A cleaning system that utilizes an organic cleaning solvent and pressurized fluid solvent is disclosed. The system has no 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 an organic solvent cleaning cycle, the solvent is extracted from the textiles at high speed in a rotating drum in the same way conventional solvents are extracted from textiles in conventional evaporative hot air dry cleaning machines. Instead of proceeding to a conventional drying cycle, the extracted textiles are then immersed in pressurized fluid solvent to extract the residual organic solvent from the textiles. This is possible because the organic solvent is soluble in pressurized fluid solvent. After the textiles are immersed in pressurized fluid solvent, pressurized fluid solvent is pumped from the drum. Finally, the drum is de-pressurized to atmospheric pressure to evaporate any remaining pressurized fluid solvent, yielding clean, solvent free textiles. The organic solvent is preferably selected from terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, esters of glycol ethers, esters of fatty acids and other long chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters, and aliphatic hydrocarbons solvents or similar solvents or mixtures of such solvents and the pressurized fluid solvent is preferably densified carbon dioxide.
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1. A process for removing contaminants from one or more substrates that comprise contaminants, the process comprising steps of:
(a) placing the one or more substrates in a rotatable cleaning unit;
(b) placing the rotatable cleaning unit in a pressurizable vessel;
(c) adding organic solvent to at least one of the vessel and the cleaning unit;
(d) imparting movement of the cleaning unit under substantially non-pressurized conditions;
(e) removing a first portion of the organic solvent from the vessel;
(f) pressurizing the vessel;
(g) adding pressurized fluid solvent to the vessel to form an organic solvent-pressurized fluid solvent mixture;
(h) removing at least a portion of the mixture from the pressurized vessel;
(i) depressurizing the vessel to form vaporized fluid solvent and substantially dry, clean one or more substrates; and
(j) removing at least a portion of the dry, clean one or more substrates from the vessel; wherein:
steps (a)-(b) occur in any order or substantially simultaneously.
3. The process of
5. The process of
6. The process of
7. The process of
8. The process of
9. The process of
10. The process of
13. The process of
14. The process of
15. The process of
17. The process of
18. The process of
19. The process of
22. The process of
23. The process of
24. The process of
26. The process of
a=5n and 1≦n≦3;
each X is independently F, Cl, Br or I;
0≦z≦4;
0≦j≦10;
0≦k 10; and
0≦(j+k)≦10n.
27. The process of
1≦n≦20;
each X is independently F, Cl, Br or I;
0≦j;
k≦2n+2; and
2n−4≦(j+k)≦2n+2.
28. The process of
Riv=CjHuXv;
Rii=CkHyXz or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
0≦u, v≦2j+1;
0≦(u+v)≦2j+1;
0≦y,z≦2k+1;
0≦(y+z)≦2k+1;
0≦u,v,y,z≦37;
R1-4 and R9-12 are independently CmHnXp,
where 0≦m≦2;
0≦(n+p)≦5; and
n+p=2m+1;
R5-8 and R13-16 are independently CaHbXd,
wherein a is 0 or 1;
0≦(b+d)≦3; and
b+d=2a+1; and
each X is independently F, Cl, Br or I.
29. The process of
Riv=CjHuXv;
Rii=CkHyXz or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
j and k each equal 0 independently or
14−3(x+y+z)≦j≦22−3(x+y+z);
14−3(x+y+z)≦k≦22−3(x+y+z) and
14−3(x+y+z)≦(j+k)≦22−3(x+y+z);
0≦x,y,z≦1;
0≦(x+y+z)≦3;
0≦u,v,y,z≦37;
0≦(u+v)≦2j+1;
0≦(y+z)≦2k+1;
R1-3 and R7-9 are independently CmHnXp,
where 0≦m≦2;
0≦(n+p)≦5; and
n+p=2m+1;
R4-6 and R10-12 are independently CaHbXd,
wherein a is 0 or 1;
0≦(b+d)≦3; and
b+d=2a+1; and
each X is independently F, Cl, Br or I.
30. The process of
each X is independently F, Cl, Br or I;
1≦n≦20;
0≦r≦4;
0≦j≦2n+2−r;
0≦k≦2n+2−r; and
2n−4−r≦(j+k)≦2n+2−r.
31. The process of
each X is independently F, Cl, Br or I;
2≦n≦20;
0≦j≦2n+2;
0≦k≦2n+2;
2n−4≦(j+k)≦2n+2; and
1≦b≦6.
32. The process of
Rv=CjHuXv;
Rii=CkHaXb;
15≦j,k≦32−3(w+x+y+z);
15≦j+k≦32−3(w+x+y+z);
0≦u,v≦2j+1;
0≦a;
b2k+1;
2j−7≦(u+v)≦2j+1;
2k−7≦(y+z)≦2k+1; and
R1-4 and R9-12 are independently CmHnXp,
wherein 0≦m≦2;
0≦(n+p)≦5; and
n+p=2m+1;
R5-8 and R13-16 are independently CaHbXd,
wherein a is 0or 1;
0≦(b+d)≦3; and
b+d=2a+1; and
each X is independently F, Cl, Br or I.
33. The process of
Riv=CjHuXv;
Rv=CjHuXv;
Rii=CkHaXb;
15≦j,k≦32−3(w+x+y+z);
15≦j+k≦32−3(w+x+y+z);
0≦u,v≦2j+1;
0≦a;
b≦2k+1;
2j−7≦(u+v)≦2j+1;
2k−7≦(y+z)≦2k+1; and
R1-4 and R9-12 are independently CmHnXp,
wherein 0≦m≦2;
0≦(n+p)≦5; and
n+p=2m+1;
R5-8 and R13-16 are independently CaHbXd,
wherein a is 0 or 1;
0≦(b+d)≦3; and
b+d=2a+1; and
each X is independently F, Cl, Br or I.
34. The process of
wherein:
each X is independently F, Cl, Br or I;
2≦n≦21;
1≦m≦3;
0≦a;
b≦2n+2; and
2n−2≦(a+b)≦2n+z.
35. The process of
wherein:
each X is independently F, Cl, Br or I;
2≦n≦18;
m=1;
0≦a;
b≦2n+2; and
2n−4≦(a+b)≦2n+z.
36. The process of
wherein:
Rl=CjHaXb
1≦j≦6
0≦a;
b≦2j+1; and
2j−7≦(a+b)≦2j+1;
R2=CkHdXe
1≦k≦6;
0≦d;
e≦2k+1; and
d+e=2k+1;
R3=CmHeXf
1≦m≦6;
0≦e;
f≦2m+1; and
e+f=2m+1; and
each X is independently F, Cl, Br or I.
37. The process of
wherein:
each X is independently F, Cl, Br or I;
1≦e≦2;
2≦n≦8;
0≦j;
k≦2a+1; and
2n≦(j+k)≦2n+1.
38. The process of
wherein:
1≦n≦10;
1≦a;
b≦2 and a=b; and
2n−1≦y≦2n+1.
39. The process of
wherein:
each R equals CaXyHz independently;
each X is independently F, Cl, Br or I;
1≦a≦3; and
0≦y,z≦2a+1 and y+z=2a+1.
40. The process of
wherein:
2≦n≦4;
each R equals CaHyXz independently;
each X is independently F, Cl, Br or I;
1≦n≦3
0y;
z≦2a+1 and y+z=2a+1.
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This application is a
wherein:
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
CnXjHk
wherein:
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures: ##STR00001##
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
CnHjXk(OR)r
wherein:
wherein:
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures: ##STR00003##
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the following general chemical structure:
Cn(CO2)mHaXb
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures:
Cn(CO3)mHaXb
In another embodiment of the invention, the organic solvent of the invention is composed, at least in part, of a chemical having the one of the following general chemical structures: ##STR00006##
wherein:
wherein:
Referring now to
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 line 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 line 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. In the cleaning process, 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.
After the textiles are placed in the cleaning drum 112, 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. Of course, if pressurized fluid solvent is included in the cleaning cycle, the cleaning vessel 110 will need to be pressurized in the same manner as the drying vessel 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 vessel 110, the motor (not shown) is activated and the perforated cleaning drum 112 is agitated and/or rotated within cleaning vessel 110. During this phase, the organic solvent is continuously cycled through the filtration assembly 140 by opening valves 170 and 172, closing valves 171, 173 and 174, and activating pump 191. 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 Ser. No. 08/994,583 incorporated herein by 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 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. Of course, in the event the cleaning vessel 110 is pressurized, this recirculation system will be maintained at the same pressure/temperature levels as those in cleaning vessel 110.
After sufficient time has passed so that the desired level of contaminants is removed from the textiles and organic solvent, 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 400-800 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, 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. Furthermore, 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.
After a desired amount of the organic solvent is removed from the textiles by rotating the cleaning drum 112 at high speed, 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. In an alternate embodiment, 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. Once the textiles have been placed in the drying drum 122, pressurized fluid solvent, such as that contained in the carbon dioxide tank 132, 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. When pressurized fluid solvent is added to the drying vessel 120, the organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
After a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved, 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.
After a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drying drum 122, the drying vessel 120 is pressurized 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. As a result, 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.
While 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 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. Thus, the conventional system is converted for use with a pressurized fluid solvent. For example, the system in
Furthermore, while the system shown in
Referring now to
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 than 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 line 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 line 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. In the cleaning process, 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.
After the textiles are placed in the drum 212, 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 or other additives to impart other desirable attributes to the articles being treated. 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.
When the desired amount of the organic solvent, or combination of organic solvent and pressurized fluid solvent as described above, is added to the vessel 210, the motor (not shown) is activated and the 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 assembly 224 by opening valves 252 and 253, closing valves 250, 251 and 254, and activating pump 241. 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 Ser. No. 08/994,583 incorporated herein by reference. As a result, 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.
After sufficient time has passed so that the desired level of contaminants is removed from the textiles and solvents, 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. If 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.
After a desired amount of organic solvent is removed from the textiles by rotating the drum 212, 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. When pressurized fluid solvent is added to the vessel 210, organic solvent remaining on the textiles dissolves in the pressurized fluid solvent.
After a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved, the 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. Note that 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 150-350 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. Note that while a single pump is shown as 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.
As discussed above, terpenes, halohydrocarbons, certain glycol ethers, polyols, ethers, esters of glycol ethers, esters of fatty acids and other long chain carboxylic acids, fatty alcohols and other long-chain alcohols, short-chain alcohols, polar aprotic solvents, siloxanes, hydrofluoroethers, dibasic esters, and aliphatic hydrocarbons 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 1 shows results of detergency testing for each of a number of solvents that may be suitable for use in the present invention. Table 2 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 Forschungs 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. After measuring their Whiteness Indices, two WFK standard soil swatches and two WFK white cotton swatches were placed in a Launder-Ometer cup with 25 stainless steel ball bearings and 150 mL of the solvent of interest. The cup was then sealed, placed in the Launder-Ometer and agitated for a specified length of time. Afterwards, the swatches were removed and placed in a Parr Bomb equipped with a mesh basket. Approximately 1.5 liters of liquid carbon dioxide between 5° C. and 25° C. and 570 psig and 830 psig was transferred to the Parr Bomb. After several minutes the Parr Bomb was vented and the dry swatches removed and allowed to reach room temperature. Testing of densified carbon dioxide was carried out in the same manner but test swatches were treated for 20 minutes. During this time the liquid carbon dioxide was stirred using an agitator mounted on the inside cover of the Parr bomb. The Whiteness Index of the processed swatches was determined using the reflectometer. The two Delta Whiteness Indices obtained for each pair of swatches were averaged. The results are presented in Table 1.
Because 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 soil removal capabilities. 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.
TABLE 1
Delta Whiteness Values
Cleaning
Insoluble
Insoluble Soil
Solvent
Time (min.)
Soil Removal
Redeposition
Liquid carbon
20
336
−1.23
dioxide (neat)
Pine oil
12
8.49
−6.84
d-limonene
12
10.6
−9.2
1,1-2
12
11.7
−14.46
trichlorotrifluoroethane
N-propyl bromide
12
11.18
−9.45
Perfluorohexane
12
2.09
−6.42
triethylene glycol mono-
12
10.54*
−1.86*
oleyl ether (Volpo 3)
α-phenyl-ω-hydroxy-
12
1.54**
−13.6**
poly(oxy-1,2-ethanediyl)
Hexlene glycol
12
6.9
−1.4
Tetraethylene glycol
12
10.08
−4.94
dimethyl ether
Ethylene glycol diacetate
12
6.29
−3.39
Decyl acetates
12
11.69
−8.6
(Exxate 1000)
Tridecyl acetates (Exxate
12
11.24
−4.86
1300)
Soy methyl esters
12
5.81
−7.71
(SoyGold 1100)
2-ethylhexanol
12
12.6
−3.4
Propylene carbonate
12
2.99
−1.82
Dimethylsulfoxide
12
5.84
−0.22
Dimethylformamide
12
7.24
−10.09
Isoparaffins (DF-2000)
12
11.23
−5.95
Dimethylglutarate
12
9.04
−1.23
*After two extraction cycles.
**After three extraction cycles.
To evaluate the ability of densified carbon dioxide to extract organic solvent from a substrate, WFK white cotton swatches were used. One swatch was weighed dry and then immersed in an organic solvent sample. Excess solvent was removed from the swatch using a ringer manufactured by Atlas Electric Devices Company. The damp swatch was re-weighed to determine the amount of solvent retained in the fabric. After placing the damp swatch in a Parr Bomb densified carbon dioxide was transferred to the Parr Bomb. The temperature and pressure of the densified carbon dioxide for all of the trials ranged from 5° C. to 20° C. and from 570 psig-830 psig. After five minutes the Parr Bomb was vented and the swatch removed. 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. After determining the concentration of the organic solvent in the extract using gas chromatography, 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 2. As the results indicate, the extraction process using densified carbon dioxide is extremely effective.
TABLE 2
Percentage by
Weight of Solvent on
Weight of
Test Swatch (grams)
Solvent
Before
After
Removed from
Solvent
Extraction
Extraction
Swatch
Pine oil
7.8
0.1835
97.66%
d-Limonene
5.8
0.0014
99.98%
1,1 2-Trichlorotrifluoroethane
1.4
0.0005
99.96%
N-Propyl bromide
2.8
<0.447
>84%
Perfluorohexane
1.0
0.0006
99.94%
Triethylene glycol monooleyl
0.8
0.1824
77.88%
ether(7)
α-phenyl-ω-hydroxy-poly
16.0
5.7
645%
(oxy 1,2-ethanediyl);
(Ethylan HB4)
Hexylene glycol
4.9
0.3481
92.87%
Tetraethylene glycol
5.2
.1310
97.48%
dimethyl ether
Ethylene glycol diacetate
53
0.0418
99.21%
Decyl acetate(2)
2.4
0.0015
99.94%
Tridecyl acetate(1)
4.8
0.0605
98.75%
Soy methyl esters(8)
4.9
0.0720
98.54%
2-Ethylhexanol
0.5
0.0599
99.09%
Propylene carbonate
6.6
0.0599
99.09%
Dimethyl sulfoxide
33
0.5643
82.69%
Dimethylformamide
3.0
0.0635
97.88%
Octamethylcyclooctasiloxane/
5.5
0.0017
99.97%
Decamethylcyclopentasiloxane
(4)
1-Methoxynonofluorobutane(6)
0.7
not
−100%
detected
Isoparaffin(5)
4.3
0.0019
99.96%
Dimethyl glutarate(3) ‡
5.8
0.0090
99.85%
Notes on 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 (Crods);
(8)Soy Gold 1100 (AG Environmental Products)
It is to be understood that a wide range of changes and modifications to the embodiments described above will be apparent to those skilled in the art and are contemplated. It is therefore, intended that the foregoing detailed description be regarded as illustrative rather than limiting, and that it be understood that it is the following claims, including all equivalents, that are intended to define the spirit and scope of the invention.
Racette, Timothy L., Damaso, Gene R., Schulte, James E.
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