BR0209037A

Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent

Abstract

"CLEANING SYSTEM USING AN ORGANIC CLEANING SOLVENT AND A PRESSURIZED FLUID SOLVENT". a cleaning system is disclosed which uses an organic cleaning solvent and pressurized fluid solvent. The system does not have a conventional evaporative hot air drying cycle. Instead, the system uses the solubility of the organic solvent in pressurized fluid solvent as well as the physical properties of pressurized fluid solvent. After a cleaning cycle with organic solvent, the solvent is extracted from textile articles at high speed in a rotating drum (112, 122) in the same way that conventional solvents are extracted from textile articles in dry cleaning machines with evaporative hot air , conventional. Instead of proceeding to a conventional drying cycle, the extracted textile articles are then immersed in a pressurized fluid solvent in order to extract the residual organic solvent from the textile articles. This is possible because the organic solvent is soluble in pressurized fluid solvent. After immersing the textile articles in pressurized fluid solvent, pressurized fluid solvent is pumped from the drum (112, 122). Finally, the drum is depressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, providing clean, solvent-free textile articles. The organic solvent is preferably selected from terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, glycol ethers esters, fatty acid esters and other long chain carboxylic acids, long chain alcohols, fatty alcohols and other fatty alcohols long chain, short chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters and aliphatic hydrocarbon solvents or similar solvents or mixtures of these solvents and the pressurized fluid solvent is preferably densified carbon dioxide.

BR0209037A, drawing sheet 1 — Sheet 1 of 13

Term

Term ended

Projected expiry passed 18 April 2022, 4.4 years ago.

107 claims: 2 independent, 105 dependent

1
CLAIMS REIVINDICAÇÕES 1. Process for cleaning substrates, FEATURED for understanding:1. Processo para limpeza de substratos, CARACTERIZADO por compreender: colocar os substratos a serem limpos, em um recipiente ;put the substrates to be cleaned, in a container;add organic solvent to the container;clean the substrates with an organic solvent;removing a portion of the organic solvent from the container;adicionar solvente orgânico ao recipiente;limpar os substratos com um solvente orgânico;remover uma porção do solvente orgânico, do recipiente ;adding a pressurized fluid solvent to the container;adicionar um solvente fluido pressurizado ao recipiente ;remover o solvente fluido pressurizado do recipiente;e remover os substratos do recipiente. removing the pressurized fluid solvent from the container;and removing the substrates from the container.
54
55. Substrate cleaning system, FEATURED for understanding:55. Sistema de limpeza de substratos, CARACTERIZADO por compreender: a cleaning container adapted to contain contaminated substrates and organic solvent;um recipiente de limpeza adaptado para conter substratos contaminados e solvente orgânico;an organic solvent tank efficiently connected to the cleaning container;um tanque de solvente orgânico conectado eficientemente ao recipiente de limpeza;a pump for pumping organic solvent from the organic solvent tank to the cleaning container;uma bomba para bombear solvente orgânico do tanque de solvente orgânico para o recipiente de limpeza;a drying container adapted to contain clean substrates and pressurized fluid solvent;um recipiente de secagem adaptado para conter substratos limpos e solvente fluido pressurizado;a pressurized fluid solvent tank efficiently connected to the drying container;and a pump for pumping pressurized fluid solvent from the pressurized fluid solvent tank to the drying container. um tanque de solvente fluido pressurizado conectado eficientemente ao recipiente de secagem;e uma bomba para bombear solvente fluido pressurizado do tanque de solvente fluido pressurizado para o recipiente de secagem.

Independent claims2

559 paragraphs in 33 sections, as filed

(54) Title: CLEANING SYSTEM USING AN ORGANIC CLEANING SOLVENT AND A PRESSURIZED FLUID SOLVENT (30) Unionist Priority: 18/04/2001 us 09 / 837.849 (71) Depositor (s): Timothy L. Racette (US) , Gene R. Damaso (US), James E. Schulte (US) (72) Inventor (s): Timothy L. Racette, Gene R. Damaso, James E. Schulte (74) Attorney: Nellie Anne Daniel Shores (86) International Request: pct US2002 / 012304 of 18/04/2002 (87) International Publication: W02002 / O86223 of 10/31/2002 (57) Summary: CLEANING SYSTEM THAT USE AN ORGANIC CLEANING SOLVENT AND A PRESSURIZED FLUID SOLVENT. A cleaning system using an organic cleaning solvent and pressurized fluid solvent is disclosed. The system does not have a conventional evaporative hot air drying cycle. Instead, the system utilizes the solubility of the organic solvent in pressurized fluid solvent as well as the physical properties of pressurized fluid solvent. After a cleaning cycle with organic solvent, the solvent is extracted from the textile articles at high speed in a rotating drum (112, 122) in the same way that conventional solvents are extracted from the textile articles in dry cleaning machines with evaporative hot air. , conventional. Instead of proceeding to a conventional drying cycle, the extracted textile articles are then immersed in a pressurized fluid solvent in order to extract the residual organic solvent from the textile articles. This is possible because the organic solvent is soluble in pressurized fluid solvent. After immersing the textile articles in pressurized fluid solvent, pressurized fluid solvent is pumped from the drum (112, 122). Finally, the drum is depressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, providing clean, solvent-free textile articles. The organic solvent is preferably selected from terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, glycol ethers esters, fatty acid esters and other long chain carboxylic acids, long chain alcohols, fatty alcohols and other fatty alcohols long chain, short chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters and aliphatic hydrocarbon solvents or similar solvents or mixtures of these solvents and the pressurized fluid solvent is preferably densified carbon dioxide.

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CLEANING SYSTEM USING AN ORGANIC CLEANING SOLVENT AND A PRESSURIZED FLUID SOLVENT

BACKGROUND

Field of the Invention

The present invention relates generally to cleaning systems and more specifically to substrate cleaning systems, such as textile cleaning systems, using an organic cleaning solvent and a pressurized fluid solvent.

Related Technique

A variety of methods and systems are known for cleaning substrates such as textile articles, 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, perchlorethylene, petroleum and other solvents that are liquid at or substantially close to atmospheric pressure and room temperature for cleaning the substrate.

i. These conventional methods and systems have been generally considered satisfactory for their intended purpose. Recently, however, the desire to employ these conventional methods and systems has been questioned due to environmental, hygienic, occupational risk and waste disposal concerns, among other things. For example, perchlorethylene is often used as a solvent to clean delicate substrates, such as textile articles in a process referred to as dry cleaning. Some locations require the use and disposal of this solvent to be regulated by environmental agencies, even when only residual amounts of that solvent should be introduced into refuse streams.

In addition, there are significant regulatory burdens placed on solvents such as perchlorethylene by bodies such as EPA, OSHA and DOT. Such regulation results in increased costs for the user, which, in turn, are passed on to the final consumer. For example, filters that were used

- in conventional perchlorethylene dry cleaning systems they must be disposed of according to hazardous waste regulations or other environmental regulations. Other solvents used in dry cleaning, such as hydrocarbon solvents, are extremely flammable, resulting in greater occupational risks for the user and increased costs to control their use.

In addition, textile articles that have been cleaned using conventional cleaning methods are typically dried by circulating hot air through the textile articles as they are tipped onto a drum. The solvent must have a relatively high vapor pressure and low boiling point to be used effectively in a system that uses hot air drying. The heat used in drying can permanently fix some stains on the textile articles. In addition, the drying cycle adds significant time to the total processing time. During the conventional drying process, moisture adsorbed on textile fibers is often removed in addition to the solvent. This often results in the development of unwanted static electricity and shrinkage of articles. Also, textile articles are subject to greater wear and tear due to the need to tip textile articles in hot air for a relatively long period of time. Conventional drying methods are inefficient and often leave excess residual solvent in textile articles, particularly in heavy textile articles, components constructed of multiple layers of fabric and structural components of articles such as shoulder padding. This can result in unpleasant odors and, in extreme cases, can cause irritation to the user's skin. In addition to being time consuming and of limited efficiency, conventional drying results in significant loss of cleaning solvent in the form of ephemeral solvent vapor. The heating required to evaporate combustible solvents in a conventional drying process increases the risk of fire and / or explosions. In many cases, heating the solvent will require explosion-proof components and other expensive safety devices to minimize the risk of fire and explosions. Finally, drying with conventional hot air is an energy intensive process that results in relatively high utility costs and accelerated wear and tear on equipment.

Traditional cleaning systems can use distillation in combination with filtration and adsorption to remove dissolved and suspended dirt in the cleaning solvent. The filters and adsorption materials become saturated with solvent, therefore, elimination of any filter waste is regulated by state or federal laws. Evaporation of solvent in particular during the drying cycle is one of the main sources of solvent loss in conventional systems. Reducing solvent loss improves the environmental and economic aspects of cleaning substrates using cleaning solvents. Therefore, it is advantageous to provide a method and system for cleaning substrates that use a solvent with less adverse attributes than those currently used solvents and reduces solvent losses.

As an alternative to conventional cleaning solvents, pressurized fluid solvents or densified fluid solvents have been used for cleaning various substrates, where densified fluids are widely understood to encompass gases that are pressurized under subcritical or supercritical conditions to obtain a liquid or a supercritical fluid that has a density approaching that of a liquid. In particular, some patents have disclosed the use of a solvent such as carbon dioxide that is maintained in a liquid state or a subcritical or supercritical condition for cleaning such substrates as textile articles, as well as other flexible, precision, delicate or porous which are sensitive to soluble and insoluble contaminants.

For example, US patent no. 5,279,615 discloses a process for cleaning textile articles using dense carbon dioxide in combination with a non-polar cleaning agent. Preferred adjuncts are paraffin oils such as mineral oil or petrolatum. These substances are a mixture of alkanes including a portion of which are hydrocarbons

Ç16 or higher. The process uses a heterogeneous cleaning system formed by combining the adjunct which is applied to the textile article before 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 aid is not as effective in removing dirt from the fabric as conventional cleaning solvents or as the solvents described for use in the present invention as disclosed below.

US patent no. 5,316,591 reveals 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 of several means to perform cavitation in order to increase the cleaning performance of liquid carbon dioxide. In all the revealed modalities, the dense carbon dioxide is the cleaning medium. This patent does not describe the use of a solvent other than liquefied gas for cleaning substrates. Although the combination of ultrasonic cavitation and liquid carbon dioxide may be well suited to process complex hardware and substrates containing extremely dangerous contaminants, this process is too expensive for regular cleaning of textile substrates. In addition, the use of ultrasonic cavitation is less effective for removing contaminants from textile articles than it is for removing contaminants from hard surfaces.

US patent no. 5,377,705, shipped to Smith and others, reveals a system designed to clean parts that use supercritical carbon dioxide and an environment-friendly co-solvent. Parts to be cleaned are placed in a cleaning container together with the solvent. After adding supercritical carbon dioxide, mechanical agitation is applied through sonication or brushing. Loose contaminants are then removed from the cleaning container using additional carbon dioxide. The use of this system for cleaning textile articles is neither suggested nor revealed. In addition, the use of this system for cleaning textile articles would result in the repositioning of loose dirt and damage to some fabrics.

US patent no. 5,417,768, issued to Smith et al., Reveals a process for precision cleaning of a workpiece using a multi-solvent system in which one of the solvents is liquid or super15 critical carbon dioxide. The process results in minimal solvent mixing and incorporates ultrasonic cavitation in such a way as to prevent ultrasonic transducers from coming into contact with cleaning solvents that could degrade the piezoelectric transducers. 0 use of this system in cleaning textile articles

0 it is neither suggested nor revealed. In reality, its use in cleaning textile articles would result in the repudiation of loose dirt and damage to some fabrics.

US patent no. 5,888,250 reveals the use of a binary azeotrope comprised of tertiary butyl ether of propylene glycol and water as an attractive substitute for the environment, in place of perchlorethylene in grease removal and dry cleaning processes. Although the use of propylene glycol tertiary butyl ether is attractive from an environmental regulatory point of view, its use as disclosed in the present invention is in a conventional dry cleaning process using conventional dry cleaning equipment and a drying cycle with conventional evaporative hot air. As a result, it has many of the same disadvantages as the conventional dry cleaning processes described above.

US patent no. 6,200,352 discloses a process for cleaning substrates in a cleaning mixture comprising carbon dioxide, water, surfactant and organic co-solvent. This process uses carbon dioxide as the primary cleaning medium with the other components included to increase the overall cleaning efficiency of the process. There is no suggestion of a separate low pressure cleaning step, followed by the use of thick fluid to remove the cleaning solvent. As a result, this process has many of the same disadvantages of cleaning performance and cost as other liquid carbon dioxide cleaning processes. Additional patents have been issued to the assignee of US patent no. 6,200,352 covering related matter. All of these patents reveal processes in which liquid carbon dioxide is the cleaning solvent. Consequently, these processes have the same disadvantages of cleaning performance and cost.

Several of the pressurized fluid solvent cleaning methods described in the above patents can lead to substrate recontamination and efficiency degradation because the contaminated solvent is not continuously purified or removed from the system. In addition, the pressurized fluid solvent alone is not as effective at removing some types of dirt as are conventional cleaning solvents. Consequently, pressurized fluid solvent cleaning methods require individual treatment of stains and very dirty areas of textile articles, which is an intensive process in terms of labor. Additionally, systems that use pressurized fluid solvents for cleaning are more expensive and complex to manufacture and maintain than conventional cleaning systems. Finally, few if any conventional surfactants can be used effectively in pressurized fluid solvents. Surfactants and additives that can be used in pressurized fluid solvent cleaning systems are much more expensive than those used in conventional cleaning systems. Thus there remains a need for an efficient and economical method and system for cleaning substrates that incorporate the benefits of previous systems and minij mitigate the difficulties encountered in each of them. There remains also a need for a method and system in which the drying time with hot air is eliminated or at least reduced, thereby reducing wear on the substrate and preventing the stains from being permanently fixed on the substrate.

SUMMARY

In the present invention, certain types of organic solvents, such as terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, glycol ethers esters, fatty acid esters and other long-chain carboxylic acids, fatty alcohols and other long-chain alcohols , short chain alcohols, polar aprotic solvents, siloxanes, hydrofluorethers, dibasic esters and solvents of hi5 aliphatic drocarbons or similar solvents or mixtures of these solvents are used in cleaning substrates. Any type of organic solvent that is within the range of properties revealed below can be used for cleaning substrates. However, unlike conventional cleaning systems, in the present invention, a conventional drying cycle is not performed. Instead, the system uses 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.

As used herein, the term pressurized fluid solvent refers to both pressurized liquid solvents and densified fluid solvents. The term pressurized liquid solvent as used herein refers to solvents which are liquids between approximately 4.238 and 7.340 MPa and between approximately 5 and 30 degrees Celsius, but are gaseous at atmospheric pressure and room temperature. The term densified fluid solvent as used herein refers to a gas or mixture of gas which is compressed to sub-critical or supercritical conditions in order to obtain a liquid or supercritical fluid having a density approaching that of a liquid. Preferably, the pressurized fluid solvent used in the present invention is an inorganic substance such as carbon dioxide, xenon, nitrous oxide or sulfur hexafluoride. More preferably, the pressurized fluid solvent is dense carbon dioxide.

The substrates are cleaned in a perforated drum inside a container on a cleaning cycle using an organic solvent. A perforated drum is preferred to allow solvent-free interchange between the drum and the container as well as for transporting dirt from the substrates to the filter. After cleaning the substrates in the perforated drum, the organic solvent is extracted from the substrates by rotating the cleaning drum at high speed inside the cleaning container in the same way that conventional solvents are extracted from substrates in conventional cleaning machines. However, instead of proceeding to a conventional evaporative hot air drying cycle, the substrates are immersed in a 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. After the substrates are immersed in a pressurized fluid solvent, the pressurized fluid solvent is transferred from the drum. Finally, the container is depressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, providing clean, solvent-free substrates.

The solvents used in the present invention tend to be soluble in pressurized fluid solvents such as supercritical or subcritical carbon dioxide so that a drying cycle with conventional hot air is not necessary. The types of solvents used in conventional cleaning systems must have relatively high vapor pressures and low boiling points because they must be removed from the substrates by evaporation in a stream of hot air. However, solvents that have a high vapor pressure and a low boiling point generally also have a low flash point. From a safety point of view, organic solvents used in cleaning substrates should have a flash point that is as high as possible, or preferably, should have no flash point. By eliminating the evaporative drying process with conventional hot air, a wide range of solvents can be used in the present invention which have much lower evaporation rates, higher boiling points and higher flash points than those used in heating systems. conventional cleaning. For situations where the desired solvent has a relatively low flash point, eliminating the evaporative drying cycle with hot air significantly increases the safety level with respect to fire and explosions.

Thus, the cleaning system described here uses solvents that are less regulated and less combustible, and that efficiently remove different types of dirt typically deposited on textile articles through normal use. The cleaning system reduces solvent consumption and waste generation compared to conventional dry cleaning systems. Operating and machine costs are reduced compared to currently used pressurized fluid solvent systems and conventional additives can be used in the cleaning system.

In addition, one of the main sources of solvent loss from conventional dry cleaning systems, which occurs in the drying step with hot evaporative air, is substantially reduced or eliminated entirely. Due to the elimination of the drying process with conventional evaporative hot air, there are no fixed heat stains on the substrates, risk of fire and / or explosion is reduced, the cleaning cycle time is reduced, and the residual solvent on the substrates is substantially reduced. or deleted. Substrates are also subject to less wear, less static buildup and less shrinkage because there is no need to tip the substrates into a hot air stream to dry them.

Although systems according to the invention using pressurized fluid solvent to remove organic solvent can be constructed as entirely new systems, existing conventional solvent systems can also be converted to use the present invention. An existing conventional solvent system can be used for cleaning substrates with organic solvent, and an additional pressurized chamber for drying substrates with pressurized fluid solvent can be added to the existing system.

Therefore, according to the present invention, textile articles to be cleaned are placed in a cleaning drum inside a cleaning container, an organic solvent is added to the cleaning container, cleaning the textile articles with the organic solvent, removing a portion of the organic solvent from the cleaning container, rotation of the cleaning drum to extract a portion of the organic solvent5 from the textile articles, placing the textile articles in a drying drum inside a pressurizable drying container, adding a pressurized fluid solvent to the drying container, removing a portion of the pressurized fluid solvent from the drying container, rotating the drying drum to extract a portion of the pressurized fluid solvent from the textile articles, depressurizing the drying container to remove the rest of the pressurized fluid solvent by evaporation, and removing the textile articles from the depressurized container.

These and other features and advantages of the invention will be evident upon consideration of the following detailed description of the currently preferred embodiment of the invention, taken in combination with the attached claims and wishes, as well as will be learned from the practice of the invention. 20 BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a block diagram of a cleaning system that uses separate containers for cleaning and drying.

Figure 2 is a block diagram of a cleaning system that uses a single container for cleaning and drying.

DETAILED DESCRIPTION

Reference will now be made in detail to the modalities 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 combination with the detailed description of the system.

The methods and systems presented here can be used for cleaning a variety of substrates. The present invention is particularly suitable for cleaning substrates such as textile articles, as well as other flexible, precision, delicate or porous structures that are sensitive to soluble and insoluble contaminants. The term textile article includes, but is not limited to, woven or nonwoven materials, as well as articles made from them. Textile articles include, but are not limited to, fabrics, clothing, protective covers, carpets, upholstery, window treatments and furniture. For purposes of explanation and illustration, and not limitation, exemplary modalities of a system for cleaning textile articles according to the invention are shown in figures 1 and 2.

As noted above, the pressurized fluid solvent used in the present invention is a pressurized liquid solvent or a densified fluid solvent. Although a variety of solvents can be used, it is preferred that an inorganic substance such as carbon dioxide, xenon, nitrous oxide, or sulfur hexafluoride, is used as the pressurized fluid solvent. For environmental and cost reasons, liquid carbon dioxide, supercritical or cost, liquid carbon dioxide, supercritical or subcritical is the preferred pressurized fluid solvent.

In addition, to maintain the pressurized fluid solvent in the appropriate fluid state, the internal pressure and temperature of the system must be appropriately controlled in relation to the critical pressure and temperature of the pressurized fluid solvent. For example, the critical pressure and temperature of carbon dioxide is approximately 73 atmospheres and 31 degrees Celsius, 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 the temperature. Similarly, system pressurization can be performed using a pressure regulator and a pump and / or compressor in combination with a pressure gauge. These components are conventional and are not shown in figures 1 and 2 since the placement and operation of these components are known in the prior art.

j System pressure and temperature can be monitored and controlled manually or by a conventional automated controller (which may include, for example, a properly 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. Unless otherwise noted, temperature and pressure are properly maintained throughout the system during operation. As such, elements contained in the system are constructed of sufficient size and material to withstand the temperature, pressure and flow parameters required for operation, and can be selected from, or designed using, any of a variety of high-pressure hardware currently available.

In the present invention, the preferred organic solvent must have a flash point greater than 37.77 ° C to allow for increased safety and less government regulation, such as having a low evaporation rate to minimize ephemeral emissions, being able to remove dirt that consists of dirt from insoluble particles and greases and solvent-soluble oils, and to prevent or reduce the re-deposit of dirt on the textile articles being cleaned.

Preferably, organic solvents suitable for use in the present invention include any of the following individually or in combination:

1. cyclic terpenes, specifically atherpene isomers; pine oil; α-pinene and d-limonene isomers. Additionally, any cyclic terpene having the following physical characteristics is suitable for use in the present invention: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.0 - 17.5 (MPa)1/2for dispersion, approximately 0.5 - 9.0 (MPa)1/2 to polar and approximately 0.0 - 10.5 (MPa)1/2 for hydrogen bonding.

2. Halocarbons, specifically, chlorinated, fluorinated and brominated hydrocarbons that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 1,100 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 10.0 - 17.0 (MPa)1/2 for dispersion, approximately 0.0 - 7.0 (MPa)1/2 to polar and approximately 0.0 - 5.0 (MPa)1/2 for hydrogen bonding.

3. Glycol ethers, specifically mono-, di-triethylene and mono-, di- and tripropylene glycol ethers that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4,238 and 7,340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.0 - 19.5 (MPa)1/2 for dispersion, approximately 3.0 20 7.5 (MPa)1/2 to polar and approximately 8.0 - 17.0 (MPa)1/2 for hydrogen bonding.

4. Polyols, specifically, glycols and other organic compounds that contain two or more hydroxyl radicals and have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.920 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 14.0 - 18.2 (MPa)1/2for dispersion, approximately 4.5 - 2 0.5 (MPa)1/2 to polar and approximately 15.0 30.0 (MPa)1/2 for hydrogen bonding.

5. Ethers, specifically, ethers that do not contain free hydroxyl radicals and that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 14.5 - 20.0 (MPa)1/2 for dispersion, approximately 1.5 - 6.5 (MPa)1/2 to polar and approximately 5.0 - 10.0 (MPa)1/2 for hydrogen bonding.

6. Glycol ethers esters, specifically, glycol ethers esters that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 15.0 - 20.0 (MPa)1/2 for dispersion, approximately 0.3 - 10.0 (MPa)1/2 to polar and approximately 8.0 - 16.0 (MPa)1/2 for hydrogen bonding.

7. Esters of monobasic carboxylic acids that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.0 - 17.0 (MPa)1/2 for dispersion, approximately 2.0 7.5 (MPa)1/2 to polar and approximately 1.5 - 6.5 (MPa)1/2 for hydrogen bonding.

8. Fatty alcohols, specifically alcohols in which the carbon chain adjacent to the hydroxyl group contains five or more carbon atoms and have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4,238 and 7,340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.3 - 18.4 (MPa)1/2 for dispersion, approximately 3.1 - 18.8 (MPa)1/2 to polar and approximately 8.4 - 22.3 (MPa)1/2 for hydrogen bonding.

9. Short-chain alcohols in which the carbon chain adjacent to the hydroxyl group contains four or less carbon atoms and has the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4,238 and 7,340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.5 - 18.0 (MPa)1/2 for dispersion, approximately 3.0 - 9.0 (MPa)1/2 to polar and approximately 9.0

- 16.5 (MPa)1/2 for hydrogen bonding.

10. Siloxanes having the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.900 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 14.0 - 18.0 (MPa)1/2 for dispersion, approximately 0.0 - 4.5 (MPa)1/2 to polar and approximately 0.0 - 4.5 (MPa)1/2 for hydrogen bonding.

11. Hydrofluoroethers that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 1.50; (3) total Hansen solubility parameters of approximately 12.0 to 18.0 (MPa)1/2 for dispersion, approximately 4.0 - 10.0 (MPa)1/2 to polar and approximately 1.5 - 9.0 (MPa)1/2 for hydrogen bonding.

12. Aliphatic hydrocarbons having the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.700 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 14.0 - 17.0 (MPa)1/2 for dispersion, approximately 0.0 - 2.0 (MPa)1/2 to polar and approximately 0.0 - 2.0 (MPa)1/2 for hydrogen bonding.

13. Esters of dibasic carboxylic acids that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.900 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately

13.5 - 18.0 (MPa)1/2 for dispersion, approximately 4.0 6.5 (MPa)1/2 to polar and approximately 4.0 - 11.0 (MPa)1/2 for hydrogen bonding.

14. Ketones that have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.800 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately 13.0 19.0 (MPa)1/2 for dispersion, approximately 3.0 - 8.0 (MPa)1/2 to polar and approximately 3.0 - 11.0 (MPa)1/2 for connection ofJãidSOlrêeiàbes aprotic. These include solvents that do not belong to any of the aforementioned solvent groups, do not contain dissociable hydrogens and have the following physical characteristics: (1) soluble in carbon dioxide at a pressure between 4.238 and 7.340 MPa and a temperature between 5 and 30 degrees Celsius; (2) specific gravity greater than approximately 0.900 (the higher the specific gravity, the better the organic solvent); (3) Hansen solubility parameters of approximately

15.0 - 21.0 (MPa)1/2 for dispersion, approximately 6.0 17.0 (MPa)1/2 to polar and approximately 4.0 - 13.0 (MPa)1/2 for hydrogen bonding.

Preferably, in addition to the three physical properties described with respect to each group above, the organic solvent used in the present invention must also have one or more of the following physical properties: (4) flash point greater than approximately 37.77 degrees Celsius; and (5) an evaporation rate of less than approximately 50 (where n-butyl acetate = 100). More preferably, the organic solvent used in the present invention has each of the above characteristics (i.e., those identified as (1) through (5)).

The Hansen solubility parameters were developed to characterize solvents for comparison purposes. Each of the three parameters (ie, dispersion, polar and hydrogen bond) represents a different solvency characteristic. In combination, the three parameters are a measure of the total strength and selectivity of a solvent. The Hansen solubility parameter ranges above identify solvents that are good solvents for a wide range of substances and also exhibit a degree of solubility in liquid carbon dioxide. The Hansen Total solubility parameter, which is the square root of the sum of the squares of the three parameters mentioned above, provides a more general description of the solvency of organic solvents.

Any organic solvent or mixture of organic solvents of the specified groups and which meet at least properties 1 through 3, and preferably all 5 properties, is suitable for use in the present invention. In addition, the organic solvent must also have low toxicity and low environmental impact. Table 1 below shows the physical properties of several organic solvents that may be suitable for use in the present invention. In Table 1, the solvents are soluble in carbon dioxide between 4.031

MPa / 5 ° C and 5.823 MPa / 20 ° C.

Gravity Soluble Solvent Evapor Rate Point Solubility Parameters Hansen <e ní β cu £ s to5 o

(ΰ

O)

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Referring now to Figure 1, a block diagram of a cleaning system is shown which has separate containers for cleaning and drying textile articles. The cleaning system 100 generally comprises a cleaning machine 102 that has a cleaning container 110 efficiently connected to, through one or more motor-activated axes (not shown), a rotating, perforated, cleaning wheel or drum 112 within the cleaning container 110 with an inlet 114 for cleaning container 110 and an outlet 116 of cleaning container 110 through which cleaning fluids can pass. A drying machine 104 has a drying container 120 capable of being pressurized. The pressurizable drying container 120 is efficiently connected to, via one or more motor-activated axes (not shown), a perforated rotating drying drum or drum, 122, inside the drying container 120 with an inlet 124 for the drying 120 and an outlet 126 of the drying container 120, through which pressurized fluid solvent can pass. The cleaning container 110 and the drying container 120 can be parts of the same machine or can comprise separate machines. In addition, the cleaning and drying steps of the present invention can be carried out in the same container, as described with reference to figure 2 below.

An organic solvent tank 130 contains any suitable organic solvent, as previously described, to be introduced into cleaning container 110 through inlet 114. A pressurized fluid solvent tank 132 contains pressurized fluid solvent to be added to pressurized drying container 120 via of entry 124. 0 filtration set 140 contains one or more filters that continuously remove contaminants from the organic solvent from the cleaning container 110 as cleaning takes place.

The components of the cleaning system 100 are connected to lines 150-156, which transfer organic and vaporized and pressurized fluid solvents between system components. The term line as used herein implies that it refers to a network of pipes or similar ducts capable of transporting fluid and, for certain purposes, is capable of being pressurized. The transfer of organic solvents and vaporized and pressurized fluid solvents through lines 150-156 is driven by valves 170-176 and pumps 190-193. Although 190-193 pumps are shown in the described mode, any method of transferring liquid and / or vapor between components can be used, such as by adding pressure to the component using a compressor to force the liquid and / or vapor from the component.

Textile articles are cleaned with an organic solvent such as those previously described or mixtures thereof. Textile articles can also be cleaned with a combination of organic solvent and pressurized fluid solvent, and that combination can be in varying proportions from approximately 50% by weight to 100% by weight of organic solvent and 0% by weight up to 50% by weight of pressurized fluid solvent. In the cleaning process, the textile articles are first separated as necessary to place the textile articles in groups suitable for cleaning together. Textile articles can then be treated on the spot as needed to remove any stains that cannot be removed during the cleaning process. The textile articles are then placed in the cleaning drum 112 of the cleaning system 100. It is preferred that the cleaning drum 112 is perforated to allow solvent-free interchange between the cleaning drum 112 and the cleaning container 110 as well as for transporting dirt from the textile articles to the filter assembly 140.

After placing the textile articles in the cleaning drum 112, an organic solvent contained in the organic solvent tank 130 is added to the cleaning container 110 through line 152 by opening valve 171, closing valves 170, 172, 173 and 174 and activating of the pump 190 to pump organic solvent through the inlet 114 of the cleaning container 110. 0 Organic solvent can contain one or more co-solvents, water, detergents or other additives to increase the cleaning capacity of the cleaning system 100. Alternatively, one or more additives can be added directly to the cleaning container 110. Pressurized fluid solvent can also be added to the cleaning container 110 together with the organic solvent to increase cleaning. Pressurized fluid solvent can be added to cleaning container 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 inlet 114 fluid solvent pressurized through the inlet 114 of the cleaning container 110. Of course, if pressurized fluid solvent is included in the cleaning cycle, the cleaning container 110 will need to be pressurized in the same way as the drying container 120, as discussed below.

When a sufficient amount of the organic solvent or combination of organic solvent and pressurized fluid solvent is added to the cleaning container 110, the motor (not shown) is activated and the perforated cleaning drum 112 is shaken and / or rotated inside the cleaning container. cleaning 110. During this phase, the organic solvent is continuously cycled through filtration set 140 by opening valves 170 and 172, closing valves 171, 173 and 174 and activating pump 191. 0 filtration set 140 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent that passes through them and may alternatively or in addition include one or more absorption or higher absorption filters to remove water, dyes and the like contaminants dissolved in the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from the organic solvent or pressurized fluid solvent are described more fully in US Order no. serial number 08 / 994.583 incorporated here for reference. As a result, the organic solvent is pumped through outlet 116, valve 172, line 151, filter assembly 140, line 150, valve 170 and re-enters cleaning container 110 through line 114. This cycling advantageously removes contaminants, including particulate contaminants and / or soluble contaminants, from the organic solvent and reintroduces the filtered organic solvent into the cleaning container 110 and shakes or rotates the cleaning drum 112. Through this process, contaminants are removed from the textile articles . Of course, in the case of pressurization of the cleaning container 110, this recirculation system will be maintained at the same pressure / temperature levels as those in the cleaning container 110.

After sufficient time has passed so that the desired level of contaminants is removed from the textile articles and organic solvent, the organic solvent is removed from the cleaning drum 112 and cleaning container 110 by opening valve 173, closing valves 170, 171, 172 and 174 and activation of pump 191 to pump the organic solvent through outlet 116 via line 153. The cleaning drum 112 is then spun at a high speed, such as 400-800 rpm, to remove even more organic solvent from the textile articles. The cleaning drum 112 is preferably perforated so that when the textile articles are rotated in the cleaning drum 112 at a high speed, the organic solvent can drain from the cleaning drum 112. Any organic solvent removed from the textile articles by rotating the cleaning drum 112 at high speed is also removed from the cleaning drum 112 in the manner described above. After removing the organic solvent from the cleaning drum 112, it can be disposed of or recovered and decontaminated for reuse using solvent recovery systems known in the art. In addition, multiple technical cleaning cycles. In addition, 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 take place in the same cleaning container or a separate cleaning container can be used for each cleaning cycle.

After removing a desired amount of the organic solvent from the textile articles by rotating the cleaning drum 112 at high speed, the textile articles are moved from the cleaning drum 112 to the drying drum 122 inside the drying container 120 in the same way as textile articles are moved between machines in conventional cleaning systems. In an alternative embodiment, a single drum can be used in both the cleaning cycle and the drying cycle, so that, instead of transferring the textile articles between the cleaning drum 112 and the drying drum 122, a single drum containing the textile articles, is transferred between the cleaning container 110 and the drying container 120. If the cleaning container 110 is pressurized during the cleaning cycle, it must be depressurized before removing the textile articles. After placing the textile articles in the drying drum 122, pressurized fluid solvent, such as that contained in the carbon dioxide tank 132, is added to the drying container 120 through lines 154 and 155 by opening valve 175, closing valves 174 and 176 and activation of pump 192 to pump pressurized fluid solvent through inlet 124 of drying container 120 through lines 154 and 155. When pressurized fluid solvent is added to drying container 120, the organic solvent that remains in the textile articles dissolves in the pressurized fluid solvent.

After adding a sufficient amount of pressurized fluid so that the desired level of organic solvent has been dissolved, the combination of pressurized fluid solvent and organic solvent is removed from the drying container 120 and therefore also from the drying drum 122, by opening the opening. valve 176, valve closing 175 and activation of pump 193 to pump the combination of pressurized fluid solvent and organic solvent through outlet 126 via line 156. If desired, this process can be repeated to remove additional organic solvent. The drying drum 122 is then spun at a high speed, such as 150-350 rpm. to further remove the combination of pressurized fluid solvent and organic solvent from textile articles. The drying drum 122 is preferably perforated so that when the textile articles are spun in the drying drum 122 at a high speed, the combination of pressurized fluid solvent and organic solvent can drain from the drying drum 122. Any combination of pressurized fluid solvent and organic solvent removed from the textile articles by rotating the drying drum 122 at high speed 25 is also pumped from the drying container 120 in the manner described above. After removing the combination of pressurized fluid solvent and organic solvent from the drying container 120, it can be disposed of or separated and recovered for reuse with solvent recovery systems known in the art. Note that, although preferred, it is not necessary to include a high speed rotation cycle to remove pressurized fluid solvent from textile articles.

After removing a desired amount of the pressurized fluid solvent from the textile articles by rotating the drying drum 122, the drying container 120 is depressurized over a period of approximately 5-15 minutes. Depressurizing the drying container 120 vaporizes any remaining pressurized fluid solvent, leaving textile articles without solvents, dried in the drying drum 122. The pressurized fluid solvent that has been vaporized is then removed from the drying container 120 by opening valve 176, closing valve 175 and activating pump 193. As a result, the vaporized pressurized fluid solvent is pumped through outlet 126, line 156 and valve 176, where it can then be bled into the atmosphere or recovered and re-compressed for reuse.

Although the cleaning system 100 has been described as a complete system, an existing, conventional dry cleaning system can be converted for use in accordance with the present invention. To convert a conventional dry cleaning system, the organic solvent described above is used for cleaning textile articles in the conventional system. A separate pressurized container is added to the conventional system for drying textile articles with pressurized fluid solvent. In this way, the conventional system is converted for use with a pressurized fluid solvent. For example, the system in figure 1 could represent such a converted system, where the components of the cleaning machine 102 are conventional and the pressurized fluid solvent tank 132 is not in communication with the cleaning container 100. In such a situation, the drying machine 104 is the addition part of the conventional cleaning machine.

In addition, although the system shown in figure 1 comprises a single cleaning container, multiple cleaning containers could be used, so that the textile articles are subjected to multiple cleaning steps, with each cleaning step performed in a cleaning container different using the same or different organic solvents at each stage. The description of the single cleaning container is for description purposes only and should not be construed as limiting the scope of the invention.

Referring now to Figure 2, a block diagram of an alternative embodiment of the present invention, a cleaning system is shown which has a single chamber for cleaning and drying textile articles. The cleaning system 200 generally comprises a cleaning machine that has a pressurizable container 210. 0 container 210 is efficiently connected to, via one or more motor-driven axles (not shown), a perforated rotating wheel or drum 212 within container 210 with an inlet 214 for container 210 and an outlet 216 of container 210, through which dry cleaning fluids can pass.

An organic solvent tank 220 contains any suitable organic solvent, such as those described above, to be introduced into container 210 through inlet 214. A pressurized fluid solvent tank 222 contains pressurized fluid solvent to be added to container 210 through inlet 214. The filtration set 224 contains one or more filters that continuously remove contaminants from the organic solvent from container 210 and drum 212 as cleaning takes place.

The cleaning system components 200 are connected to lines 230-234 that transfer organic solvents and pressurized and vaporized fluid solvent between system components. The term line as used herein implies that it refers to a network of piping or similar duct capable of transporting fluid and, for certain purposes, is capable of being pressurized. The transfer of organic solvents and pressurized and vaporized fluid solvent through lines 230-234 is directed by valves 250-254 and pumps 240-242. Although pumps 240-242 are shown in the described mode, any method of transferring liquid and / or vapor between components can be used, such as by adding pressure to the component using a compressor to force the liquid and / or vapor from the component.

Textile articles are cleaned with an organic solvent like those previously described. Textile articles can also be cleaned with a combination of organic solvent and pressurized fluid solvent and that combination can be in varying proportions of 50-100% by weight of organic solvent and 0-50% by weight of pressurized fluid solvent. In the cleaning process, the textile articles are first separated as necessary to place the textile articles in groups suitable for cleaning together. Textile articles can then be treated on the spot as needed to remove any stains that cannot be removed during the cleaning process. The textile articles are then placed on the drum 212 inside the vessel 210 of the cleaning system 200. It is preferred that the drum 212 is perforated to allow solvent-free interchange between the drum 212 and the container 210 as well as for transporting dirt from the textile articles to the filter assembly 224.

After placing the textile articles in the cleaning drum 212, an organic solvent contained in the organic solvent tank 220 is added to container 210 through line 231 by opening valve 251, closing valves 250, 252, 253 and 254, and activating the pump 242 for pumping organic solvent through inlet 214 of container 210. The organic solvent may contain one or more cosolvents, water, detergents or other additives to increase the cleaning capacity of the cleaning system 200 or other additives to impart other desirable attributes to the articles being treated. Alternatively, one or more additives can be added directly to the container. Pressurized fluid solvent can also be added to container 210 along with the organic solvent to increase cleanliness. Pressurized fluid solvent is added to container 210 via line 230 by opening valve 250, closing valves 251, 252, 253 and 254, and activating pump 240 to pump pressurized fluid solvent through inlet 214 of container 210.

When the desired amount of the organic solvent or combination of organic solvent and pressurized fluid solvent, as described above, is added to container 210, the motor (not shown) is activated and drum 212 is agitated and / or rotated. During this phase, the organic solvent, as well as pressurized fluid solvent if used in combination, is continuously cycled through the filtration set 224 by opening valves 253 and 253, closing valves 250, 251 and 254 and activating pump 241. The filtration assembly 224 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent and pressurized fluid solvent that pass through them and may alternatively or in addition include one or more absorption or higher absorption filters to remove water, dyes and other contaminants dissolved in the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from the organic solvent or pressurized fluid solvent are described more fully in US Order no. serial number 08 / 994.583 incorporated here for reference. As a result, the organic solvent is pumped through outlet 216, valve 253, line 233, filter assembly 224, line 232, valve 252 and re-enters container 210 through line 214. This cycling advantageously removes contaminants, including particulate contaminants and / or soluble contaminating contaminants, from the organic solvent and pressurized fluid solvent and reintroduces the filtered solvent into container 210. Through this process, contaminants are removed from the textile articles.

After enough time has passed so that the desired level of contaminants is removed from the textile and solvent products, the organic solvent is removed from the 210 and drum 212 by opening valve 254, closing valves 250, 251, 252 and 253, and activating the pump 241 to pump the organic solvent through outlet 216 and line 234. If pressurized fluid solvent is used in combination with organic solvent, it may be necessary to separate the pressurized fluid solvent from the organic solvent first. The organic solvent can then be eliminated or, preferably, contaminants can be removed from the organic solvent and the organic solvent recovered for further use. Contaminants can be removed from the organic solvent with solvent recovery systems known in the art. Drum 212 is then spun at a high speed 20 such as 400 - 800 rpm, to remove even more organic solvent from the textile articles. The drum 212 is preferably perforated so that when the textile articles are spun on the drum 212 at a high speed, the organic solvent can drain from the cleaning drum 212. Any organic solvent removed from the textile articles by rotating the drum 212 at high speed it can also be deleted or recovered for additional use.

After removing a desired amount of the organic solvent from the textile articles by rotating drum 212, pressurized fluid solvent contained in the pressurized fluid tank 222 is added to container 210 by opening valve 250, closing valves 252, 252, 253 and

254, and activation of pump 240 to pump pressurized fluid solvent through inlet 214 of pressurizable container 210 through line 230. When pressurized fluid solvent is added to container 210, the remaining organic solvent in the textile articles dissolves in the pressurized fluid solvent.

After adding a sufficient amount of pressurized fluid so that the desired level of organic solvent has been dissolved, the combination of pressurized fluid solvent and organic solvent is removed from container 210 and by opening valve 254, closing valves 250, 251, 252 and 253, and activation of pump 241 to pump the combination of pressurized fluid solvent and organic solvent through outlet 216 and line 234. Note that the 20 241 pump may actually require two pumps, one to pump the low pressure organic solvent in the cleaning cycle and one to pump the pressurized fluid solvent in the drying cycle.

The combination of pressurized fluid solvent and organic solvent can be eliminated or the combination can be separated and the organic solvent and pressurized fluid solvent separately recovered for further use. Drum 212 is then spun at a high speed like 15041

350 rpm, to remove even more combination of pressurized fluid solvent and organic solvent from textile articles. Any combination of pressurized fluid solvent and organic solvent removed from textile articles by rotating drum 212 at high speed can also be eliminated or retained for further use. Note that, although preferred, it is not necessary to include a high speed rotation cycle to remove pressurized fluid solvent from textile articles.

After removing a desired amount of the pressurized fluid solvent from the textile articles by rotating the drum 212, the container 210 is depressurized over a period of approximately 5-15 minutes. Depressurizing container 210 vaporizes the pressurized fluid solvent, leaving textile articles without solvent, dried in drum 212. 0 pressurized fluid solvent that has been vaporized is then removed from container 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. Note that although a single pump is shown as pump 241, separate pumps may be required to pump organic solvent, pressurized fluid solvent and pressurized fluid solvent vapors into pump 241. 0 remaining vaporized pressurized fluid solvent can then be bled into the atmosphere or compressed again into pressurized fluid solvent for further use.

As discussed above, terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, glycol ethers esters, fatty acid esters and other long-chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, solvents polar aprotics, cyclic hydrofluoroethyl methyl siloxanes, dibasic esters and aliphatic hydrocarbon solvents or similar solvents or mixtures of such solvents are organic solvents that can be used in the present invention, as shown in the test results below. Table 2 shows detergency test results for each of several solvents that may be suitable for use in the present invention. Table 3 shows results of the drying test and extraction of those solvents using dense carbon dioxide.

Detergency tests were carried out using several 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 researched - removal of dirt and deposit of dirt. 0 the first refers to the ability of a solvent to remove dirt from a substrate while the latter refers to the ability of a solvent to prevent dirt from being re-deposited on a substrate during the cleaning process. Standard dirty pads from Wascherei Forschungs Institute, Krefeld Germany (WFK) that have been stained with a range of insoluble materials and WFK white cotton pads, both obtained from TESTFABRICS, Inc., have been used to assess dirt removal and dirt replenishment, respectively.

The removal and deposit of dirt for each solvent were quantified using the Delta Whiteness index. This method allows you to measure the Whiteness index of each pad before and after processing. The Delta Whiteness index is calculated by subtracting the Whiteness index of the pad before processing from the Whiteness index of the pad after processing. 0 Whiteness index is a function of the light reflectance of the pad and in this order is an indication of the amount of dirt on the pad. More dirt results in lower light reflectance and Whiteness for the pad. Whiteness indexes were measured using a reflectometer manufactured by Hunter Laboratories.

The organic solvent test was performed in a Launder-Orneter while the dense carbon dioxide test was performed in a Parr Pump. After measuring their whiteness indexes, two WFK standard dirty pads and two WFK white cotton pads were placed in a Launder-Ometer cup with 25 spherical stainless steel bearings and 150 ml of the solvent in question. The cup was then sealed, placed in the Launder-Ometer and stirred for a specified period of time. Subsequently, the pads were removed and placed in a Parr Pump equipped with a mesh basket. Approximately 1.5 liters of liquid carbon dioxide between 5 ° C and 25 ° C and 4.031 MPa and 5.823 MPa were transferred to the Parr Pump. After several minutes, the Parr Pump was bled and the dry pellets removed and allowed to reach room temperature. The dense carbon dioxide test was carried out in the same way, however test pads were treated for 20 minutes. During that time the liquid carbon dioxide was stirred using a stirrer mounted on the inner cover of the Parr pump. The Whiteness index of the processed pads was determined using the reflectometer. The two Delta Whiteness indexes obtained for each pair of pads were taken on average. The results are shown in Table 2.

Since the Delta Whiteness index is calculated by subtracting the Whiteness index from a pad before processing from the Whiteness index value after processing, a positive Delta Whiteness index indicates that there has been an increase in the Whiteness index as a result of processing. In practical terms, this means that the dirt was removed during processing. In fact, the higher the Delta Whiteness Value, the more dirt was removed from the pad during processing. Each of the organic solvents tested showed dirt removal capacity. The WFK white cotton pads showed a reduction in Delta Whiteness indexes indicating that dirt was deposited on the pads during the cleaning process. Therefore, a less negative Delta Whiteness index suggests that

Table 2

<td></td><td></td><td colspan="2">Delta Whiteness Values</td>

<td>Solvent</td><td>Cleaning time (min.)</td><td>Removing insoluble dirt</td><td>Repository of insoluble dirt</td>

<td>dioxide liquid carbon (pure)</td><td> 20</td><td> 3,36</td><td> -1,23</td>

<td>d-limonene</td><td> 12</td><td> 10,6</td><td> -9,2</td>

<td>1,1-2 trichloro- rotrifluoroe- tano</td><td> 12</td><td> 11,7</td><td> -14,46</td>

<td>N- bromide propyl</td><td> 12</td><td> 11,18</td><td> -9,45</td>

<td>perfluoroexane</td><td> 12</td><td> 2,09</td><td> -3,42</td>

<td>mono- ether triethyl oleyl leno glycol (Volpo 3)</td><td> 12</td><td> 10,54*</td><td> -1,86*</td>

<td>α-phenyl - ω - hydroxy-poly (oxy-1,2- eta- nodiila)</td><td> 12</td><td> 1,54**</td><td> -13,6**</td>

<td>hexylene glycol</td><td> 12</td><td> 6,9</td><td> -1,4</td>

<td>dimethyl ether tetraethylene |</td><td> 12</td><td> 10,08</td><td> -4,94</td>

<td>glycol</td><td></td><td></td><td></td>

<td>diacetate of ethylene glycol</td><td> 12</td><td> 6,29</td><td> -3,39</td>

<td>acetates of decila (Exxate 1000)</td><td> 12</td><td> 11,69</td><td> -8,6</td>

<td>acetates of tridecyl (Exxate 1300)</td><td> 12</td><td> 11,24</td><td> -4,86</td>

<td>methyl soy esters (Soy- Gold 1100)</td><td> 12</td><td> 5,81</td><td> -7,71</td>

<td>2-ethylexanol</td><td> 12</td><td> 12,6</td><td> -3,4</td>

<td>carbonate propylene</td><td> 12</td><td> 2,99</td><td> -1,82</td>

<td>dimethyl sulfoxide</td><td> 12</td><td> 5,84</td><td> -0,22</td>

<td>dimethylforma- mida</td><td> 12</td><td> 7,24</td><td> -10,09</td>

<td>isoparaffins (DF-2000)</td><td> 12</td><td> 11,23</td><td> -5,95</td>

<td>glutarate dimethyl</td><td> 12</td><td> 9,04</td><td> -1,23</td>

* After two extraction cycles ** after three extraction cycles.

To assess the capacity of the dense carbon dioxide to extract organic solvent from a substrate, WFK white cotton pads were used. A pad was weighed dry and then immersed in a sample of organic solvent. Excess solvent was removed from the pad using a torsion device manufactured by Atlas Electric Devices Company. The wet pad was weighed again to determine the amount of solvent retained in the tissue. After placing the wet pad in a Parr Pump, dense carbon dioxide was transferred to the Parr Pump. The temperature and pressure of the dense carbon dioxide for all experiments varied from 5 ° C to 20 ° C and from 4.031 MPa - 5.823 MPa. After five minutes, the Parr Pump was bled and the pad was removed. The pad was subjected to Soxhlet extraction using methylene chloride for a minimum of two hours. This device allows the pad to be continuously extracted to remove the organic solvent from the pad. After determining the concentration of the organic solvent in the extract using gas chromatography, the amount of organic solvent remaining in the pad after exposure to dense carbon dioxide was calculated by multiplying the concentration of the organic solvent in the extract by the volume of the extract. A different pad was used for each of the tests. The results of these tests are included in Table 3. As the results indicate, the extraction process using dense carbon dioxide is extremely effective.

Table 3

<td></td><td>Weight of</td><td>solvent</td><td>Percentage</td>

<td></td><td colspan="2">in wad of</td><td>by weight of</td>

<td></td><td colspan="2">test (grams)</td><td>solvent</td>

<td>Solvent</td><td>before</td><td>after ex-</td><td>removed from</td>

<td></td><td>extraction</td><td>traction</td><td>wad</td>

<td>d-limonene</td><td> 5,8</td><td> 0,0014</td><td> 99,98%</td>

<td>1,1-2 trichlorotrifluoroethane</td><td> 1,4</td><td> 0,0005</td><td> 99,96%</td>

<td>N-propyl bromide</td><td> 2,8</td><td> <0,447</td><td> >84%</td>

<td>perfluoroexane</td><td> 1,0</td><td> 0,0006</td><td> 99,94%</td>

<td>triethyl mono-oleyl ether</td><td> 0,8</td><td> 0,1824</td><td> 77,88%</td>

<td>glycol (7)</td><td></td><td></td><td></td>

<td>α-phenyl - ω - hydroxy-poly</td><td> 16,0</td><td> 5,7</td><td> 64,5%</td>

<td>(oxy-1,2-ethanediyl) (Eth-</td><td></td><td></td><td></td>

<td>hexylene glycol</td><td> 4,9</td><td> 0,3481</td><td> 92,87%</td>

<td>tetraethylene dimethyl ether</td><td> 5,2</td><td> 0,1310</td><td> 97,48%</td>

<td>glycol</td><td></td><td></td><td></td>

<td>ethylene glycol diacetate</td><td> 5,3</td><td> 0,0418</td><td> 99,21%</td>

<td>decyl acetate (2)</td><td> 2,4</td><td> 0,0015</td><td> 99,94%</td>

<td>tridecyl acetate (1)</td><td> 4,8</td><td> 0,0605</td><td> 98,75%</td>

<td>soy methyl esters (8)</td><td> 4,9</td><td> 0,0720</td><td> 98,54%</td>

<td>2-ethylexanol</td><td> 0,5</td><td> 0,0599</td><td> 99,09%</td>

<td>propylene carbonate</td><td> 6,6</td><td> 0,0599</td><td> 99,09%</td>

<td>dimethyl sulfoxide</td><td> 3,3</td><td> 0,5643</td><td> 82,69%</td>

<td>dimethylformamide</td><td> 3,0</td><td> 0,0635</td><td> 97,88%</td>

<td>octamethylcyclooctasiloxane /</td><td> 5,5</td><td> 0,0017</td><td> 99,97% |</td>

<td>decamethylcyclopentasiloxane (4)</td><td></td><td></td><td></td>

<td>1-methoxy nonofluorobutane (6)</td><td> 0,7</td><td>not detected</td><td> -100%</td>

<td>Isoparaffins (5)</td><td> 4,3</td><td> 0,0019</td><td> 99,96%</td>

<td>dimethyl glutarate (3) +</td><td> 5,8</td><td> 0,0090</td><td> 99,85%</td>

Observations in Table 3: (1) Exxate 1300 (Exxon);

(2) Exxate 1000 (Exxon); (3) DBE-5 (DuPont); (4) SF1204 (General Electric Silicones); (5) DF-2000 (Exxon); (6) HFE-7100 (3M); (7) Volpo 3 (Croda); (8) Soy Gold 1100 (AG Environmen5 tal Products)

It should be understood that a wide range of changes and modifications to the modalities described above will be evident to those skilled in the art and are considered. Therefore, it is intended that the detailed description10 of the above is considered to be illustrative rather than limiting, and that it is to be understood that the following claims, including all equivalents, are intended to define the spirit and scope of the invention.

···· ····

Contents33

78 members in 13 offices

This recordMember, by publication datePriority claim3 more offices are in the list below

Priority claims2

Priority claims
Document	Office	Kind	Date
83784901	United States of America	A	2001-04-18
0212304	United States of America	W	2002-04-18

Members78

Family members, oldest first
Document	Office	Kind
CA2388500A1	Canada	A1	2001-04-26
CA2388913A1	Canada	A1	2001-04-26
WO0129305A1	World Intellectual Property Organization (WIPO)	A1	2001-04-26
WO0129306A1	World Intellectual Property Organization (WIPO)	A1	2001-04-26
AU8021700A	Australia	A	2001-04-30
AU8021800A	Australia	A	2001-04-30
US2002010965A1	United States of America	A1	2002-01-31
US2002011258A1	United States of America	A1	2002-01-31
US6355072B1	United States of America	B1	2002-03-12
NO20021764D0	Norway	D0	2002-04-15
NO20021765D0	Norway	D0	2002-04-15
NO20021764L	Norway	L	2002-06-14
NO20021765L	Norway	L	2002-06-17
EP1224351A1	European Patent Office (EPO)	A1	2002-07-24
EP1224352A1	European Patent Office (EPO)	A1	2002-07-24
US2002100124A1	United States of America	A1	2002-08-01
BR0014770A	Brazil	A	2002-09-17
CA2444807A1	Canada	A1	2002-10-31
CA2445448A1	Canada	A1	2002-10-31
CA2647080A1	Canada	A1	2002-10-31
WO02086222A1	World Intellectual Property Organization (WIPO)	A1	2002-10-31
WO02086223A1	World Intellectual Property Organization (WIPO)	A1	2002-10-31
AU2002256275B9	Australia	B9	2002-11-05
WO02086223B1	World Intellectual Property Organization (WIPO)	B1	2002-12-19
JP2003512111A	Japan	A	2003-04-02
US6558432B2	United States of America	B2	2003-05-06
BR0014772A	Brazil	A	2003-06-10
NZ518788A	New Zealand	A	2003-09-26
US2003220219A1	United States of America	A1	2003-11-27
EP1381728A1	European Patent Office (EPO)	A1	2004-01-21
EP1383951A1	European Patent Office (EPO)	A1	2004-01-28
CA2388500C	Canada	C	2004-03-30
CA2388913C	Canada	C	2004-04-13
US6736859B2	United States of America	B2	2004-05-18
JP2004515560A	Japan	A	2004-05-27
US6755871B2	United States of America	B2	2004-06-29
US2004168262A1	United States of America	A1	2004-09-02
MXPA02003817A	Mexico	A	2004-09-06
US2004173246A1	United States of America	A1	2004-09-09
MXPA02003816A	Mexico	A	2004-10-14
AU777996B2	Australia	B2	2004-11-11
MXPA03009617A	Mexico	A	2004-12-06
AU778581B2	Australia	B2	2004-12-09
NZ529724A	New Zealand	A	2005-01-28
BR0209201A	Brazil	A	2005-02-22
MXPA03009721A	Mexico	A	2005-03-07
NZ526305A	New Zealand	A	2005-03-24
EP1224351B1	European Patent Office (EPO)	B1	2006-08-23
EP1224352B1	European Patent Office (EPO)	B1	2006-08-23
US7097715B1	United States of America	B1	2006-08-29
NZ529457A	New Zealand	A	2006-08-31
AT337427T	Austria	T	2006-09-15
AT337428T	Austria	T	2006-09-15
DE60030304D1	Germany	D1	2006-10-05
DE60030305D1	Germany	D1	2006-10-05
BR0209037AThis record	Brazil	A	2006-10-10
US7147670B2	United States of America	B2	2006-12-12
US2007017036A1	United States of America	A1	2007-01-25
ES2270877T3	Spain	T3	2007-04-16
US2007087955A1	United States of America	A1	2007-04-19
AU2002256275B2	Australia	B2	2007-08-09
DE60030304T2	Germany	T2	2007-08-23
DE60030305T2	Germany	T2	2007-08-23
AU2002309578B2	Australia	B2	2007-10-11
US2008127427A1	United States of America	A1	2008-06-05
US7435265B2	United States of America	B2	2008-10-14
US2008263781A1	United States of America	A1	2008-10-30
CA2445448C	Canada	C	2008-12-02
US7534308B2	United States of America	B2	2009-05-19
US7566347B2	United States of America	B2	2009-07-28
US2009193594A1	United States of America	A1	2009-08-06
US2009255061A1	United States of America	A1	2009-10-15
CA2444807C	Canada	C	2010-02-09
USRE41115E	United States of America	E	2010-02-16
JP4563638B2	Japan	B2	2010-10-13
US7867288B2	United States of America	B2	2011-01-11
US2011073138A1	United States of America	A1	2011-03-31
BR0014770B1	Brazil	B1	2012-03-20

7 legal events, as the office reported them to INPADOC

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Events

Legal events, newest first
	Event	Code
2015-09-15	Decision: refusalB09B	B09B
2015-06-16	Decision: refusalB09B	B09B
2014-09-02	Technical examination (opinion): publication of technical examination (opinion)B07A	B07A
2014-08-26	Technical and formal requirements: publication cancelledB06I	B06I
2014-08-12	Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent lawB06A	B06A
2013-10-29	Application fees: restorationB08G	B08G
2013-07-02	Application fees: dismissal - article 86 of industrial property lawB08F	B08F