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EP96103894A
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German (de)
French (fr)
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EP0732154B1 (en
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Stephan Dipl.-Ing. Rief
Robert Dipl.-Ing. Adler
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Linde Gas AG
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Linde GmbH
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0021Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • C11D2111/20

Definitions

  • the invention relates to a method for cleaning objects in a pressure vessel with liquefied gases.
  • DE-42 30 485 discloses a cleaning device for smaller workpieces using liquefied gases, a drum being rotatably and / or pivotably arranged in a pressure-resistant container and being connected to a drive device. By rotating the drum, both the cleaning fluid in the pressure-resistant container and the objects in the drum are set in turbulent motion, which increases the cleaning effect. Chemical solvents, mechanical abrasives and inflowing inert gases can also increase cleaning success.
  • at least one lock is provided on the pressure-resistant container for loading and unloading the objects. These locks make a complete ventilation of the pressure-resistant container for the removal of the objects or for loading unnecessary.
  • Liquid carbon dioxide at temperatures between 20 and approximately 30 ° C. with pressures corresponding to the vapor pressure values is used for the processes of the two steps mentioned.
  • WO 94/01613 a method for cleaning textiles using liquefied or supercritical carbon dioxide is known, which is introduced at temperatures between 20 and 100 ° C. and corresponding pressures between 60 and 350 bar into a pressure vessel loaded with the textiles. After the textiles have been washed, there is a displacement flushing with a second fluid, again a compressed gas, such as air or nitrogen.
  • a compressed gas such as air or nitrogen.
  • WO 90/06189 a method for removing impurities from a substrate is known in that the substrate is brought into contact by means of a compressed gas with liquid-like density at critical or supercritical pressure, the phase of the gas between liquid state and supercritical state being varied the temperature of the gas is shifted in a number of stages between supercritical and subcritical temperatures.
  • This multi-stage temperature variation is based on a change in the cohesive energy content of the gas dense phase.
  • the aim is to make the solubility of the compressed gas effective with regard to contamination. Mechanical interactions between the compressed gas and the contaminants are not taken into account.
  • the object of the present invention is therefore to develop a cleaning process with liquefied gases in which the same cleaning results can be achieved with less effort.
  • This object is achieved in that the gas liquefied under pressure is introduced into the pressure vessel which contains the objects to be cleaned, that subsequently or previously the temperature of the liquefied gas is lowered below the critical temperature of the gas and that the cleaning at least is carried out essentially below the critical temperature and below the critical pressure of the gas.
  • the increased mechanical interaction is due to a higher mass transport of fluid to the surface to be cleaned due to the increased density and the greater shear forces between the fluid and the substrate surface due to the increased viscosity of the fluid.
  • the viscosity increases exponentially with the reciprocal of the temperature.
  • noble gases such as helium or argon
  • hydrocarbons such as methane, ethane, propane, ethene or propene, as well as trifluoromethane, carbon dioxide, nitrous oxide and sulfur hexafluoride are suitable as fluids.
  • the liquefied gas is poured into the pressure vessel until it fills part of the same.
  • the liquefied gas is then in equilibrium with its gaseous phase.
  • the pressure vessel can be filled with liquefied gas until it is only in the liquid phase. Then the density and viscosity of the liquid can be increased even further if the pressure in the pressure vessel is increased while the temperature is kept constant.
  • carbon dioxide is particularly preferable, being liquid and gaseous at pressures of below 60 bar Phase with temperatures between -20 and + 20 ° C is used for the cleaning process according to the invention.
  • the pressure vessel can be completely filled with liquid carbon dioxide, the temperature then being kept constant at a value between -20 and + 20 ° C. and the pressure being increased to a value above the corresponding value on the vapor pressure curve .
  • the mechanical interactions can be increased if the liquefied gas and / or the objects to be cleaned are circulated in the pressure vessel. This is done in a known manner by means of an impeller or a rotatable drum in the pressure vessel.
  • the pressure vessel is only partially filled with liquefied gas, there is an additional frictional effect on the surface of the soiled objects when the objects to be cleaned are circulated by constant immersion and immersion out of or into the liquid phase.
  • the mechanical interaction can be increased if it is operated intermittently and / or with an alternating direction of rotation.
  • the method according to the invention has proven to be effective in many tests, in particular for cleaning textiles. It is also suitable to clean metal surfaces or electronic assemblies such as circuit boards from contaminants, which mostly contain organic residues.
  • contaminated test tissues soiled with various fats are cleaned in a pressure vessel into which liquefied carbon dioxide is introduced.
  • the pressure vessel contains a drum that rotates in the pressure vessel, whereby the textiles and the liquefied gas are moved relative to one another.
  • the gas is removed from a storage container in which carbon dioxide liquefied under pressure is present at ambient temperature, and the pressure container is partially filled.
  • the temperature in the pressure vessel is then reduced to approx. 10 ° C while the drum is rotated.
  • the pressure container can be completely filled after a certain cleaning time, the temperature of the liquid carbon dioxide then being kept constant at about 10 ° C. while the pressure is increased to over 45 bar.
  • the pressure can be increased, for example, up to 70 bar (below critical pressure).
  • the cleaning results are completely sufficient even at low pressure increases, so that operating and system costs can be significantly reduced compared to previous cleaning methods.
  • the procedure and a possible addition of surfactants will be selected. After cleaning, the contaminated carbon dioxide is removed and can be reused after relaxation, during which the contaminants fail. This contributes to environmental protection and further reduces costs.

Abstract

The process involves pressurised liquified gas being introduced into the pressure container containing the objects to be cleaned. The temperature of the gas is then or already previously dropped to below the critical temperature of the gas. The cleaning is carried out below the critical temperature and below the critical pressure of the gas. The pressure container is filled completely or only in part with the liquefied gas. Carbon dioxide is used in the liquefied phase wherein the temperature is kept constant at a value between -20 and +20 degs. C and the pressure is raised to a value above the corresponding steam pressure. The liquefied gas and/or objects being cleaned can be circulated in the pressure container using a drum.

Description

Die Erfindung betrifft ein Verfahren zur Reinigung von Gegenständen in einem Druckbehälter mit verflüssigten Gasen.The invention relates to a method for cleaning objects in a pressure vessel with liquefied gases.

Aus der Patentanmeldung WO 92/14558 ist ein derartiges Verfahren zur Reinigung von Werkstücken, insbesondere Metallrohren, mit organischen Rückständen, wie Ölen und Fetten, bekannt, wobei verflüssigte Gase wie Kohlendioxid als Reinigungsfluid verwendet werden. Das Reinigungsfluid wird in einen mit den Werkstücken beladenen Druckbehälter geleitet und dort mittels eines Laufrades umgewälzt. Nach Beendigung des Reinigungsvorgangs wird ein Teil des mit den organischen Rückständen beladenen Fluids aus dem Druckbehälter zusammen mit frischem Reinigungsfluid in einen weiteren Druckbehälter geleitet. Der andere Teil des mit den Verunreinigungen beladenen Fluids wird über eine Turbine entspannt, wodurch die Verunreinigungen ausfallen. Aus dem entleerten Druckbehälter werden nun die gereinigten Werkstücke entnommen, während weitere Werkstücke in dem zweiten Druckbehälter gereinigt werden können.From the patent application WO 92/14558, such a method for cleaning workpieces, in particular metal pipes, with organic residues, such as oils and fats, is known, with liquefied gases such as carbon dioxide being used as the cleaning fluid. The cleaning fluid is passed into a pressure vessel loaded with the workpieces and circulated there by means of an impeller. After the cleaning process has ended, part of the fluid loaded with the organic residues is passed from the pressure vessel together with fresh cleaning fluid into another pressure vessel. The other part of the fluid loaded with the contaminants is expanded via a turbine, causing the contaminants to fail. The cleaned workpieces are now removed from the emptied pressure vessel, while further workpieces can be cleaned in the second pressure vessel.

Weiterhin ist aus der DE-42 30 485 eine Reinigungsvorrichtung für kleinere Werkstücke mit Verwendung verflüssigter Gase bekannt, wobei in einem druckfesten Behälter eine Trommel dreh- und/oder schwenkbar angeordnet und an eine Antriebseinrichtung angeschlossen ist. Durch Rotation der Trommel werden sowohl das Reinigungsfluid in dem druckfesten Behälter als auch die in der Trommel befindlichen Gegenstände in turbulente Bewegung versetzt, wodurch die Reinigungswirkung erhöht wird. Chemische Lösungsmittel, mechanische Scheuermittel und auch einströmende Inertgase können zusätzlich den Reinigungserfolg erhöhen. Um einen quasi-kontinuierlichen Betrieb zu ermöglichen, ist am druckfesten Behälter mindestens eine Schleuse zur Beschickung und Entnahme der Gegenstände vorgesehen. Diese Schleusen machen eine vollständige Belüftung des druckfesten Behälters zur Entnahme der Gegenstände oder zum Beladen unnötig.Furthermore, DE-42 30 485 discloses a cleaning device for smaller workpieces using liquefied gases, a drum being rotatably and / or pivotably arranged in a pressure-resistant container and being connected to a drive device. By rotating the drum, both the cleaning fluid in the pressure-resistant container and the objects in the drum are set in turbulent motion, which increases the cleaning effect. Chemical solvents, mechanical abrasives and inflowing inert gases can also increase cleaning success. In order to enable quasi-continuous operation, at least one lock is provided on the pressure-resistant container for loading and unloading the objects. These locks make a complete ventilation of the pressure-resistant container for the removal of the objects or for loading unnecessary.

Für die Verfahren der beiden genannten Schritten wird flüssiges Kohlendioxid bei Temperaturen zwischen 20 und etwa 30°C verwendet mit den Dampfdruckwerten entsprechenden Drücken.Liquid carbon dioxide at temperatures between 20 and approximately 30 ° C. with pressures corresponding to the vapor pressure values is used for the processes of the two steps mentioned.

Weiterhin ist aus der WO 94/01613 ein Verfahren zur Reinigung von Textilien mittels verflüssigten oder überkritischen Kohlendioxid bekannt, das bei Temperaturen zwischen 20 und 100°C und entsprechenden Drücken zwischen 60 und 350 bar in einen mit den Textilien beladenen Druckbehälter eingeleitet wird. Nach dem Waschen der Textilien erfolgt eine Verdrängungsspülung mit einem zweiten Fluid, wiederum ein verdichtetes Gas, wie Luft oder Stickstoff.Furthermore, from WO 94/01613 a method for cleaning textiles using liquefied or supercritical carbon dioxide is known, which is introduced at temperatures between 20 and 100 ° C. and corresponding pressures between 60 and 350 bar into a pressure vessel loaded with the textiles. After the textiles have been washed, there is a displacement flushing with a second fluid, again a compressed gas, such as air or nitrogen.

Aus der WO 90/06189 ist ein Verfahren zur Entfernung von Verunreinigungen von einem Substrat bekannt, indem das Substrat mittels eines verdichteten Gases mit flüssigkeitsähnlicher Dichte bei kritischem oder überkritischem Druck in Kontakt gebracht wird, wobei die Phase des Gases zwischen Flüssigzustand und überkritischem Zustand durch Variation der Temperatur des Gases in einer Reihe von Stufen zwischen überkritischen Temperaturen und unterkritischen Temperaturen verschoben wird. Diese mehrstufige Temperaturvariation ist auf eine Veränderung des Kohäsionsenergieinhaltes des Gases dichter Phase abgestellt. Es wird dabei angestrebt, das Lösevermögen des verdichteten Gases in bezug auf eine Verunreinigung wirksam zu gestalten. Mechanische Wechselwirkungen zwischen dem verdichteten Gas und den Verunreinigungen werden nicht in Betracht gezogen.From WO 90/06189 a method for removing impurities from a substrate is known in that the substrate is brought into contact by means of a compressed gas with liquid-like density at critical or supercritical pressure, the phase of the gas between liquid state and supercritical state being varied the temperature of the gas is shifted in a number of stages between supercritical and subcritical temperatures. This multi-stage temperature variation is based on a change in the cohesive energy content of the gas dense phase. The aim is to make the solubility of the compressed gas effective with regard to contamination. Mechanical interactions between the compressed gas and the contaminants are not taken into account.

Diese bekannten Reinigungsverfahren nutzen das Lösungsvermögen verdichteter Fluide, das im überkritischen Bereich drastisch zunimmt. Überkritisches Kohlendioxid mit Temperaturen oberhalb 31°C und Drücken oberhalb 73,7 bar weist eine mit der flüssigen Phase vergleichbare Dichte auf und ein gutes Lösungsvermögen, das mit steigender Temperatur noch zunimmt. Selbstverständlich sind auch die Wechselwirkungen des Fluids mit der zu lösenden Substanz (Verunreinigungen) für den Reingungserfolg bedeutsam.These known cleaning methods use the solubility of compressed fluids, which increases drastically in the supercritical area. Supercritical carbon dioxide with temperatures above 31 ° C and pressures above 73.7 bar has a density comparable to that of the liquid phase and good dissolving power, which increases with increasing temperature. Of course, the interactions of the fluid with the substance to be dissolved (impurities) are also important for the cleaning success.

In der praktischen Anwendung zeigen die genannten Reinigungsverfahren einen wesentlichen Nachteil, der in der Verwendung der hohen (überkritischen) Drücke begründet liegt, die wiederum den Einsatz kostspieliger Druckbehälter mit hohen Energie- und Anlagenkosten notwendig macht.In practical use, the cleaning processes mentioned have a major disadvantage, which is due to the use of high (supercritical) pressures, which in turn necessitates the use of expensive pressure vessels with high energy and system costs.

Aufgabe folgender Erfindung ist es deshalb, ein Reinigungsverfahren mit verflüssigten Gasen zu entwickeln, bei dem mit geringerem Aufwand gleiche Reinigungsergebnisse erzielt werden können.The object of the present invention is therefore to develop a cleaning process with liquefied gases in which the same cleaning results can be achieved with less effort.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das unter Druck verflüssigte Gas in den Druckbehälter, der die zu reinigenden Gegenstände enthält, eingeleitet wird, daß anschließend oder bereits vorher die Temperatur des verflüssigten Gases unterhalb der kritischen Temperatur des Gases abgesenkt wird und daß die Reinigung zumindest im wesentlichen unterhalb der kritischen Temperatur und unterhalb des kritischen Druckes des Gases durchgeführt wird.This object is achieved in that the gas liquefied under pressure is introduced into the pressure vessel which contains the objects to be cleaned, that subsequently or previously the temperature of the liquefied gas is lowered below the critical temperature of the gas and that the cleaning at least is carried out essentially below the critical temperature and below the critical pressure of the gas.

Überraschenderweise zeigt sich, daß die Dichte und Viskosität von bis zur flüssigen Phase verdichteten Gasen durch Absenken der Temperatur genügend weit unterhalb ihrer kritischen Temperatur derart erhöht werden können, daß die mechanischen Wechselwirkungen zwischen Reinigungsfluid und den Verunreinigungen den Reinigungserfolg garantieren, obwohl das Lösungsvermögen des verflüssigten Gases bei diesen physikalischen Parametern im Vergleich zu bisherigen Verfahren drastisch verringert ist.Surprisingly, it is found that the density and viscosity of gases compressed to the liquid phase can be increased sufficiently far below their critical temperature by lowering the temperature that the mechanical interactions between the cleaning fluid and the impurities guarantee the cleaning success, although the solubility of the liquefied gas with these physical parameters is drastically reduced compared to previous methods.

Die erhöhte mechanische Wechselwirkung liegt in einem höheren Massentransport von Fluid an die zu reinigende Oberfläche aufgrund der erhöhten Dichte sowie in den größeren Scherkräften zwischen Fluid und Substratoberfläche aufgrund der erhöhten Viskosität des Fluids begründet. Die Viskosität steigt hierbei exponentiell mit dem Kehrwert der Temperatur.The increased mechanical interaction is due to a higher mass transport of fluid to the surface to be cleaned due to the increased density and the greater shear forces between the fluid and the substrate surface due to the increased viscosity of the fluid. The viscosity increases exponentially with the reciprocal of the temperature.

Zur Entfernung beispielsweise organischer Rückstände sind als Fluide beispielsweise Edelgase, wie Helium oder Argon, Kohlenwasserstoffe, wie Methan, Äthan, Propan, Äthen oder Propen, sowie Trifluormethan, Kohlendioxid, Distickstoffmonoxid und Schwefelhexafluorid geeignet.For the removal of organic residues, for example, noble gases such as helium or argon, hydrocarbons such as methane, ethane, propane, ethene or propene, as well as trifluoromethane, carbon dioxide, nitrous oxide and sulfur hexafluoride are suitable as fluids.

Zur Reinigung wird das verflüssigte Gas in den Druckbehälter gefüllt, bis es einen Teil desselbigen ausfüllt. Das verflüssigte Gas liegt dann im Gleichgewicht mit seiner gasförmigen Phase vor. Es kann - eventuell nach einer bestimmten Reinigungszeit - der Druckbehälter weiter mit verflüssigtem Gas gefüllt werden, bis dieses ausschließlich in flüssiger Phase vorliegt. Dann können Dichte und Viskosität der Flüssigkeit noch weiter erhöht werden, wenn bei konstant gehaltener Temperatur der Druck im Druckbehälter vergrößert wird.For cleaning, the liquefied gas is poured into the pressure vessel until it fills part of the same. The liquefied gas is then in equilibrium with its gaseous phase. After a certain cleaning time, the pressure vessel can be filled with liquefied gas until it is only in the liquid phase. Then the density and viscosity of the liquid can be increased even further if the pressure in the pressure vessel is increased while the temperature is kept constant.

Aus bekannten Gründen ist Kohlendioxid besonders vorzuziehen, wobei es bei Drücken von bis unterhalb 60 bar im Gleichgewicht von flüssiger und gasförmiger Phase mit Temperaturen zwischen -20 und +20°C für das erfindungsgemäße Reinigungsverfahren verwendet wird.For known reasons, carbon dioxide is particularly preferable, being liquid and gaseous at pressures of below 60 bar Phase with temperatures between -20 and + 20 ° C is used for the cleaning process according to the invention.

In unerwarteter Weise überwiegen in diesem Parameterbereich die mechanischen Wechselwirkungen des verflüssigten Kohlendioxids mit hoher Dichte und Viskosität das herabgesetzte Lösungsvermögen.In this parameter range, the mechanical interactions of the liquefied carbon dioxide with high density and viscosity unexpectedly outweigh the reduced solvency.

Während der Reinigung oder zu Beginn derselbigen kann der Druckbehälter vollständig mit flüssigem Kohlendioxid gefüllt werden, wobei dann die Temperatur auf einem Wert zwischen -20 und +20°C konstant gehalten wird und der Druck auf einen Wert oberhalb des entsprechenden Werts auf der Dampfdruckkurve erhöht wird.During cleaning or at the beginning of the same, the pressure vessel can be completely filled with liquid carbon dioxide, the temperature then being kept constant at a value between -20 and + 20 ° C. and the pressure being increased to a value above the corresponding value on the vapor pressure curve .

Die mechanischen Wechselwirkungen lassen sich erhöhen, wenn in dem Druckbehälter das verflüssigte Gas und/oder die zu reinigenden Gegenstände umgewälzt werden. Dies geschieht in bekannter Weise mittels eines Laufrades oder einer drehbaren Trommel in dem Druckbehälter.The mechanical interactions can be increased if the liquefied gas and / or the objects to be cleaned are circulated in the pressure vessel. This is done in a known manner by means of an impeller or a rotatable drum in the pressure vessel.

Ist der Druckbehälter nur zum Teil mit verflüssigtem Gas gefüllt, erfolgt bei Umwälzung der zu reinigenden Gegenstände eine zusätzliche Reibungswirkung auf die Oberfläche der verschmutzten Gegenstände durch beständiges Auf- und Eintauchen aus der oder in die flüssige Phase.If the pressure vessel is only partially filled with liquefied gas, there is an additional frictional effect on the surface of the soiled objects when the objects to be cleaned are circulated by constant immersion and immersion out of or into the liquid phase.

Bei Verwendung einer Drehtrommel kann die mechanische Wechselwirkung erhöht werden, wenn diese intermittierend und/oder mit wechselnder Drehrichtung betrieben wird.When using a rotating drum, the mechanical interaction can be increased if it is operated intermittently and / or with an alternating direction of rotation.

Besonders gute Reinigungsergebnisse für Verschmutzungen mit organischen Rückständen, wie Öle und Fette, erhält man bei Verwendung von Kohlendioxid bei Temperaturen von 5 bis 15°C, vorzugsweise bei 10°C.Particularly good cleaning results for soiling with organic residues, such as oils and fats, are obtained when using carbon dioxide at temperatures of 5 to 15 ° C, preferably at 10 ° C.

Besonders vorteilhaft sind bei dieser Art der Reinigung die im Vergleich zu den bekannten Verfahren geringeren Druckwerte, einhergehend mit einer Temperaturabsenkung im Gegensatz zu der notwendigen Temperaturerhöhung bei früheren Reinigungsverfahren. Dies bedeutet zum einen einen geringeren Energieaufwand, zum anderen geringere Anlagenkosten für hochdruckbeständige Anlagenkomponenten. Für das erfindungsgemäße Reinigungsverfahren wird beispielsweise bei Raumtemperatur vorliegendes verflüssigtes Kohlendioxid (25°C; 67 bar) auf 10°C abgekühlt und in einen Druckbehälter, der auf etwa 100 bar ausgelegt ist, eingeleitet. Der Zusatz von beispielsweise für verflüssigtes Kohlendioxid geeigneten Enzymen, Emulgatoren und/oder Tensiden (Detergenzien) kann den Reinigungserfolg weiter erhöhen. Geeignete Zusatzstoffe entnimmt der Fachmann aus einschlägigen Literaturstellen beispielsweise in der Beschreibung zur EP-0 530 949-A1.Particularly advantageous in this type of cleaning are the lower pressure values in comparison to the known methods, along with a lowering of the temperature in contrast to the necessary temperature increase in earlier cleaning methods. On the one hand, this means lower energy consumption and, on the other hand, lower system costs for high-pressure-resistant system components. For the cleaning process according to the invention, for example, liquefied carbon dioxide (25 ° C.; 67 bar) present at room temperature is cooled to 10 ° C. and introduced into a pressure vessel, which is designed for about 100 bar. The addition of enzymes, emulsifiers and / or surfactants (detergents) suitable for liquefied carbon dioxide, for example, can further increase the cleaning success. The person skilled in the art takes suitable additives from relevant literature references, for example in the description of EP-0 530 949-A1.

Das erfindungsgemäße Verfahren hat sich insbesondere zur Reinigung von Textilien in vielen Versuchen als wirkungsvoll erwiesen. Es ist außerdem geeignet, metallische Oberflächen oder elektronische Baugruppen wie Platinen von Verunreinigungen, die meist organische Rückstände enthalten, zu reinigen.The method according to the invention has proven to be effective in many tests, in particular for cleaning textiles. It is also suitable to clean metal surfaces or electronic assemblies such as circuit boards from contaminants, which mostly contain organic residues.

In einer Ausführung des erfindungsgemäßen Verfahrens werden verunreinigte Testgewebe, die mit verschiedenen Fetten angeschmutzt sind, in einem Druckbehälter, in den verflüssigtes Kohlendioxid eingeleitet wird, gereinigt. Der Druckbehälter enthält eine Trommel, die im Druckbehälter rotiert, wodurch die Textilien und das verflüssigte Gas relativ zueinander bewegt werden. Das Gas wird aus einem Vorlagebehälter, in dem unter Druck verflüssigtes Kohlendioxid bei Umgebungstemperatur vorliegt, entnommen und der Druckbehälter zum Teil gefüllt. Anschließend wird die Temperatur im Druckbehälter auf ca. 10°C abgesenkt, während die Trommel in Rotation versetzt wird.In one embodiment of the method according to the invention, contaminated test tissues soiled with various fats are cleaned in a pressure vessel into which liquefied carbon dioxide is introduced. The pressure vessel contains a drum that rotates in the pressure vessel, whereby the textiles and the liquefied gas are moved relative to one another. The gas is removed from a storage container in which carbon dioxide liquefied under pressure is present at ambient temperature, and the pressure container is partially filled. The temperature in the pressure vessel is then reduced to approx. 10 ° C while the drum is rotated.

Während der Reinigung vermischen sich flüssige und gasförmige Phase, durch die die Testgewebe transportiert werden, wodurch wiederum reinigungsunterstützende Reibungseffekte eintreten. Bedarfsweise kann nach einer bestimmten Reinigungszeit der Druckbehälter weiter vollständig gefüllt werden, wobei dann die Temperatur des flüssigen Kohlendioxids bei etwa 10°C konstant gehalten wird, während der Druck auf über 45 bar erhöht wird. Die Druckerhöhung kann beispielsweise bis auf 70 bar erfolgen (unterhalb kritischem Druck). Die Reinigungsergebnisse sind jedoch schon bei geringeren Druckerhöhungen vollständig ausreichend, so daß Betriebs- und Anlagekosten im Vergleich zu bisherigen Reinigungsmethoden deutlich gesenkt werden können.During cleaning, the liquid and gaseous phases mix through which the test tissues are transported, which in turn leads to cleaning-supporting friction effects. If necessary, the pressure container can be completely filled after a certain cleaning time, the temperature of the liquid carbon dioxide then being kept constant at about 10 ° C. while the pressure is increased to over 45 bar. The pressure can be increased, for example, up to 70 bar (below critical pressure). However, the cleaning results are completely sufficient even at low pressure increases, so that operating and system costs can be significantly reduced compared to previous cleaning methods.

Je nach Art der Verschmutzung wird man die Verfahrensführung und einen evtl. Zusatz von Tensiden wählen. Nach der Reinigung wird das verunreinigte Kohlendioxid entnommen und kann nach Entspannung, bei der die Verunreinigungen ausfallen, wiederverwendet werden. Dies trägt zum Umweltschutz bei und senkt weiter die Kosten.Depending on the type of contamination, the procedure and a possible addition of surfactants will be selected. After cleaning, the contaminated carbon dioxide is removed and can be reused after relaxation, during which the contaminants fail. This contributes to environmental protection and further reduces costs.

Claims (11)

Verfahren zur Reinigung von Gegenständen in einem Druckbehälter mit verflüssigten Gasen, dadurch gekennzeichnet, daß das unter Druck verflüssigte Gas in den Druckbehälter, der die zu reinigenden Gegenstände enthält, eingeleitet wird, daß anschließend oder bereits vorher die Temperatur des verflüssigten Gases unterhalb der kritischen Temperatur des Gases abgesenkt wird und daß die Reinigung zumindest im wesentlichen unterhalb der kritischen Temperatur und unterhalb des kritischen Druckes des Gases durchgeführt wird.Process for cleaning objects in a pressure vessel with liquefied gases, characterized in that the gas liquefied under pressure is introduced into the pressure vessel which contains the objects to be cleaned, that subsequently or previously the temperature of the liquefied gas is below the critical temperature of the Gas is lowered and that the cleaning is carried out at least substantially below the critical temperature and below the critical pressure of the gas. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Druckbehälter nur zum Teil mit verflüssigtem Gas gefüllt wird.Method according to claim 1, characterized in that the pressure vessel is only partially filled with liquefied gas. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Druckbehälter vollständig mit verflüssigtem Gas gefüllt wird.Method according to claim 1 or 2, characterized in that the pressure vessel is completely filled with liquefied gas. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß bei Drücken von bis unterhalb 60 bar verflüssigtes Kohlendioxid im Gleichgewicht der flüssigen und der gasförmigen Phase mit Temperaturen zwischen -20 und +20°C verwendet wird.A method according to claim 1 or 2, characterized in that at pressures of below 60 bar liquefied carbon dioxide in the equilibrium of the liquid and the gaseous phase with temperatures between -20 and + 20 ° C is used. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß Kohlendioxid in flüssiger Phase verwendet wird, wobei die Temperatur auf einen Wert zwischen -20 und +20°C konstant gehalten wird und der Druck auf einen Wert oberhalb des entsprechenden Dampfdrucks erhöht wird.Method according to one of claims 1 to 4, characterized in that carbon dioxide is used in the liquid phase, the temperature being kept constant at a value between -20 and + 20 ° C and the pressure being increased to a value above the corresponding vapor pressure. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß in dem Druckbehälter das verflüssigte Gas und/oder die zu reinigenden Gegenstände umgewälzt werden.Method according to one of claims 1 to 5, characterized in that the liquefied gas and / or the objects to be cleaned are circulated in the pressure vessel. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß zur Umwälzung eine im Druckbehälter dreh- und/oder schwenkbar angeordnete Trommel verwendet wird, die intermittierend und/oder mit wechselnder Drehrichtung betrieben wird.Method according to Claim 6, characterized in that a drum which is arranged in the pressure vessel and which can be rotated and / or pivoted is used for the circulation and is operated intermittently and / or with a changing direction of rotation. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß Kohlendioxid bei Temperaturen von 5 bis 15°C, vorzugsweise bei 10°C, verwendet wird.Process according to one of claims 1 to 7, characterized in that carbon dioxide is used at temperatures of 5 to 15 ° C, preferably at 10 ° C. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß dem verflüssigten Gas Enzyme, Emulgatoren und/oder Tenside und Detergenzien zugesetzt werden.Method according to one of claims 1 to 8, characterized in that enzymes, emulsifiers and / or surfactants and detergents are added to the liquefied gas. Verwendung eines Verfahrens nach den Ansprüchen 1 bis 9 zur Reinigung von Textilien.Use of a method according to claims 1 to 9 for cleaning textiles. Verwendung eines Verfahrens nach den Ansprüchen 1 bis 9 zur Reinigung von Bauteilen.Use of a method according to claims 1 to 9 for cleaning components.
EP96103894A 1995-03-16 1996-03-12 Cleaning with liquid gases Expired - Lifetime EP0732154B1 (en)

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USRE38001E1 (en) 2003-02-25
DE19509573C2 (en) 1998-07-16
DE59602213D1 (en) 1999-07-22
ATE181261T1 (en) 1999-07-15
EP0732154B1 (en) 1999-06-16
DE19509573A1 (en) 1996-09-19
US5759209A (en) 1998-06-02

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