WO2000077135A2 - Liquid carbon dioxide cleaning utilizing natural and modified natural solvents - Google Patents
Liquid carbon dioxide cleaning utilizing natural and modified natural solvents Download PDFInfo
- Publication number
- WO2000077135A2 WO2000077135A2 PCT/US2000/013079 US0013079W WO0077135A2 WO 2000077135 A2 WO2000077135 A2 WO 2000077135A2 US 0013079 W US0013079 W US 0013079W WO 0077135 A2 WO0077135 A2 WO 0077135A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon dioxide
- bio
- article
- cleaning
- diesel
- Prior art date
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000004140 cleaning Methods 0.000 title claims abstract description 90
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 71
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title description 20
- 239000002904 solvent Substances 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 239000003225 biodiesel Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002689 soil Substances 0.000 claims abstract description 22
- 102000004190 Enzymes Human genes 0.000 claims abstract description 19
- 108090000790 Enzymes Proteins 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 30
- 239000004744 fabric Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 3
- 238000002203 pretreatment Methods 0.000 abstract description 17
- 238000013019 agitation Methods 0.000 abstract description 15
- 239000012071 phase Substances 0.000 description 37
- 239000002609 medium Substances 0.000 description 33
- 239000000654 additive Substances 0.000 description 21
- 239000012530 fluid Substances 0.000 description 11
- 238000013459 approach Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 description 9
- 239000008158 vegetable oil Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 239000004519 grease Substances 0.000 description 6
- 239000010730 cutting oil Substances 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 2
- 235000006008 Brassica napus var napus Nutrition 0.000 description 2
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 2
- 244000188595 Brassica sinapistrum Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000020518 Carthamus tinctorius Species 0.000 description 2
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 2
- 244000020551 Helianthus annuus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000828 canola oil Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000779 depleting effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000647 material safety data sheet Toxicity 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 235000019462 natural additive Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101001091385 Homo sapiens Kallikrein-6 Proteins 0.000 description 1
- 102100034866 Kallikrein-6 Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0021—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/266—Esters or carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/40—Products in which the composition is not well defined
- C11D7/44—Vegetable products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
-
- C11D2111/40—
Definitions
- This invention relates to the cleaning of articles, and, more specifically, to an approach for improving carbon dioxide cleaning processes.
- Carbon dioxide is an inexpensive and unlimited natural resource that is non-toxic, non-flammable, non-smog producing, and non-ozone depleting. In its dense phases, both liquid and supercritical, it exhibits solvating properties typical of hydrocarbon solvents. Matter dissolved in dense-phase carbon dioxide may be readily recovered in its concentrated form by gasifying the carbon dioxide. No secondary waste stream is produced such as is associated with the use of conventional solvents. The carbon dioxide does not damage fabric or dissolve common dyes, and its properties make it a good dry cleaning medium for fabrics and garments. It is also a suitable degreasing/cleaning medium for the removal of light oils from commercial and industrial parts and components. Dense phase carbon dioxide has been referenced as a cleaning fluid for garments and components in numerous patents, including, for example.
- Typical additives used to enhance the organic solvating power of the dense-phase carbon dioxide have been the same compounds that are targeted for displacement because of their harmful nature.
- Examples include co-solvents such as low alkanes, terpenes, alcohols, ketones, benzene, toluene, xylenes, and chlorinated, fluorinated, or chloro-fluorinated compounds.
- This invention provides a method and apparatus for dense-phase carbon dioxide cleaning of articles.
- the approach of the invention retains good effectiveness in removing paniculate soils from the articles, and has increased effectiveness in removing grease, oil, and hydrophilic soils as compared with the use of only the dense-phase carbon dioxide.
- the approach makes use of natural and modified natural additives with good solvating properties.
- the additives are environmentally friendly, non-toxic, biodegradable, and free of sulfur and aromatics. They may be rinsed with water and form stable emulsions with other phases such as water, mineral spirits, alcohols, and some terpenes.
- the additives may be used in conjunction with known dense-phase carbon dioxide cleaning procedures.
- a method for cleaning an article comprises the steps of providing an article having soil in contact therewith, treating at least a portion of the article with a bio-diesel compound, and contacting the article, with dense-phase carbon dioxide to dislodge the soil from the article.
- the article may be rinsed to remove the bio-diesel compound, if it is present after contacting is complete.
- Bio-diesel compounds are a recognized class comprising alkyl monoesters of vegetable oils, preferably the methyl esters of vegetable oils. Examples of suitable vegetable oils are safflower, sunflower, canola, and soybean oils. The bio-diesel compounds are fully compatible with dense-phase (liquefied or supercritical) carbon dioxide. The term “bio-diesel” originates in an unrelated use of such compounds as ingredients in synthetic diesel fuel.
- the article to be cleaned may be fabric or other articles such as metallic, ceramic, or plastic parts to be degreased and cleaned.
- the contacting of the bio- diesel compound to the article and the agitating of the article may be accomplished completely or partially serially, or simultaneously, as may be appropriate for particular applications.
- the article may be pre- treated with the bio-diesel compound and thereafter placed into a pool of dense- phase carbon dioxide in a pressure chamber and agitated.
- the bio-diesel compound may instead be added to the pool of dense-phase carbon dioxide in an in-situ treatment.
- a combination of pre-treatment and in-situ treatment may be used.
- the pre-treatment may be a general pre-treatment such as soaking, or a localized pre-treatment such as the "spotting" of a fabric.
- the bio-diesel compound may be formed into an emulsion with water and/or enzymes, and used in any of these pre-treatment and in-situ treatment alternatives.
- the contacting and agitating may be accomplished by any operable approach, such as, for example, the force of liquid jets of the dense-phase carbon dioxide directed into the pool, the bubbling as some of the dense-phase carbon dioxide vaporizes, a tumbling action, stirring of the pool by an impeller, circulation of the carbon dioxide with a pump, and ultrasonic cavitation.
- Figure 1 is a block flow diagram of a preferred embodiment of a method according to the invention
- Figure 2 is a schematic system diagram of an apparatus used in the method of Figure 1;
- Figure 3 is a representation of a chemical reaction used to produce a bio- diesel compound.
- Figure 1 depicts a preferred approach for practicing the invention.
- An apparatus is provided, numeral 20.
- the apparatus may be of any operable type to accomplish the remaining steps of the process, and
- Figure 2 depicts one embodiment of a preferred apparatus 40 most suitable for commercial fabric- cleaning operations.
- the apparatus 40 includes a cleaning chamber 42 having a pressure vessel 44 and a pressure door 46 that seals to the pressure vessel 44.
- the cleaning chamber 42 is designed to withstand the internal pressures utilized in the subsequent steps, typically in the range of about 550 pounds per square inch (psi) to about 1000 psi, preferably about 700-800 psi, and is made of steel.
- a perforated basket 48 with openings therein is supported within the cleaning chamber 42, with an open end facing the pressure door 46 so that articles may be placed into or removed from the perforated basket 48 when the pressure door 46 is open.
- the pressure vessel 44 and the perforated basket 48 are cylindrically symmetric about a cylindrical axis 50.
- Dense-phase carbon dioxide cleaning medium is delivered to the interior of the cleaning chamber 42 by one or more manifolds 52. Additives are mixed with the dense-phase carbon dioxide, as will be discussed subsequently.
- Each manifold 52 has one or more jet orifices 54 therein through which the dense-phase carbon dioxide flows. The jet orifices 54 are preferably positioned so that the flow of cleaning medium from the jet orifices 54 is aimed into the interior of the perforated basket 48 through the openings therein and thence around the articles being cleaned.
- the dense-phase carbon dioxide is pumped through the manifolds 52 and into the cleaning chamber 42 by a main pump 56 operating through appropriate valves 58 and 60.
- the dense-phase carbon dioxide cleaning medium is initially pumped to a preset depth within the cleaning chamber 42 to form a pool of the liquefied cleaning medium.
- additional dense-phase carbon dioxide is forced through the jet orifices 54 to agitate the pool and the articles therein.
- the dense-phase carbon dioxide cleaning medium flows to a lint trap 62, which filters solid matter from the cleaning medium.
- Liquefied cleaning medium is supplied to the main pump 56 from a storage tank 76, operating through the valve 74.
- Optional additives to the liquefied cleaning medium to be discussed subsequently are supplied on the inlet side of the main pump 56 from an additive supply 78 through an additive pump 80.
- Cleaning medium may also flow from the cleaning chamber 42 back to the inlet side of the main pump 56 through a drain line 82 operating through the valve 74, during the "drain" portion of the process.
- the apparatus 40 further includes a vent valve 84 permitting the cleaning chamber 42 to be vented to atmosphere.
- a return path for gaseous carbon dioxide through a compressor 86 to the condenser 70 or to the storage tank 76 is provided with appropriate valves 88, 90, and 91.
- a distillation column 92 with appropriate valving 94 and 96 is provided. The distillation is typically performed off-line, when the cleaning chamber 42 is not in use for cleaning articles.
- This apparatus 40 is designed primarily for cleaning fabrics but may be used to clean other articles as well. The apparatus is ordinarily optimized for the type of article to be cleaned.
- the cleaning chamber 42 is decompressed to atmospheric pressure after the gas compressor 86 recovers the carbon dioxide vapors back to the storage tank 76. Residual gaseous carbon dioxide is vented out through the vent valve 84, the pressure door 46 is opened, and the clean load is removed.
- the method of the present invention may be performed with this exemplary apparatus 40 when it is applied to the cleaning of articles such as fabrics or garments, but it is not limited to this apparatus.
- this apparatus for example, other types of contacting and agitation devices such as an impeller to agitate the liquid pool in the cleaning chamber 42, an ultrasonic excitation transducer to produce cavitation of the liquid pool, or any of the other techniques discussed herein may be used.
- the article may be of any operable type and configuration, as long as it fits within the perforated basket 48.
- One preferred application of the present invention is the cleaning of fabric articles such as clothing, and another preferred application is the cleaning and degreasing of parts and components.
- the article is optionally pre- treated, numeral 24.
- the article is contacted with a pre- treatment fluid.
- the contacting may comprise, for example, a spot contacted with the pre-treatment fluid or a submersion and soaking in the pre-treatment fluid.
- the article is maintained in contact with the pre-treatment fluid for a period of time, typically about 1 minute to about 24 hours, preferably about 1 minute to about 60 minutes, to permit the pre-treatment fluid to solubilize any non- particulate soils fixed to the article.
- the pre-treatment fluid preferably comprises a bio-diesel compound.
- Bio-diesel compounds are alkyl monoesters (specifically, the methyl and ethyl esters) of vegetable oils or fats, preferably the methyl esters of vegetable oils. Examples of suitable vegetable oils are rapeseed, safflower, sunflower, canola, and soybean oils. Bio-diesel compounds may be prepared from used fryer cooking oil, in a re-use of this waste product. Each of the vegetable oils is made up from glycerides derived from many different carboxylic acids, but each oil has its characteristic composition that does not differ substantially from sample to sample.
- the bio-diesel compounds have the advantages that they have low viscosities, have low vapor pressures, have densities similar to that of liquefied carbon dioxide, are biodegradable, are non-toxic, are free of sulfur and aromatics, and have a relatively high Kaui-butanol value of about 60 (compared with perchloroethylene, which is about 90), indicating that they are good organic solvents. They are water rinsable and readily form emulsions with water, mineral spirits, alcohols, and some terpenes. They are compatible with dense-phase carbon dioxide, having about the same specific gravity of 0.9.
- the bio-diesel pretreatment fluid may optionally be mixed with other components, such as water and/or cleaning enzymes.
- Enzymes are proteins that speed up (catalyze) a reaction that involves the making or breaking of a covalent bond. Enzymes act by lowering the temperature under which a given bond is unstable. Numerous examples exist where well-defined molecules speed up reactions between other molecules, but not all enzymatic reactions are specific.
- carrier compound here the bio-diesel compound
- the bio-diesel compound is needed to facilitate their introduction into a dense-phase carbon dioxide process. Any operable relative amounts of the bio-diesel compound and the other components may be used.
- the bio-diesel compound, or a mixture of the bio-diesel compound with enzymes or water in any ratio is present in the dense-phase carbon dioxide in an amount of from about 0.01 to about 5 percent by volume. Lesser amounts are ineffective, and greater amounts are wasteful and lead to residual contamination of the cleaned article with the bio-diesel compound that may necessitate its removal.
- the pretreatment if used, may be performed within the cleaning chamber 42 or in a separate container.
- the article which optionally may be pretreated in step 24, is placed into the cleaning apparatus 40, numeral 26, in this preferred case into the perforated basket 48 of the cleaning chamber 42.
- the pressure door 46 is closed and sealed.
- a cleaning medium is introduced into the sealed cleaning chamber 42 to form a pool therein, numeral 28, by pumping the cleaning medium from the storage tank 76 using the main pump 56 in the manner described previously.
- the pool preferably partially or fully covers the article in the perforated basket 48.
- the cleaning medium comprises the liquefied carbon dioxide with the addition of one or more of the bio-diesel compounds discussed above.
- the cleaning medium introduced in step 28 may be the same composition as the pre- treatment cleaning medium used in step 24, or a different bio-diesel-containing medium may be used.
- Other additives may be added as well, such as the water and/or enzymes discussed earlier. The prior discussion of these various materials is incorporated herein.
- the total amount of additives is typically from about 0.01 to about 5.0 percent, with a preferred range of about 0.1 to about 1.0 percent, of the total of the carbon dioxide and the additives.
- the pool and the article therein are agitated, numeral 30.
- the agitation is accomplished in the illustrated apparatus 40 by the action of the cleaning medium pumped through the manifold 52 and the liquid jet orifices 54.
- the liquid jet orifices 54 are directed toward the interior of the perforated basket 48 through the openings therein, to impinge upon the articles to be cleaned therein.
- the agitation is continued for a period of time sufficient to dislodge particulate soil adhered to the article, and to solubilize and remove non-particulate matter such as oils, grease, and hydrophilic soils.
- This agitation time varies according to the nature of the article, the dirtiness of the article, and other factors, but is typically from about 5 to about 30 minutes.
- Agitation may be accomplished by any operable approach, such as the preferred liquid jets, but also hydrodynamic cavitation generated by a propeller, impeller, or blade, circulation with a pump or compressor, ultrasonic cavitation produced by transducers, sonic whistles, or a combination of these techniques.
- the cleaning medium is drained from the cleaning chamber 42, numeral 32.
- the article may be rinsed, numeral 34, by introducing a rinsing medium such as neat liquefied carbon dioxide into the cleaning chamber 42 and agitating the articles with the un-modified liquefied carbon dioxide.
- a rinsing medium such as neat liquefied carbon dioxide
- This step is performed if the cleaning medium was used with additives, and it is desirable to remove those additives completely from the article before the article is used.
- the article is a fabric such as clothing, and the cleaning medium contained some bio-diesel compound, it is usually desirable to rinse out the bio-diesel compound with un-modified liquefied carbon dioxide.
- the rinsing medium is drained out of the cleaning chamber 42.
- the residual pressure within the cleaning chamber 42 is vented to atmospheric pressure using the vent valve 84, and the articles are removed from the cleaning chamber 42. Any remaining carbon dioxide evaporates during this venting and removal, leaving the articles dry and clean upon removal from the cleaning chamber.
- a load of stainless steel metal parts was treated with various greases, such as CRC Industries No. MSDS SL3310, 3160, 3131, 3141, and Exxon L/M 48721 1, and with thread cutting oil type C 10326 made by W.H. Harvey.
- the parts were placed into a 12 gallon capacity liquid carbon dioxide cleaning chamber 42. Sufficient liquid carbon dioxide was introduced into the chamber to submerge the load.
- a bio-diesel compound commercially marketed by the Charbon Group, Huntington Beach, CA as SSW-1000, was added to the chamber 42 in an amount of 0.1 percent, 0.5 percent, 1.0 percent, or 2.0 percent of the total of the carbon dioxide and the bio-diesel compound.
- the liquid carbon dioxide (and bio-diesel compound, where present) cleaning medium was agitated for 10 minutes at temperatures in the range of 0-85°F, using a cavitating blade and propeller, to accelerate the removal of grease and oil.
- the solvent was then drained, the chamber was decompressed, and the parts were removed and examined for the presence of visual and tactile residue.
- no bio-diesel compound was used, only the mineral oil component of the greases was removed, and the drawing soaps and other additives in the greases remained to contaminate the parts in the form of a tough film-like coating.
- the thread cutting oil remained as a sticky residue on the parts.
- a load of stainless steel parts was treated with a polishing compound consisting of heavy waxes and aluminum powder in the 20-40 micrometer range.
- the load was pre-treated (step 24) for 30 minutes in bio-diesel compound of the same type used in Example 1. After pre-treatment, and without drying, the load was placed into the same cleaning chamber used in Example 1, and treated in the same manner as described for Example 1 (steps 26, 28, 30, and 32).
- the example was repeated without a pre-treatment, for concentrations of the bio-diesel compound of 0.1 percent, 0.5 percent, 1.0 percent, 2 percent, and 5 percent in the liquefied carbon dioxide used in steps 28 and 30.
- Full removal of the polishing compound required a 5 percent concentration of the bio-diesel compound, substantially greater than the 1.0 percent required where a pretreatment is employed.
- the 5 percent concentration of the bio-diesel compound was used, it was necessary to conduct a post-agitation rinse (step 34), because there was a light film of bio-diesel compound remaining on the parts after agitation and draining.
- Examples 1-2 demonstrate that the use of the bio-diesel compound enhances the cleaning of the parts.
- Example 2 shows that the pre-treatment lowers the amount of the bio-diesel compound required in the subsequent treatment and agitation, reducing the need for post-drain rinsing.
- a load of stainless steel parts was dipped into a saturated salt water solution, removed, and allowed to dry. The load was then placed into the cleaning chamber discussed in Example 1.
- a solution of liquid carbon dioxide and bio- diesel compound/water (0.5 percent bio-diesel compound plus water, 1 : 1 volume ratio of bio-diesel compound to water) was introduced into the chamber and agitated for 10 minutes to solubilize the salt and remove it from the part. The treatment was under the same conditions as discussed for Example 1. The chamber was then drained and the parts were removed and inspected.
- the salt was removed. Where there was no bio-diesel compound and water present in the cleaning medium, the salt was not removed.
- Example 2 The same polishing compound used in Example 2 was applied to a load of stainless steel parts, and the load was placed into the cleaning chamber discussed in Example 1.
- a solution of liquid carbon dioxide and bio-diesel compound/water/Bacto- zyme enzyme (0.5 percent of bio-diesel compound/water/Bacto-zyme, with a ratio of 1 : 1 : 1 by volume bio-diesel compound:water:Bacto-zyme) was introduced into the chamber and agitated for 10 minutes under the conditions discussed in Example 1, except that the temperature was in the range of 40-85°F.
- Bacto-zyme discussed in MSDS 1 1 13, is a natural multifaceted enzyme agent having a complex non-bacterial organic formulation that promotes the penetration and emulsification of oily or fatty substances and is marketed commercially by the Charbon Group.
- a load of fabric was spotted with thread cutting oil, the spots were treated with concentrated bio-diesel compound fluid, and the load was placed into the cleaning chamber discussed in Example 1.
- Liquid carbon dioxide was introduced at 55-65°F into the cleaning chamber, and the load was agitated for 10 minutes. The fluid was drained, the system was decompressed, and the fabrics were removed for evaluation. No residual cutting oil was visible on the fabrics, which were spot free and dry when removed.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001503975A JP2003502135A (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning using natural and modified natural solvents |
AU54402/00A AU5440200A (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning utilizing natural and modified natural solvents |
KR1020017000412A KR20010053477A (en) | 1999-06-11 | 2000-05-11 | Liquid Carbon Dioxide Cleaning Utilizing Natural and Modified Natural Solvents |
CA002337529A CA2337529A1 (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning utilizing natural and modified natural solvents |
EP00939296A EP1144565A3 (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning utilizing natural solvents |
MXPA01000334A MXPA01000334A (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning utilizing natural and modified natural solvents. |
AU2003231689A AU2003231689A1 (en) | 1999-06-11 | 2003-08-11 | Liquid carbon dioxide cleaning utilising natural and modified natural solvents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US33073699A | 1999-06-11 | 1999-06-11 | |
US09/330,736 | 1999-06-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000077135A2 true WO2000077135A2 (en) | 2000-12-21 |
WO2000077135A3 WO2000077135A3 (en) | 2001-10-04 |
Family
ID=23291096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/013079 WO2000077135A2 (en) | 1999-06-11 | 2000-05-11 | Liquid carbon dioxide cleaning utilizing natural and modified natural solvents |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1144565A3 (en) |
JP (1) | JP2003502135A (en) |
CN (1) | CN1320183A (en) |
AU (2) | AU5440200A (en) |
CA (1) | CA2337529A1 (en) |
ID (1) | ID28922A (en) |
IL (1) | IL139799A0 (en) |
MX (1) | MXPA01000334A (en) |
WO (1) | WO2000077135A2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003024630A1 (en) * | 2001-09-14 | 2003-03-27 | Micell Technologies, Inc. | Method and apparatus for cleaning substrates using liquid carbon dioxide |
JP2003206497A (en) * | 2002-01-11 | 2003-07-22 | Sony Corp | Method for cleansing and drying |
US6782900B2 (en) | 2001-09-13 | 2004-08-31 | Micell Technologies, Inc. | Methods and apparatus for cleaning and/or treating a substrate using CO2 |
EP1723224A2 (en) * | 2004-03-02 | 2006-11-22 | Troxler Electronics Laboratories, Inc. | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
US7300527B2 (en) * | 2002-04-25 | 2007-11-27 | Hideo Yoshida | Method for activating surface of base material and apparatus thereof |
EP2454359A2 (en) * | 2009-07-16 | 2012-05-23 | Rhodia Opérations | Industrial cleaning compositions and methods for using same |
US8367739B2 (en) | 2004-12-29 | 2013-02-05 | Troxler Electronic Laboratories, Inc. | Asphalt release agent |
US8475643B2 (en) * | 2003-05-16 | 2013-07-02 | Hideo Yoshida | Anodic oxidation method and production for titanium oxide coating and method of supporting catalyst |
EP2592134A3 (en) * | 2011-11-13 | 2013-07-10 | Compad Consulting GmbH | Sustainable cleaning agents and detergents |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7250259B2 (en) * | 2017-09-26 | 2023-04-03 | トタル リサーチ アンド テクノロジー フエリユイ | Cleaning method for removing red oil deposits in equipment containing fatty acid esters as cleaning agents and the use of fatty acid esters as cleaning agents in such methods |
KR20200056515A (en) | 2018-11-14 | 2020-05-25 | 삼성전자주식회사 | method for drying substrate, photoresist developing method and photolithography method using the same |
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EP0518653B1 (en) * | 1991-06-14 | 1995-09-06 | The Clorox Company | Method and composition using densified carbon dioxide and cleaning adjunct to clean fabrics |
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2000
- 2000-05-11 JP JP2001503975A patent/JP2003502135A/en active Pending
- 2000-05-11 MX MXPA01000334A patent/MXPA01000334A/en unknown
- 2000-05-11 CN CN00801421A patent/CN1320183A/en active Pending
- 2000-05-11 ID IDW20010064A patent/ID28922A/en unknown
- 2000-05-11 CA CA002337529A patent/CA2337529A1/en not_active Abandoned
- 2000-05-11 EP EP00939296A patent/EP1144565A3/en not_active Withdrawn
- 2000-05-11 AU AU54402/00A patent/AU5440200A/en not_active Abandoned
- 2000-05-11 WO PCT/US2000/013079 patent/WO2000077135A2/en not_active Application Discontinuation
- 2000-05-11 IL IL13979900A patent/IL139799A0/en unknown
-
2003
- 2003-08-11 AU AU2003231689A patent/AU2003231689A1/en not_active Abandoned
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GB1465386A (en) * | 1973-07-26 | 1977-02-23 | South African Wool Board | Method of washing animal fibres |
EP0518653B1 (en) * | 1991-06-14 | 1995-09-06 | The Clorox Company | Method and composition using densified carbon dioxide and cleaning adjunct to clean fabrics |
US5693600A (en) * | 1994-07-20 | 1997-12-02 | Bruno Unger Scandinavia Aps | Cleansing agent for printing machines and presses and a method of cleaning such machines and presses |
US5759209A (en) * | 1995-03-16 | 1998-06-02 | Linde Aktiengesellschaft | Cleaning with liquid gases |
US5858022A (en) * | 1997-08-27 | 1999-01-12 | Micell Technologies, Inc. | Dry cleaning methods and compositions |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6782900B2 (en) | 2001-09-13 | 2004-08-31 | Micell Technologies, Inc. | Methods and apparatus for cleaning and/or treating a substrate using CO2 |
US6763840B2 (en) | 2001-09-14 | 2004-07-20 | Micell Technologies, Inc. | Method and apparatus for cleaning substrates using liquid carbon dioxide |
WO2003024630A1 (en) * | 2001-09-14 | 2003-03-27 | Micell Technologies, Inc. | Method and apparatus for cleaning substrates using liquid carbon dioxide |
JP2003206497A (en) * | 2002-01-11 | 2003-07-22 | Sony Corp | Method for cleansing and drying |
US7300527B2 (en) * | 2002-04-25 | 2007-11-27 | Hideo Yoshida | Method for activating surface of base material and apparatus thereof |
US8475643B2 (en) * | 2003-05-16 | 2013-07-02 | Hideo Yoshida | Anodic oxidation method and production for titanium oxide coating and method of supporting catalyst |
US8951951B2 (en) | 2004-03-02 | 2015-02-10 | Troxler Electronic Laboratories, Inc. | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
EP1723224A4 (en) * | 2004-03-02 | 2008-02-27 | Troxler Electronics Lab Inc | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
EP1723224A2 (en) * | 2004-03-02 | 2006-11-22 | Troxler Electronics Laboratories, Inc. | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
US8951952B2 (en) | 2004-03-02 | 2015-02-10 | Troxler Electronic Laboratories, Inc. | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
US11001789B2 (en) | 2004-03-02 | 2021-05-11 | Crude Spill Cleaning Co. Inc. | Solvent compositions for removing petroleum residue from a substrate and methods of use thereof |
US8367739B2 (en) | 2004-12-29 | 2013-02-05 | Troxler Electronic Laboratories, Inc. | Asphalt release agent |
US9358579B2 (en) | 2004-12-29 | 2016-06-07 | Troxler Electronics Laboratories, Inc. | Asphalt release agent |
EP2454359A2 (en) * | 2009-07-16 | 2012-05-23 | Rhodia Opérations | Industrial cleaning compositions and methods for using same |
EP2454359A4 (en) * | 2009-07-16 | 2013-10-16 | Rhodia Operations | Industrial cleaning compositions and methods for using same |
EP2592134A3 (en) * | 2011-11-13 | 2013-07-10 | Compad Consulting GmbH | Sustainable cleaning agents and detergents |
Also Published As
Publication number | Publication date |
---|---|
CA2337529A1 (en) | 2000-12-21 |
IL139799A0 (en) | 2002-02-10 |
ID28922A (en) | 2001-07-12 |
EP1144565A2 (en) | 2001-10-17 |
WO2000077135A3 (en) | 2001-10-04 |
MXPA01000334A (en) | 2002-04-24 |
AU5440200A (en) | 2001-01-02 |
CN1320183A (en) | 2001-10-31 |
AU2003231689A1 (en) | 2003-09-11 |
JP2003502135A (en) | 2003-01-21 |
EP1144565A3 (en) | 2001-11-28 |
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