EP1224352A1 - Reinigungssystem mit einem organischen und einem unter druck stehenden flüssigen lösungsmittel - Google Patents

Reinigungssystem mit einem organischen und einem unter druck stehenden flüssigen lösungsmittel

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Publication number
EP1224352A1
EP1224352A1 EP00970902A EP00970902A EP1224352A1 EP 1224352 A1 EP1224352 A1 EP 1224352A1 EP 00970902 A EP00970902 A EP 00970902A EP 00970902 A EP00970902 A EP 00970902A EP 1224352 A1 EP1224352 A1 EP 1224352A1
Authority
EP
European Patent Office
Prior art keywords
solvent
cleaning
independently
pressurized fluid
organic solvent
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.)
Granted
Application number
EP00970902A
Other languages
English (en)
French (fr)
Other versions
EP1224352B1 (de
Inventor
Timothy L. Racette
Gene R. Damaso
James E. Schulte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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
Priority claimed from US09/419,345 external-priority patent/US6355072B1/en
Priority claimed from US09/686,773 external-priority patent/US7097715B1/en
Application filed by Individual filed Critical Individual
Publication of EP1224352A1 publication Critical patent/EP1224352A1/de
Application granted granted Critical
Publication of EP1224352B1 publication Critical patent/EP1224352B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04Cleaning involving contact with liquid
    • B08B3/10Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • 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
    • C11D7/5004Organic solvents
    • C11D7/5022Organic solvents containing oxygen
    • 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
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile
    • 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
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
    • 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
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/264Aldehydes; Ketones; Acetals or ketals
    • 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
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/266Esters or carbonates

Definitions

  • the present invention relates generally to cleaning systems, and more specifically to substrate cleaning systems, such as textile cleaning systems, utilizing an organic cleaning solvent and a pressurized fluid solvent.
  • a variety of methods and systems are known for cleaning substrates such as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants. These known methods and systems typically use water, perchloroethylene, petroleum, and other solvents that are liquid at or substantially near atmospheric pressure and room temperature for cleaning the substrate.
  • textiles that have been cleaned using conventional cleaning methods are typically dried by circulating hot air through the textiles as they are tumbled in a drum.
  • the solvent must have a relatively high vapor pressure and low boiling point to be used effectively in a system utilizing hot air drying.
  • the heat used in drying may permanently set some stains in the textiles.
  • the drying cycle adds significant time to the overall processing time.
  • moisture adsorbed on the textile fibers is often removed in addition to the solvent. This often results in the development of undesirable static electricity and shrinkage in the garments.
  • the textiles are subject to greater wear due to the need to tumble the textiles in hot air for a relatively long time.
  • pressurized fluid solvents or densified fluid solvents have been used for cleaning various substrates, wherein densified fluids are widely understood to encompass gases that are pressurized to either subcritical or supercritical conditions so as to achieve a liquid or a supercritical fluid having a density approaching that of a liquid.
  • some patents have disclosed the use of a solvent such as carbon dioxide that is maintained in a liquid state or either a subcritical or supercritical condition for cleaning such substrates as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants.
  • a solvent such as carbon dioxide
  • 5,279,615 discloses a process for cleaning textiles using densified carbon dioxide in combination with a non-polar cleaning adjunct.
  • the preferred adjuncts are paraffin oils such as mineral oil or petrolatum. These substances are a mixture of alkanes including a portion of which are C 16 or higher hydrocarbons.
  • the process uses a heterogeneous cleaning system formed by the combination of the adjunct which is applied to the textile prior to or substantially at the same time as the application of the densified fluid. According to the data disclosed in Patent No. 5,279,615, the cleaning adjunct is not as effective at removing soil from fabric as conventional cleaning solvents or as the solvents described for use in the present invention as disclosed below.
  • 5,316,591 discloses a process for cleaning substrates using liquid carbon dioxide or other liquefied gases below their critical temperature.
  • the focus of this patent is on the use of any one of a number of means to effect ultrasonic cavitation to enhance the cleaning performance of the liquid carbon dioxide.
  • densified carbon dioxide is the cleaning medium.
  • This patent does not describe the use of a solvent other than the liquefied gas for cleaning substrates. While the combination of ultrasonic cavitation and liquid carbon dioxide may be well suited to processing complex hardware and substrates containing extremely hazardous contaminants, this process is too costly for the regular cleaning of textile substrates. Furthermore, the use of ultrasonic cavitation is less effective for removing contaminants from textiles than it is for removing contaminants from hard surfaces.
  • Patent No. 5,377,705 discloses a process for cleaning precision parts utilizing a liquefied pressurized gas in the supercritical state and an environmentally acceptable co-solvent. During this process, the parts to be cleaned are pre-treated with the co-solvent and then placed in the cleaning vessel. Afterwards, the contaminants and co-solvent are removed from the parts by circulating a pressurized gas in its supercritical state through the vessel. Redeposition of co-solvent and contaminants is controlled by the amount of pressurized gas that is pumped through the vessel.
  • Co-solvents specified for use in conjunction with the cleaning solvent include aliphatics, terpenes, acetone, laminines, isopropyl alcohol, Axarel (DuPont), Petroferm (Petroferm, Inc.), kerosene, and Isopar-m (Exxon).
  • the cleaning solvent supercritical carbon dioxide
  • the cleaning solvent flows through a vessel containing the parts to be treated, through a filter or filters and directly to a separator in which the solvent is evaporated and recondensed.
  • the disclosed co-solvents for use in this patent have high evaporation rates and low flash points. The use of such co-solvents results in high solvent losses, and high fire risks.
  • many of the co-solvents are not compatible with common dyes and fibers used in textile manufacture.
  • the use of supercritical carbon dioxide necessitates the use of more expensive equipment.
  • U.S. Patent No. 5,417,768 discloses a process for precision parts cleaning using a two-solvent system.
  • One solvent can be liquid at room temperature and pressure while the second solvent can be supercritical carbon dioxide.
  • the objectives of this invention include using two or more solvents with minimal mixing of the solvents and to incorporate ultrasonic cavitation in such a way as to prevent the ultrasonic transducers from coming in contact with the first-mentioned solvent.
  • An apparatus is described which consists of an open top vessel within a covered pressurized vessel. The primary fluid is pumped into the open top vessel. After cleaning with the primary fluid, it is pumped from the open top vessel.
  • Pressurized carbon dioxide is then pumped into the open top vessel and flushed through the vessel until the level of contaminants within the vessel are reduced to the desired level.
  • the co-solvents disclosed in this patent are the same solvents specified in U.S. Patent No. 5,377,705. Use of these solvents would introduce a high risk of fire, high levels of solvent loss and potential damage to a wide range of textiles.
  • U.S. Patent No. 5,888,250 discloses the use of a binary azeotrope comprised of propylene glycol tertiary butyl ether and water as an environmentally attractive replacement for perchlorethylene in dry cleaning and degreasing processes. While the use of propylene glycol tertiary butyl ether is attractive from an environmental regulatory point of view, its use as disclosed in this invention is in a conventional dry cleaning process using conventional dry cleaning equipment and a conventional evaporative hot air drying cycle. As a result, it has many of the same disadvantages as conventional dry cleaning processes described above.
  • pressurized fluid solvent cleaning methods may lead to recontamination of the substrate and degradation of cleaning efficiency because the contaminated solvent is not continuously purified or removed from the system.
  • pressurized fluid solvent alone is not as effective at removing some types of soil as are conventional cleaning solvents. Consequently, pressurized fluid solvent cleaning methods require individual treatment of stains and heavily soiled areas of textiles, which is a labor-intensive process.
  • systems that utilize pressurized fluid solvents for cleaning are more expensive and complex to manufacture and maintain than conventional cleaning systems.
  • few if any conventional surfactants can be used effectively in pressurized fluid solvents. The surfactants and additives that can be used in pressurized fluid solvent cleaning systems are much more expensive than those used in conventional cleaning systems.
  • any type of organic solvent that falls within the chemical formulae disclosed hereinafter may be used.
  • a conventional drying cycle is not necessary. Instead, the system utilizes the solubility of the organic solvent in pressurized fluid solvents, as well as the physical properties of pressurized fluid solvents, to dry the substrate being cleaned.
  • pressurized fluid solvent refers to both pressurized liquid solvents and densified fluid solvents.
  • pressurized liquid solvent refers to solvents that are preferably liquid at between approximately 600 and 1050 pounds per square inch and between approximately 5 and 30 degrees Celsius, but are gas at atmospheric pressure and room temperature.
  • densified fluid solvent refers to a gas or gas mixture that is compressed to either subcritical or supercritical conditions so as to achieve either a liquid or a supercritical fluid having density approaching that of a liquid.
  • the pressurized fluid solvent used in the present invention is an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride. Most preferably, the pressurized fluid solvent is densified carbon dioxide.
  • the substrates are cleaned in a perforated drum within a vessel in a cleaning cycle using an organic solvent.
  • a perforated drum is preferred to allow for free interchange of solvent between the drum and vessel as well as to transport soil from the substrates to the filter.
  • the organic solvent is extracted from the substrates by rotating the cleaning drum at high speed within the cleaning vessel in the same way conventional solvents are extracted from substrates in conventional cleaning machines.
  • the substrates instead of proceeding to a conventional evaporative hot air drying cycle, the substrates are immersed in pressurized fluid solvent to extract the residual organic solvent from the substrates. This is possible because the organic solvent is soluble in the pressurized fluid solvent.
  • pressurized fluid solvent which may also serve as a cleaning solvent
  • the pressurized fluid solvent is transferred from the drum.
  • the vessel is de-pressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, yielding clean, solvent-free substrates.
  • Glycol ethers specifically poly glycol ethers, used in the present invention tend to be soluble in pressurized fluid solvents such as supercritical or subcritical carbon dioxide so that a conventional hot air drying cycle is not necessary.
  • the types of poly glycol ethers used in conventional cleaning systems must have a reasonably high vapor pressure and a low boiling point because they must be removed from the substrates by evaporation in a stream of hot air.
  • solvents, particularly non-halogenated solvents, that have a high vapor pressure and a low boiling point generally also have a low flash point. From a safety standpoint, organic solvents used in cleaning substrates should have a flash point that is as high as possible, or preferably, it should have no flash point.
  • the cleaning system described herein utilizes solvents that are less regulated and less combustible, and that efficiently remove different soil types typically deposited on textiles through normal use.
  • the cleaning system reduces solvent consumption and waste generation as compared to conventional dry cleaning systems. Machine and operating costs are reduced as compared to currently used pressurized fluid solvent systems, and conventional additives may be used in the cleaning system.
  • one of the main sources of solvent loss from conventional dry cleaning systems which occurs in the evaporative hot air drying step, is eliminated altogether. Because the conventional evaporative hot air drying process is eliminated, there are no heat set stains on the substrates, risk of fire and/or explosion is reduced, the total cycle time is reduced, and residual solvent in the substrates is substantially reduced or eliminated. Substrates are also subject to less wear, less static electricity build-up and less shrinkage because there is no need to tumble the substrates in a stream of hot air to dry them.
  • While systems according to the present invention utilizing pressurized fluid solvent to remove organic solvent can be constructed as wholly new systems, existing conventional solvent systems can also be converted to utilize the present invention.
  • An existing conventional solvent system can be used to clean substrates with organic solvent, and an additional pressurized chamber for drying substrates with pressurized fluid solvent can be added to the existing system.
  • textiles are cleaned by placing the textiles to be cleaned into a cleaning drum within a cleaning vessel, adding an organic solvent to the cleaning vessel, cleaning the textiles with the organic solvent, removing a portion of the organic solvent from the cleaning vessel, rotating the cleaning drum to extract a portion of the organic solvent from the textiles, placing the textiles into a drying drum within a pressurizable drying vessel, adding a pressurized fluid solvent to the drying vessel, removing a portion of the pressurized fluid solvent from the drying vessel, rotating the drying drum to extract a portion of the pressurized fluid solvent from the textiles, depressurizing the drying vessel to remove the remainder of the pressurized fluid solvent by evaporation, and removing the textiles from the depressurized vessel.
  • FIG. 1 is a block diagram of a cleaning system utilizing separate vessels for cleaning and drying.
  • FIG. 2 is a block diagram of a cleaning system utilizing a single vessel for cleaning and drying.
  • DETAILED DESCRIPTION Reference will now be made in detail to embodiments of the invention, examples of which are illustrated in the accompanying drawings. The steps of each method for cleaning and drying a substrate will be described in conjunction with the detailed description of the system.
  • the methods and systems presented herein may be used for cleaning a variety of substrates.
  • the present invention is particularly suited for cleaning substrates such as textiles, as well as other flexible, precision, delicate, or porous structures that are sensitive to soluble and insoluble contaminants.
  • the term "textile" is inclusive of, but not limited to, woven or non-woven materials, as well as articles therefrom. Textiles include, but are not limited to, fabrics, articles of clothing, protective covers, carpets, upholstery, furniture and window treatments. For purposes of explanation and illustration, and not limitation, exemplary embodiments of a system for cleaning textiles in accordance with the invention are shown in FIGS. l and 2.
  • the pressurized fluid solvent used in the present invention is either a pressurized liquid solvent or a densified fluid solvent.
  • a variety of solvents may be used, it is preferred that an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride, be used as the pressurized fluid solvent.
  • an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride
  • liquid, supercritical, or subcritical carbon dioxide is the preferred pressurized fluid solvent.
  • the internal temperature and pressure of the system must be appropriately controlled relative to the critical temperature and pressure of the pressurized fluid solvent.
  • the critical temperature and pressure of carbon dioxide is approximately 31 degrees Celsius and approximately 73 atmospheres, respectively.
  • the temperature may be established and regulated in a conventional manner, such as by using a heat exchanger in combination with a thermocouple or similar regulator to control temperature.
  • pressurization of the system may be performed using a pressure regulator and a pump and/or compressor in combination with a pressure gauge.
  • the system temperature and pressure may be monitored and controlled either manually, or by a conventional automated controller (which may include, for example, an appropriately programmed computer or appropriately constructed microchip) that receives signals from the thermocouple and pressure gauge, and then sends corresponding signals to the heat exchanger and pump and/or compressor, respectively.
  • a conventional automated controller which may include, for example, an appropriately programmed computer or appropriately constructed microchip
  • receives signals from the thermocouple and pressure gauge and then sends corresponding signals to the heat exchanger and pump and/or compressor, respectively.
  • the temperature and pressure is appropriately maintained throughout the system during operation.
  • elements contained within the system are constructed of sufficient size and material to withstand the temperature, pressure, and flow parameters required for operation, and may be selected from, or designed using, any of a variety of presently available high pressure hardware.
  • the preferred organic solvent should have a flash point of greater than 200°F to allow for increased safety and less governmental regulation, have a low evaporation rate to minimize fugitive emissions, be able to remove soils consisting of insoluble particulate soils and solvent soluble oils and greases, and prevent or reduce redeposition of soil onto the textiles being cleaned.
  • the organic solvent in the present invention is a glycol ether, and specifically a poly glycol ether such as dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether or tripropylene glycol methyl ether, or any combination of two or more of these.
  • H designates hydrogen
  • O oxygen
  • C designates carbon
  • S designates sulfur
  • Si designates silicon
  • CH 3 designates methyl
  • CH 2 CH 3 designates ethyl
  • R is a variable that designates a chemical structure as described further herein.
  • the organic solvent of the invention is composed, in part, of a glycol ether having a structure of: H — ( O — ) z — O — R'
  • glycol ether compounds that fall within the generic structure above and that fulfill the functional parameters of the invention takes into account some variability in the number of subunits identified by subscripts "x", “y” and “z”.
  • Subscripts "x”, “y” and “z” can each be either zero or one and each of their values is independent of the value of the other two subscripts. That is, the subscripts can have values different from each other. However, at least one of "x", "y” or “z” is one.
  • Group R' has the structure of a straight-chain or branched alkyl group; that is a structure of C j H 2j+1 .
  • Subscript value "j” is an integer ranging from one and the value of the difference calculated by 13-3(x+y+z).
  • R R 2 and R 3 are each independently either H or CH 3 .
  • the identities of R ⁇ R 2 and R 3 are selected independent of each other; therefore, R ⁇ and R 2 can be H while R 3 is CH 3 .
  • the types of glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, mono and polyethylene and propylene glycol aliphatic ethers.
  • Group R' can be any one of an O, S, carbonyl or ester groups.
  • R., .12 have a general formula of C m H n F p or C d H e F g .
  • glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, aromatic, aliphatic, and fluorinated and partially fluorinated, aliphatic and aromatic mono and poly glycol ethers and thioethers, and carbonyl and ester derivatives thereof.
  • R,. 12 are grouped together as R ⁇ , R 4-6 , R 7 - 9 , and R 10 . 12 for ease of description. Where the individual components of a group can be different elements, the elements are described in the chart in the alternative. For example, R ⁇ may be described as "H or F.” In a given solvent compound with this description, each of R.,, R 2 and R 3 may be H or each of R 1 ? R 2 and R 3 may be F. Alternatively, R and R 2 may be H while R 3 is F, and so forth with the various combinations of "H” and "F”. This is the same throughout the Tables in this specification.
  • subscripts "x”, “y” and “z” each have a value of either zero or one, but at least one of "x", “y” and “z” has a value of one.
  • Group R" has a structure of C J H 2J+1 or C j H u F v and group R' v has a structure of C k H 2k+1 or C k H r F s .
  • the values of subscripts "j” and “k” are integers ranging from one and the value of 13-3(x+y+z). Therefore, subscripts "j” and “k” can have integer values ranging from one and a maximum value of 10 (if two of "x", "y” and “z” are zero).
  • j+k is an integer ranging from two and the value of 13-3(x+y+z).
  • groups R ⁇ . 3 and R 10-12 can be hydrogen ("H"), fluorine (“F"), methyl (“CH 3 “), ethyl (“CH 2 CH 3 “), or partially or fully fluorinated methyl or ethyl groups.
  • R.,_ 3 and R 1C 2 are selected independently of each other so as to achieve various combinations of the above as contemplated by the invention.
  • R ⁇ have the formula of C m H n F p .
  • groups R 4 . 9 can each be hydrogen, fluorine or methyl groups. As with the other groups, the identity of each of R 4 . 9 is selected independent of the identity of the other groups. Finally, the identity of group R' in General Chemical Structure C is either O, S, a carbonyl group or an ester group.
  • Each of the solvent compounds characterized by General Chemical Structure C is suitable for use as an organic solvent in the cleaning processes of the invention.
  • the types of glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, aliphatic and fluorinated and partially fluorinated aliphatic mono and poly glycol diethers and ether thioethers and carbonyl and ester derivatives thereof.
  • R,. 3 may be described as "H or CH 3 independently.”
  • each of R,, R 2 and R 3 may be H or each of R R 2 and R 3 may be CH 3 .
  • R ⁇ and R 2 may be H while R 3 is CH 3 , and so forth with the various combinations of "H" and "CH 3 ".
  • substrates are cleaned with an organic solvent and the organic solvent is removed from the substrates using a pressurized fluid solvent.
  • the organic solvent can have a structural formula as follows:
  • Group R is either H or has one of the following structures:
  • R"' is H, F or combinations of H and F and group R' v is either H or one of the following structures:
  • R is H, F or combinations of H and F.
  • R' v is not H or F
  • R'" and R are either H or F groups or combinations of H and F. Therefore, within a given R" or R ⁇ v group, the R'" groups and R v groups can be both hydrogens and fluorines; they are not limited to being only hydrogen or fluorine.
  • groups R ⁇ can be H, F, CH 3 , CH 2 F, CHF 2 or CF 3 .
  • Each one of R 4.12 is independently either H or F.
  • substrates are cleaned with an organic solvent and the organic solvent is removed from the substrates using a pressurized fluid solvent.
  • the organic solvent can have a structural formula as follows: R'
  • Each R'" is O or N independently. Where R'" is O, j is 1. Where R'" is N, j is 2.
  • Each R ⁇ v is independently H, CH 3 or CH 2 CH 3 and k and n are integers between zero and two inclusive.
  • R is C y H 2y+1 and y is an integer between one and (12- (3k+3n+x)) inclusive, and x is an integer between one and (12-(3k+y)), inclusive.
  • substrates are cleaned with an organic solvent and the organic solvent is removed from the substrates using a pressurized fluid solvent.
  • the organic solvent can have a structural formula as follows:
  • R'" is O or R"' is NH.
  • Each R ⁇ v is independently H, CH 3 or CH 2 CH 3 and k is an integer between zero and two inclusive.
  • R is C y H 2y+1 and y is an integer between one and (12- (3k+x)) inclusive, and x is an integer between one and (12-(3k+y)), inclusive, and x+y is less than or equal to 12.
  • the cleaning system 100 generally comprises a cleaning machine 102 having a cleaning vessel 110 operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable cleaning drum or wheel 112 within the cleaning vessel 110 with an inlet 114 to the cleaning vessel 110 and an outlet 116 from the cleaning vessel 110 through which cleaning fluids can pass.
  • a drying machine 104 has a drying vessel 120 capable of being pressurized.
  • the pressurizable drying vessel 120 is operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable drying drum or wheel 122 within the drying vessel 120 with an inlet 124 to the drying vessel 120 and an outlet 126 from the drying vessel 120 through which pressurized fluid solvent can pass.
  • the cleaning vessel 110 and the drying vessel 120 can either be parts of the same machine, or they can comprise separate machines. Furthermore, both the cleaning and drying steps of this invention can be performed in the same vessel, as is described with respect to FIG. 2 below.
  • An organic solvent tank 130 holds any suitable organic solvent, as previously described, to be introduced to the cleaning vessel 110 through the inlet 114.
  • a pressurized fluid solvent tank 132 holds pressurized fluid solvent to be added to the pressurizable drying vessel 120 through the inlet 124.
  • Filtration assembly 140 contains one or more filters that continuously remove contaminants from the organic solvent from the cleaning vessel 110 as cleaning occurs.
  • the components of the cleaning system 100 are connected with lines 150- 156, which transfer organic solvents and vaporized and pressurized fluid solvents between components of the system.
  • the term "line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized.
  • the transfer of the organic solvents and vaporized and pressurized fluid solvents through the lines 150-156 is directed by valves 170-176 and pumps 190-193. While pumps 190-193 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
  • the textiles are cleaned with an organic solvent such as those previously described or mixtures thereof.
  • the textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions from about 50% by weight to 100% by weight of organic solvent and 0% by weight to 50% by weight of pressurized fluid solvent.
  • the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together.
  • the textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process.
  • the textiles are then placed into the cleaning drum 112 of the cleaning system 100. It is preferred that the cleaning drum 112 be perforated to allow for free interchange of solvent between the cleaning drum 112 and the cleaning vessel 110 as well as to transport soil from the textiles to the filtration assembly 140.
  • an organic solvent contained in the organic solvent tank 130 is added to the cleaning vessel 110 via line 152 by opening valve 171 , closing valves 170, 172, 173 and 174, and activating pump 190 to pump organic solvent through the inlet 114 of the cleaning vessel 110.
  • the organic solvent may contain one or more co-solvents, water, detergents, or other additives to enhance the cleaning capability of the cleaning system 100. Alternatively, one or more additives may be added directly to the cleaning vessel 110. Pressurized fluid solvent may also be added to the cleaning vessel 110 along with the organic solvent to enhance cleaning.
  • Pressurized fluid solvent can be added to the cleaning vessel 110 via line 154 by opening valve 174, closing valves 170, 171 , 172, 173, and 175, and activating pump 192 to pump pressurized fluid solvent through the inlet 114 of the cleaning vessel 110.
  • the cleaning vessel 110 will need to be pressurized in the same manner as the drying vessel 120, as discussed below.
  • the motor (not shown) is activated and the perforated cleaning drum 112 is agitated and/or rotated within cleaning vessel 110.
  • Filtration assembly 140 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water, dyes and other dissolved contaminants from the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in U.S. Application Serial No. 08/994,583 incorporated herein by reference.
  • the organic solvent is pumped through outlet 116, valve 172, line 151 , filter assembly 140, line 150, valve 170 and re-enters the cleaning vessel 110 via inlet 114.
  • This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the organic solvent and reintroduces filtered organic solvent to the cleaning vessel 110 and agitating or rotating cleaning drum 112. Through this process, contaminants are removed from the textiles.
  • this recirculation system will be maintained at the same pressure/temperature levels as those in cleaning vessel 1 10.
  • the organic solvent is removed from the cleaning drum 112 and cleaning vessel 110 by opening valve 173, closing valves 170, 171 , 172 and 174, and activating pump 191 to pump the organic solvent through outlet 116 via line 153.
  • the cleaning drum 112 is then rotated at a high speed, such as 150-800 rpm, to further remove organic solvent from the textiles.
  • the cleaning drum 112 is preferably perforated so that, when the textiles are rotated in the cleaning drum 112 at a high speed, such as 150-800 rpm, the organic solvent can drain from the cleaning drum 112.
  • any organic solvent removed from the textiles by rotating the cleaning drum 112 at high speed is also removed from the cleaning drum 112 in the manner described above. After the organic solvent is removed from the cleaning drum 112, it can either be discarded or recovered and decontaminated for reuse using solvent recovery systems known in the art.
  • multiple cleaning cycles can be used if desired, with each cleaning cycle using the same organic solvent or different organic solvents. If multiple cleaning cycles are used, each cleaning cycle can occur in the same cleaning vessel, or a separate cleaning vessel can be used for each cleaning cycle.
  • the textiles are moved from the cleaning drum 112 to the drying drum 122 within the drying vessel 120 in the same manner textiles are moved between machines in conventional cleaning systems.
  • a single drum can be used in both the cleaning cycle and the drying cycle, so that, rather than transferring the textiles between the cleaning drum 112 and the drying drum 122, a single drum containing the textiles is transferred between the cleaning vessel 110 and the drying vessel 120. If the cleaning vessel 110 is pressurized during the cleaning cycle, it must be depressurized before the textiles are removed.
  • pressurized fluid solvent such as that contained in the carbon dioxide tank 132
  • pressurized fluid solvent is added to the drying vessel 120 via lines 154 and 155 by opening valve 175, closing valves 174 and 176, and activating pump 192 to pump pressurized fluid solvent through the inlet 124 of the drying vessel 120 via lines 154 and 155.
  • pressurized fluid solvent is added to the drying vessel 120, the organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
  • the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120, and therefore also from the drying drum 122, by opening valve 176, closing valve 175 and activating pump 193 to pump the pressurized fluid solvent and organic solvent combination through outlet 126 via line 156. If desired, this process may be repeated to remove additional organic solvent.
  • the drying drum 122 is then rotated at a high speed, such as 150-800 rpm, to further remove the pressurized fluid solvent and organic solvent combination from the textiles.
  • the drying drum 122 is preferably perforated so that, when the textiles are rotated in the drying drum 122 at a high speed, the pressurized fluid solvent and organic solvent combination can drain from the drying drum 122. Any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drying drum 122 at high speed is also pumped from the drying vessel 120 in the manner described above. After the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120, it can either be discarded or separated and recovered for reuse with solvent recovery systems known in the art. Note that, while preferred, it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles.
  • the drying vessel 120 is depressurized over a period of about 5-15 minutes.
  • the depressurization of the drying vessel 120 vaporizes any remaining pressurized fluid solvent, leaving dry, solvent-free textiles in the drying drum 122.
  • the pressurized fluid solvent that has been vaporized is then removed from the drying vessel 120 by opening valve 176, closing valve 175, and activating pump 193.
  • the vaporized pressurized fluid solvent is pumped through the outlet 126, line 156 and valve 176, where it can then either be vented to the atmosphere or recovered and recompressed for reuse.
  • the cleaning system 100 has been described as a complete system, an existing conventional dry cleaning system may be converted for use in accordance with the present invention.
  • a conventional dry cleaning system the organic solvent described above is used to clean textiles in the conventional system.
  • a separate pressurized vessel is added to the conventional system for drying the textiles with pressurized fluid solvent.
  • the conventional system is converted for use with a pressurized fluid solvent.
  • the system in FIG. 1 could represent such a converted system, wherein the components of the cleaning machine 102 are conventional, and the pressurized fluid solvent tank 132 is not in communication with the cleaning vessel 100. In such a situation, the drying machine 104 is the add-on part of the conventional cleaning machine.
  • FIG. 1 comprises a single cleaning vessel
  • multiple cleaning vessels could be used, so that the textiles are subjected to multiple cleaning steps, with each cleaning step carried out in a different cleaning vessel using the same or different organic solvents in each step.
  • the description of the single cleaning vessel is merely for purposes of description and should not be construed as limiting the scope of the invention.
  • FIG. 2 a block diagram of an alternate embodiment of the present invention, a cleaning system having a single chamber for cleaning and drying the textiles, is shown.
  • the cleaning system 200 generally comprises a cleaning machine having a pressurizable vessel 210.
  • the vessel 210 is operatively connected to, via one or more motor activated shafts (not shown), a perforated rotatable drum or wheel 212 within the vessel 210 with an inlet 214 to the vessel 210 and an outlet 216 from the vessel 210 through which dry cleaning fluids can pass.
  • An organic solvent tank 220 holds any suitable organic solvent, such as those described above, to be introduced to the vessel 210 through the inlet 214.
  • a pressurized fluid solvent tank 222 holds pressurized fluid solvent to be added to the vessel 210 through the inlet 214.
  • Filtration assembly 224 contains one or more filters that continuously remove contaminants from the organic solvent from the vessel 210 and drum 212 as cleaning occurs.
  • the components of the cleaning system 200 are connected with lines 230-234 that transfer organic solvents and vaporized and pressurized fluid solvent between components of the system.
  • the term "line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized.
  • the transfer of the organic solvents and vaporized and pressurized fluid solvent through the lines 230-234 is directed by valves 250-254 and pumps 240-242. While pumps 240-242 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
  • the textiles are cleaned with an organic solvent such as those previously described.
  • the textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions of 50-100% by weight organic solvent and 0-50% by weight pressurized fluid solvent.
  • the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together.
  • the textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process.
  • the textiles are then placed into the drum 212 within the vessel 210 of the cleaning system 200. It is preferred that the drum 212 be perforated to allow for free interchange of solvent between the drum 212 and the vessel 210 as well as to transport soil from the textiles to the filtration assembly 224.
  • an organic solvent contained in the organic solvent tank 220 is added to the vessel 210 via line 231 by opening valve 251 , closing valves 250, 252, 253 and 254, and activating pump 242 to pump organic solvent through the inlet 214 of the vessel 210.
  • the organic solvent may contain one or more co-solvents, detergents, water, or other additives to enhance the cleaning capability of the cleaning system 200. Alternatively, one or more additives may be added directly to the vessel.
  • Pressurized fluid solvent may also be added to the vessel 210 along with the organic solvent to enhance cleaning. The pressurized fluid solvent is added to the vessel 210 via line 230 by opening valve 250, closing valves 251 , 252, 253 and 254, and activating pump 240 to pump the pressurized fluid solvent through the inlet 214 of the vessel 210.
  • Filtration assembly 224 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent and pressurized fluid solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water, dyes, and other dissolved contaminants from the organic solvent.
  • Exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in U.S. Application Serial No. 08/994,583 incorporated herein by reference.
  • the organic solvent is pumped through outlet 216, valve 253, line 233, filter assembly 224, line 232, valve 252 and reenters the vessel 210 via inlet 214.
  • This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the organic solvent and pressurized fluid solvent and reintroduces filtered solvent to the vessel 210. Through this process, contaminants are removed from the textiles.
  • the organic solvent is removed from the vessel 210 and drum 212 by opening valve 254, closing valves 250, 251 , 252 and 253, and activating pump 241 to pump the organic solvent through outlet 216 and line 234.
  • pressurized fluid solvent is used in combination with organic solvent, it may be necessary to first separate the pressurized fluid solvent from the organic solvent.
  • the organic solvent can then either be discarded or, preferably, contaminants may be removed from the organic solvent and the organic solvent recovered for further use. Contaminants may be removed from the organic solvent with solvent recovery systems known in the art.
  • the drum 212 is then rotated at a high speed, such as 150-800 rpm, to further remove organic solvent from the textiles.
  • the drum 212 is preferably perforated so that, when the textiles are rotated in the drum 212 at a high speed, the organic solvent can drain from the cleaning drum 212. Any organic solvent removed from the textiles by rotating the drum 212 at high speed can also either be discarded or recovered for further use.
  • pressurized fluid solvent contained in the pressurized fluid tank 222 is added to the vessel 210 by opening valve 250, closing valves 251 , 252, 253 and 254, and activating pump 240 to pump pressurized fluid solvent through the inlet 214 of the pressurizable vessel 210 via line 230.
  • pressurized fluid solvent is added to the vessel 210, organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
  • pressurized fluid solvent and organic solvent combination is removed from the vessel 210 by opening valve 254, closing valves 250, 251 , 252 and 253, and activating pump 241 to pump the pressurized fluid solvent and organic solvent combination through outlet 216 and line 234.
  • pump 241 may actually require two pumps, one for pumping the low pressure organic solvent in the cleaning cycle and one for pumping the pressurized fluid solvent in the drying cycle.
  • the pressurized fluid solvent and organic solvent combination can then either be discarded or the combination may be separated and the organic solvent and pressurized fluid solvent separately recovered for further use.
  • the drum 212 is then rotated at a high speed, such as 150-800 rpm, to further remove pressurized fluid solvent and organic solvent combination from the textiles. Any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drum 212 at high speed can also either be discarded or retained for further use. Note that, while preferred, it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles. After a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drum 212, the vessel 210 is depressurized over a period of about 5-15 minutes.
  • the depressurization of the vessel 210 vaporizes the pressurized fluid solvent, leaving dry, solvent-free textiles in the drum 212.
  • the pressurized fluid solvent that has been vaporized is then removed from the vessel 210 by opening valve 254, closing valves 250, 251 , 252 and 253, and activating pump 241 to pump the vaporized pressurized fluid solvent through outlet 216 and line 234.
  • pump 241 separate pumps may be necessary to pump organic solvent, pressurized fluid solvent and pressurized fluid solvent vapors, at pump 241.
  • the remaining vaporized pressurized fluid solvent can then either be vented into the atmosphere or compressed back into pressurized fluid solvent for further use.
  • dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and tripropylene glycol methyl ether are the preferred organic solvents for use in the present invention, as shown in the test results below.
  • Table 3 shows results of detergency testing for each of a number of solvents that may be suitable for use in the present invention.
  • Table 4 shows results of testing of drying and extraction of those solvents using densified carbon dioxide.
  • Detergency tests were performed using a number of different solvents without detergents, co-solvents, or other additives.
  • the solvents selected for testing include organic solvents and liquid carbon dioxide.
  • Two aspects of detergency were investigated - soil removal and soil redeposition.
  • the former refers to the ability of a solvent to remove soil from a substrate while the latter refers to the ability of a solvent to prevent soil from being redeposited on a substrate during the cleaning process.
  • Wascherei Anlagens Institute, Krefeld Germany (“WFK”) standard soiled swatches that have been stained with a range of insoluble materials and WFK white cotton swatches, both obtained from TESTFABRICS, Inc., were used to evaluate soil removal and soil redeposition, respectively.
  • Soil removal and redeposition for each solvent was quantified using the Delta Whiteness Index.
  • This method entails measuring the Whiteness Index of each swatch before and after processing.
  • the Delta Whiteness Index is calculated by subtracting the Whiteness Index of the swatch before processing from the Whiteness Index of the swatch after processing.
  • the Whiteness Index is a function of the light reflectance of the swatch and in this application is an indication of the amount of soil on the swatch. More soil results in a lower light reflectance and Whiteness Index for the swatch.
  • the Whiteness indices were measured using a reflectometer manufactured by Hunter Laboratories. Organic solvent testing was carried out in a Launder-Ometer while the densified carbon dioxide testing was carried out in a Parr Bomb.
  • the Delta Whiteness index is calculated by subtracting the Whiteness Index of a swatch before processing from the Whiteness Index value after processing, a positive Delta Whiteness Index indicates that there was an increase in Whiteness Index as a result of processing. In practical terms, this means that soil was removed during processing. In fact, the higher the Delta Whiteness Value, the more soil was removed from the swatch during processing. Each of the organic solvents tested exhibited significant soil removal. Densified carbon dioxide alone, on the other hand, exhibited no soil removal. The WFK white cotton swatches exhibited a decrease in Delta Whiteness Indices indicating that the soil was deposited on the swatches during the cleaning process. Therefore, a "less negative" Delta Whiteness Index suggests that less soil was redeposited.
  • the swatch was next subjected to Soxhlet extraction using methylene chloride for a minimum of two hours.
  • This apparatus enables the swatch to be continuously extracted to remove the organic solvent from the swatch.
  • the amount of organic solvent remaining on the swatch after exposure to densified carbon dioxide was calculated by multiplying the concentration of the organic solvent in the extract by the volume of the extract.
  • a different swatch was used for each of the tests. The results of these tests are included in Table 4. As the results indicate, the extraction process using densified carbon dioxide is extremely effective.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
  • Manufacturing Of Printed Wiring (AREA)
EP00970902A 1999-10-15 2000-10-13 Reinigungssystem mit einem organischen und einem unter druck stehenden flüssigen lösungsmittel Expired - Lifetime EP1224352B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US686773 1984-12-27
US419345 1999-10-15
US09/419,345 US6355072B1 (en) 1999-10-15 1999-10-15 Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
US09/686,773 US7097715B1 (en) 2000-10-11 2000-10-11 Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
PCT/US2000/028433 WO2001029306A1 (en) 1999-10-15 2000-10-13 Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent

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EP1224352A1 true EP1224352A1 (de) 2002-07-24
EP1224352B1 EP1224352B1 (de) 2006-08-23

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AT (1) ATE337428T1 (de)
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CA (1) CA2388913C (de)
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US7097715B1 (en) 2000-10-11 2006-08-29 R. R. Street Co. Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
US6755871B2 (en) * 1999-10-15 2004-06-29 R.R. Street & Co. Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
US6558432B2 (en) 1999-10-15 2003-05-06 R. R. Street & Co., Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
JP4646199B2 (ja) * 2004-09-29 2011-03-09 日東電工株式会社 多孔質膜の製造方法
US7575604B2 (en) 2006-10-06 2009-08-18 Lyondell Chemical Technology, L.P. Drycleaning method
JP6715134B2 (ja) * 2016-09-05 2020-07-01 ライオン株式会社 衣料用液体洗浄剤組成物

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JP2970933B2 (ja) * 1990-10-02 1999-11-02 健 風間 ドライクリーニング用洗浄剤
JPH0551598A (ja) * 1991-08-23 1993-03-02 Asahi Chem Ind Co Ltd ドライクリーニング溶剤
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JPH08245989A (ja) * 1995-03-10 1996-09-24 Toho Chem Ind Co Ltd 洗浄剤組成物
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JP2004515560A (ja) 2004-05-27
DE60030305T2 (de) 2007-08-23
DE60030305D1 (de) 2006-10-05
NO20021765D0 (no) 2002-04-15
WO2001029306A1 (en) 2001-04-26
BR0014770B1 (pt) 2012-03-20
MXPA02003816A (es) 2004-10-14
CA2388913C (en) 2004-04-13
AU8021800A (en) 2001-04-30
CA2388913A1 (en) 2001-04-26
NO20021765L (no) 2002-06-17
AU777996B2 (en) 2004-11-11
EP1224352B1 (de) 2006-08-23
ATE337428T1 (de) 2006-09-15
BR0014770A (pt) 2002-09-17

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