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3 5,267,45 4 CO2 isoften stored and/or transported inrefrigerated tanks at approximately 300 psi and — 18” C. In charging the inventive system with CO2, pump 21 isadapted to drawlowpressureliquidCO2throughline92thatis connected to a refrigerated tank (not shown) through make-up heater 42 which raises the temperature of the C01. The heater preferably has ?nned coils through which ambient air ?ows and employs resistive electric Suitable compounds as the ?rst ?uid are either liquid or are in a supercritical state within the temperature and pressure hatched area illustrated by FIG. 3. The partic ularlypreferred?rst?uidinpracticingthisinventionis carbondioxideduetoitsreadyavailabilityandenviron mental safety. The critical temperature of carbon diox ide is 31° C. and the dense (or compressed) gas phase above the critical temperature and near (or above) the critical pressure is often referred to as a “supercritical heating.Pump 21isadirectdrive,single-pistonpump. LiquidCO1isthenstoredinthestoragevessel12at10 ?uid."Otherdensi?edgasesknownfortheirsupercriti approximately 915 psi and 25° C. The storage vessel is preferably made of stainless steel. As shown in FIG. 1, conventional temperature gauges (each depicted as an encircled “T”), pressure gauges (each depicted as an encircled“P”),liquidCO2levelmeters(eachdepicted 15 as an encircled “L”), and a ?owmeter (depicted as an encircled “F”) are employed in the system. In addition, conventional valves are used. In operation, after placing soiled substrate into the cleaningvessel,thecleaningvesselisthenchargedwith20 gaseous CO2 (from the storage vessel) to an intermedi ate pressure of approximately 200-300 psi to prevent extreme thermal shock to the chamber. The gaseous CO2 istransferred into the cleaning vessel through lines 82and84.Thereafter,liquidCO2ispumpedintothe25 cleaningvesselfromthestoragevesselthroughlines80, 91, 81, and 82 by pump 20 which preferably has dual pistons with either direct or hydraulic/electric drive. The pump raises the pressure of the liquid CO; to ap proximately 900 to 1500 psi. Subcooler 30 lowers the temperature of the CO2 by 2° to 3° below the boiling point to prevent pump cavitation. The temperature of the CD; can be adjusted by heating/cooling coils 95 locatedinsidethecleaningvessel.Beforeorduringthe 35 cleaningcycle,cleaningadditivesmaybeaddedintothe cleaning vessel by pump 23 through lines 82 and 83. Moreover, pump 23 through lines 82 and 83 can also be used to deliver a compressed gas into the cleaning ves sel as described below. Practice of the invention requires contact of a sub strate having a contaminant with the ?rst, substantially non-polar ?uid that is in a liquid or in a supercritical state. With reference to FIG. 3, when using CO2 as the ?rst ?uid, its temperature can range broadly from 45 slightly below about 20° C. to slightly above about 100° C. as indicated on the horizontal axis and the pressure can range from about 1000 psi to about 5000 psi as shown on the vertical axis. However, within this broad rangeoftemperatureandpressure,ithasbeendiscov 50 ered that there is a zone (represented by the hatched area of the left, or on the convex side, of the curve) where surface blistering to components such as buttons can be reduced, whereas practice outside of the zone tends to lead to button damage that can be quite severe. 55 As is seen by the hatched region of FIG. 3, preferred conditions are between about 900 psi to 2000 psi at temperatures between about 20° C. to about 45° C., with more preferred conditions being pressure from about 900 psi to about 1500 psi at temperatures between about 20° C. and 100° C. or from about 3500 psi to about 5000 psi at temperatures between about 20° C. and 37° C. Where fabrics are being cleaned, one preferably works within a temperature range between about 20° C. to about100°C.Inaddition,ithasbeenfoundwithinthis65 range that processes which raise the temperature prior to decompression reduce the damage to polymeric parts. cal properties, as well as carbon dioxide, may also be employed as the first ?uid by themselves or in mixture. Thesegasesincludemethane,ethane,propane,ammoni um-butane, n-pentane, n-hexane, cyclohexane, n-hep tane,ethylene,propylene,methanol,ethanol,isopropa n01, benzene, toluene, p-xylene, chlorotri?uorometh ane, trichloro?uoromethane, per?uoropropane, chlo rodi?uoromethane, sulfur hexa?uoride, and nitrous oxide. Althoughthe?rst?uiditselfissubstantiallynon polar, it may include other components, such as a source of hydrogen peroxide and an organic bleach activatortherefor,asisdescribedincopendingapplica tion Ser. No. 754,809, ?led Sep. 4, 1991, inventors Mitchelletal.,ofcommonassignmentherewith.For example, the source of hydrogen peroxide can be se lected from hydrogen peroxide or an inorganic perox ide and the organic bleach activator can be a carbonyl ester such as alkanoyloxybenzene. Further, the ?rst ?uid may include a cleaning adjunct such as another liquid (e.g., alkanes, alcohols, aldehydes, and the like, particularly mineral oil or petrolatum), as described in Ser. No 715,299, ?led Jun. 14, 1991, inventor Mitchell, ofcommon assignmentherewith. Inapreferredmode ofpracticingthepresentinven tion, fabrics are initially pretreated before being con tacted with the ?rst ?uid. Pretreatment may be per— formed at about ambient pressure and temperature, or at elevated temperature. For example, pretreatment can include contacting a fabric to be cleaned with one or more of water, a surfactant, an organic solvent, and other active cleaning materials such as enzymes. Sur prisingly, ifthese pretreating components are added to the bulk solution of densi?ed carbon dioxide (rather than as a pretreatment), the stain removal process can actuallybeimpeded. Since water is not very soluble in carbon dioxide, it can adhere to the substrate being cleaned in a dense carbon dioxide atmosphere, and impede the cleaning process.Thus,whenapretreatingstepincludeswater, then a step after the ?rst ?uid cleaning is preferable where the cleaning ?uid is contacted with a hygro scopic ?uid, such as glycerol, to eliminate water other wise absorbed onto fabric. Prior art cleaning with carbon dioxide has typically involved an extraction type of process where clean, dense gas is pumped into a chamber containing the substratewhile“dirty”densegasisdrainedThistypeof continuous extraction restricts the ability to quickly process, and further when pressure in the cleaning chamber is released, then residual soil tends to be rede posited on the substrate and the chamber walls. This problemisavoidedbypracticeoftheinventivemethod (although the present invention can also be adapted for useascontinuousextractionprocess,ifdesired). The time during which articles being cleaned are exposed to the ?rst ?uid will vary, depending upon the nature of the substrate being cleaned, the degree ofPDF Image | SUPERCRITICALCARBON DIOXIDE DRY CLEANING SYSTEM
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