EP0571246A1 - Process for degreasing of a plurality of objects - Google Patents
Process for degreasing of a plurality of objects Download PDFInfo
- Publication number
- EP0571246A1 EP0571246A1 EP93401217A EP93401217A EP0571246A1 EP 0571246 A1 EP0571246 A1 EP 0571246A1 EP 93401217 A EP93401217 A EP 93401217A EP 93401217 A EP93401217 A EP 93401217A EP 0571246 A1 EP0571246 A1 EP 0571246A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- degreasing
- liquid
- phase
- degreasing liquid
- fatty substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005238 degreasing Methods 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 239000000725 suspension Substances 0.000 claims abstract description 10
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 106
- 239000000126 substance Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 13
- 238000002604 ultrasonography Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010908 decantation Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 52
- 239000012071 phase Substances 0.000 description 28
- 229940099259 vaseline Drugs 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 235000019271 petrolatum Nutrition 0.000 description 5
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 208000031968 Cadaver Diseases 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- -1 propylene glycol ethers Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
-
- 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
- C11D7/261—Alcohols; Phenols
-
- 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
- C11D7/264—Aldehydes; Ketones; Acetals or ketals
-
- 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
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation
Definitions
- the present invention relates to the technical field of the treatment of surfaces of manufactured objects, and, more specifically, to the industrial degreasing of a plurality of objects.
- degreasing is to remove from the surface of an object all the fatty products and the various soiling it contains, so that this surface, made clean, regains the intrinsic physicochemical properties of the matter which forms it.
- This material is generally a metal or a metal alloy, in particular based on copper, iron, aluminum, zinc or even a precious metal such as gold or platinum. It can also be a mineral glass, a ceramic or a plastic.
- degreasing operations are an essential step in all production processes and lead to improved product quality and reliability.
- residues from degreasing with chlorinated solvents mainly contain oils and greases.
- the level of chlorinated solvent in these residues can be lowered by distillation.
- the highly concentrated final residue must be disposed of in accordance with current legislation - (see reference: Handling of residues and waste of chlorinated solvents Chimie et Industrie, (1988), 522-525.
- aqueous processes In terms of energy, aqueous processes generally require more energy than processes operating with chlorinated solvents mainly when a drying step is required. If this step can be avoided, the energy consumption of aqueous processes may be lower.
- the energy considered above covers the production of the chemical substances used, cleaning proper as well as recycling and disposal of waste.
- the object of the present invention is to find an industrial degreasing process which does not have the drawbacks of the two processes mentioned above, in particular as regards the possible impact on the environment.
- step a / the layer of fatty substance is covered with the degreasing liquid by any suitable means and in particular by spraying with a jet or spray or else by immersion of the surface of the object in the degreasing liquid.
- pressurized jet also causes a mechanical action facilitating the release of the layer of fatty substance covering the surface of the object.
- the degreasing liquid being chosen in such a way that it is practically immiscible or only partially miscible with the fatty substance, there is no phenomenon of total dilution of the fatty substance by a solvent as is the case for example with chlorinated solvents.
- the fatty substance is collected practically undiluted or very little diluted, which corresponds to a collection of the different layers of the fatty substances of the objects subjected to the process according to the invention.
- the degreasing liquid, forming a second phase distinct from that forming the combined fatty substance, is recycled with an excellent recovery yield.
- this liquid contains dissolved at equilibrium only a small percentage by weight of fatty substance. There is therefore no significant pollution of the degreasing liquid by the fatty substance.
- the degreasing liquid may not contain a surfactant.
- this has the advantage of simplifying the formulation of this same liquid.
- the degreasing liquid does not contain an organic halogen atom.
- organic halogen is meant a halogen entering the chemical formula of an organic compound.
- the degreasing liquid comprises benzyl alcohol.
- the degreasing liquid comprises diacetone alcohol.
- the liquid can be pure diacetone alcohol or contain additives, in particular a small amount in percentage by weight of methanol or water relative to the total weight of the liquid or alternatively mono- and / or di-methyl phosphoric esters.
- the degreasing liquid has an adhesion tension equal to or greater than 30 x 10 ⁇ 3 N / m; this adhesion tension is in fact generally greater than that of a fatty substance on a metal surface.
- the fatty substances capable of being treated by the process can be of any kind, in particular of animal, vegetable, mineral or even synthetic origin.
- each object is chosen so that its surface has hydrophilic polar groups. This facilitates the departure of the layer of fatty substances having a marked lipophilic character.
- the surface to be cleaned is metallic, but it can also be made of mineral glass or ceramic, or even an organic polymer.
- step a / the degreasing liquid can be maintained at a temperature close to room temperature, for example in a range between 15 ° C and 40 ° C.
- step c / it is possible in step c /, to facilitate the separation of the two phases, to provide cooling of the suspension to further reduce, if necessary, the very low solubility of the fatty substance in the degreasing liquid and the very poor solubility of the degreasing liquid in the fatty substance.
- the degreasing liquid is chosen so that it can be evaporated at a temperature less than or equal to 100 ° C. under normal pressure. This allows that after step b /, the thin layer of said liquid is evaporated covering the surface of the object.
- the degreasing liquid is chosen to be miscible with an evaporable solvent at a temperature less than or equal to 100 ° C. under normal pressure.
- diacetone alcohol (DA) or 4-hydroxy-4-methyl pentanone-2 which is, in the process according to the invention, one of the preferred degreasing liquids, is miscible with alcohols, esters and water.
- diacetone alcohol has a very low vapor pressure (133 Pa at 20 ° C), 100 times lower than that of the chlorinated solvent T 111, a flash point of + 62 ° C (in closed cup), a good stability in neutral medium, at room temperature and in the presence of metals.
- the evaporable solvent is chosen from water, acetone, methanol, ethanol or one of their mixtures.
- step b / the surface of the object covered with a thin layer of degreasing liquid is washed with the evaporable solvent, which has the effect of eliminating this layer of liquid and temporarily replacing it with a layer of solvent.
- the surface is then dried which gives a surface without fatty substance.
- a second phase is obtained essentially comprising degreasing liquid.
- the fatty substance even if it is practically immiscible with this liquid, can dissolve therein very slightly.
- This purification can also be done by rectification.
- Step c / can be carried out by decantation. Two distinct phases are then obtained, one of these phases covering the other, the assembly being contained in a suitable container.
- the degreasing of each object could be carried out by immersion of each object in the second phase passing through the first then extracting each object in the opposite direction, passing last through the first phase based on fatty substances. Indeed, the fatty substance rolls or slides on the thin layer of degreasing liquid covering the surface of the object.
- a NM 22S stainless steel plate coated with petroleum jelly oil (fully aliphatic oil) is quenched for 15 min. in the solvent tested at room temperature and without using ultrasound.
- the plate is quickly rinsed with methanol (this alcohol is a bad degreaser), then dried at room temperature.
- Ten drops of water are distributed on the two sides of the plate, which gives a total of 20 contact angle measurements determined with the goniometer (This angle is determined according to "Testing Surfaces for Cleanliness, WC Jones, Metal Finishing, October 1985 , p. 13 ").
- the degreasing performance is evaluated by calculating the average.
- the standard deviation of the measurements gives a idea of the homogeneity of degreasing.
- This static procedure by simple soaking without using ultrasound has the advantage of only evaluating the suitability of a determined solvent.
- the use of ultrasound, agitation, sprinkling, a rise in temperature are all factors that increase the effectiveness of degreasing.
- a mixture of polar and non-polar oils was used to replace the above petroleum jelly oil.
- the mixture consists of 50% by volume of vaseline oil, 25% of ELF Aleda EE 40 oil (phosphochlorinated mineral oil), 25% by volume of Etirelf BFE 53 oil (completely chlorine-free oil).
- adhesion tensions were determined at 20 ° C, for petroleum jelly oil and the various solvents indicated in the examples below, and are expressed in milli-Newton per meter.
- Diacetone alcohol performs better than T 111 at boiling point or T 111 in the vapor phase, which is particularly remarkable since DA is used at room temperature.
- the diacetone alcohol additive with 3% (w / w) of methanol and used at room temperature is as effective as a boiling T 111 boiling cycle, T 111 soaking cycle at room temperature, T 111 rinsing in the vapor phase. This cycle is commonly used in degreasing machines. It is also much more efficient than just one of the 3 operations.
- Diacetone alcohol even without methanol additive, is more effective than degreasers based on 2-methoxy-propanol-1.
- the NM 22S stainless steel plates were coated with an oil chosen from three different oils, then degreased with a liquid composition comprising, in percentages by weight, 89% of DA, 10% of water and 1% of a mixture 50/50 by weight of mono- and di-methyl ester of phosphoric acid, neutralized with triethanolamine.
- This example describes, with reference to the single figure, a prototype of a degreasing machine 1 with two baths using diacetone alcohol (DA). The degreasing evaluation tests are carried out according to the second procedure.
- DA diacetone alcohol
- This machine 1 comprises a first tank 2 partially filled with the first bath which is in the form of a first oil phase 6 covering a second phase 5 essentially comprising diacetonalcohol (DA).
- DA diacetonalcohol
- the supernatant phase 6 overflows into the decanter 4 by forming an oil column 7 whose height in the decanter increases during the successive cleaning of the objects.
- This column of oil 7 floats above a layer 8 of DA coming from the overflow of the tank 2 or from the finish of the settling of the phases 5, 6.
- This pipe and its pump make it possible to recycle the layer 8 of DA in the second phase 5 of the tank 2 or to direct the oil from column 7 to a pipe 12 for recovering the oil for its subsequent treatment as waste.
- This machine 1 also includes a second tank 3 partially filled with a bath 13 of DA which receives the objects or parts to be degreased only after their successive passage in phases 5 and 6 of the first tank 2.
- the degreasing path, by immersion of the objects, is shown by the dotted line 14 for an object 15.
- the first bath removes most of the oil. This settles on the surface of the DA and is found in the upper phase of the settling tank 4. A good part of the pollution of the first bath is thus eliminated. However, some polar oils are soluble in DA. To have a very good degreasing, the installation is completed by the second bath 13 of clean DA which is used for finishing the degreasing and whose service life is very high.
- This degreasing process at room temperature is therefore particularly effective. In addition, it causes very slow pollution of the degreasing baths. In extreme pollution conditions, it is still effective.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Management, Administration, Business Operations System, And Electronic Commerce (AREA)
- Control Of Vending Devices And Auxiliary Devices For Vending Devices (AREA)
Abstract
Description
La présente invention se rapporte au domaine technique du traitement de surfaces d'objets manufacturés, et, plus précisément, au dégraissage industriel d'une pluralité d'objets.The present invention relates to the technical field of the treatment of surfaces of manufactured objects, and, more specifically, to the industrial degreasing of a plurality of objects.
Un dégraissage a pour but d'éliminer de la surface d'un objet tous les produits gras et les diverses salissures qu'il contient, afin que cette surface rendue propre retrouve les propriétés physico-chimiques intrinsèques de la matière qui la forme.The purpose of degreasing is to remove from the surface of an object all the fatty products and the various soiling it contains, so that this surface, made clean, regains the intrinsic physicochemical properties of the matter which forms it.
Cette matière est en général un métal ou un alliage métallique notamment à base de cuivre, fer, aluminium, zinc ou encore un métal précieux comme l'or ou le platine. Elle peut être également un verre minéral, une céramique ou une matière plastique.This material is generally a metal or a metal alloy, in particular based on copper, iron, aluminum, zinc or even a precious metal such as gold or platinum. It can also be a mineral glass, a ceramic or a plastic.
Comme le rappelle la publication : "Comparaison des différentes méthodes de dégraissage des métaux, Procédés aqueux et procédés aux solvants - European chlorinated solvent association - CEFIC - Brussels Décembre 1990 pp. 1-15", les opérations de dégraissage constituent une étape essentielle dans tous les processus de production et conduisent à l'amélioration de la qualité et de la fiabilité des produits.As the publication recalls: "Comparison of different methods of degreasing metals, Aqueous processes and solvent processes - European chlorinated solvent association - CEFIC - Brussels December 1990 pp. 1-15", degreasing operations are an essential step in all production processes and lead to improved product quality and reliability.
Selon cette publication, les procédés de dégraissage se divisent essentiellement en deux catégories:
- 1° les procédés de dégraissage à base de solvants chlorés, - au trempé ou en phase vapeur - utilisés dans l'industrie depuis les années 1920 ;
- 2° les procédés aqueux nécessitant des formulations complexes à base d'eau, d'agents de saponification (soude, potasse, silicates, borates ou carbonates) et de tensio-actifs, et une opération de rinçage à l'eau déminéralisée pour l'obtention d'une surface exempte de taches.
- 1 ° degreasing processes based on chlorinated solvents, - by quenching or in the vapor phase - used in industry since the 1920s;
- 2 ° aqueous processes requiring complex formulations based on water, saponification agents (soda, potash, silicates, borates or carbonates) and surfactants, and a rinsing operation with demineralized water for the obtaining a stain-free surface.
L'impact de ces procédés sur l'environnement peut être considéré par les thèmes suivants:
- (a) les rejets dans l'eau
- (b) les problèmes de déchets
- (c) les émissions atmosphériques
- (d) l'énergie.
- (a) releases to water
- (b) waste issues
- (c) air emissions
- (d) energy.
En ce qui concerne les rejets dans l'eau, les pollutions résultent d'une mauvaise gestion des déchets ou, dans le cas des solvants chlorés, de déversements accidentels liés à un stockage ou des manipulations inadaptés.With regard to discharges into water, pollution results from poor waste management or, in the case of chlorinated solvents, accidental spills linked to improper storage or handling.
Les effluents générés par les procédés aqueux peuvent être purifiés par ultrafiltration et/ou distillation et recyclés. Néanmoins, ces techniques demeurent complexes, coûteuses et consommatrices d'énergie.The effluents generated by the aqueous processes can be purified by ultrafiltration and / or distillation and recycled. However, these techniques remain complex, expensive and energy consuming.
En ce qui concerne les déchets, les résidus provenant du dégraissage aux solvants chlorés contiennent essentiellement des huiles et des graisses. Le taux de solvant chloré de ces résidus peut être abaissé par distillation. Le résidu final très concentré doit être éliminé selon la législation en vigueur - (voir la référence : Manipulation des résidus et déchets de solvants chlorés Chimie et Industrie, (1988), 522-525.With regard to waste, residues from degreasing with chlorinated solvents mainly contain oils and greases. The level of chlorinated solvent in these residues can be lowered by distillation. The highly concentrated final residue must be disposed of in accordance with current legislation - (see reference: Handling of residues and waste of chlorinated solvents Chimie et Industrie, (1988), 522-525.
Le dégraissage par procédé aqueux génère des effluents contenant les produits chimiques de départ contaminés par les huiles et graisses éliminées. Ces effluents doivent être traités en station d'épuration et les boues produites posent le problème de leur élimination.Degreasing by an aqueous process generates effluents containing the starting chemicals contaminated by the eliminated oils and greases. These effluents must be treated in a treatment plant and the sludge produced poses the problem of their disposal.
En ce qui concerne les émissions atmosphériques, les législations en vigueur deviennent très sévères et en ce qui concerne le trichloroéthane-1,1,1, le protocole de Montréal révisé à Londres en 1990 prévoit un gel des utilisations à partir de 1993 et son interdiction à partir de 2005.With regard to air emissions, the laws in force are becoming very strict and with regard to 1,1,1 trichloroethane, the Montreal Protocol revised in London in 1990 provides for a freeze on uses from 1993 and its prohibition from 2005.
En matière d'énergie, les procédés aqueux nécessitent, en général, plus d'énergie que les procédés fonctionnant aux solvants chlorés principalement lorsqu'une étape de séchage est nécessaire. Si cette étape peut être évitée, la consommation d'énergie des procédés aqueux peut se révéler inférieure.In terms of energy, aqueous processes generally require more energy than processes operating with chlorinated solvents mainly when a drying step is required. If this step can be avoided, the energy consumption of aqueous processes may be lower.
L'énergie considérée ci-dessus couvre la production des substances chimiques utilisées, le nettoyage proprement dit ainsi que le recyclage et l'élimination des déchets.The energy considered above covers the production of the chemical substances used, cleaning proper as well as recycling and disposal of waste.
La publication R.E. Brunig et J.F. Fallot, Nettoyage industriel état actuel des techniques, Oberfläche Surface, N° 6, 1991,SHZ Fachverlag Zurich, Suisse, attire l'attention sur l'évolution de la législation face aux techniques de nettoyage utilisant des solvants chlorés. C'est ainsi que le nettoyage industriel par solvants chlorés sera éventuellement interdit aux USA (Californie) et qu'en Allemagne la législation imposera à court terme une étanchéité quasi parfaite des machines utilisant des solvants chlorés.The publication RE Brunig and JF Fallot, Industrial cleaning current state of the techniques, Oberfläche Surface, N ° 6, 1991, SHZ Fachverlag Zurich, Switzerland, draws attention to the development of legislation regarding cleaning techniques using chlorinated solvents . This is how industrial cleaning with chlorinated solvents will eventually be prohibited in the USA (California) and that in Germany the legislation will impose in the short term an almost perfect sealing of machines using chlorinated solvents.
Dans le cas des procédés aqueux, notamment nettoyage industriel par lessives, il est question d'édicter des normes strictes, en particulier en Allemagne, pour limiter la consommation d'eau et éviter des problèmes de traitement des eaux usées dans les stations d'épuration communales.In the case of aqueous processes, in particular industrial cleaning with detergents, it is a question of enacting strict standards, in particular in Germany, to limit water consumption and avoid problems of wastewater treatment in treatment plants. communal.
Le but de la présente invention est de trouver un procédé de dégraissage industriel qui n'ait pas les inconvénients des deux procédés rappelés ci-dessus, notamment en ce qui concerne l'impact possible sur l'environnement.The object of the present invention is to find an industrial degreasing process which does not have the drawbacks of the two processes mentioned above, in particular as regards the possible impact on the environment.
Dans le domaine technique de l'industrie du pétrole, le problème de la récupération des fractions lourdes de pétrole, emprisonnées dans les structures poreuses des champs pétrolifères, a fait l'objet d'études, en particulier par M.V. Ostrovky et E. Nestaas dans Colloids and Surfaces, 26(1987) 351-373.In the technical field of the petroleum industry, the problem of recovering heavy fractions of petroleum, trapped in porous structures in oil fields, has been the subject of studies, in particular by MV Ostrovky and E. Nestaas in Colloids and Surfaces, 26 (1987) 351-373.
Ces auteurs ont étudié théoriquement l'équilibre mécanique d'une goutte d'huile sur une surface solide et plane, en présence d'une phase aqueuse. L'huile peut se détacher de la surface solide si sa tension superficielle multipliée par le cosinus de son angle de contact, à savoir sa tension d'adhésion, est inférieure à la tension d'adhésion de la phase aqueuse de cette même surface solide. Leurs études de laboratoire ont montré que la présence d'un agent tensio-actif dans la phase aqueuse était indispensable pour obtenir le détachement de l'huile.These authors have theoretically studied the mechanical equilibrium of a drop of oil on a solid and flat surface, in the presence of an aqueous phase. Oil can detach from the solid surface if its surface tension multiplied by the cosine of its contact angle, namely its adhesion tension, is less than the adhesion tension of the aqueous phase of this same solid surface. Their laboratory studies showed that the presence of a surfactant in the aqueous phase was essential to obtain the detachment of the oil.
M. V. Ostrovsky dans Colloids and Surfaces, 32 (1988) 173-175 a publié une étude théorique portant sur les paramètres que doivent avoir les tensio-actifs dans un liquide pour détacher une huile d'une surface solide, lisse, homogène, isotrope et non déformable.MV Ostrovsky in Colloids and Surfaces, 32 (1988) 173-175 published a theoretical study on the parameters which the surfactants must have in a liquid to detach an oil from a solid, smooth, homogeneous, isotropic and not deformable.
Le but de la présente invention, tel qu'indiqué ci-dessus, est obtenu par un procédé de dégraissage d'une pluralité d'objets à l'aide d'un liquide de dégraissage, chaque objet ayant une surface recouverte au moins partiellement d'une couche d'un corps gras, caractérisé en ce que ledit liquide ayant une tension d'adhésion supérieure à celle du corps gras sur la surface de chaque objet et étant pratiquement immiscible ou seulement partiellement miscible avec le corps gras, ledit procédé consiste, pour chaque objet :
- a/ à recouvrir la couche de corps gras par le liquide de dégraissage, avec éventuellement une action mécanique conjointe notamment ultra-sons, afin de décrocher le corps gras de la surface en le mettant en suspension dans le liquide, la surface de l'objet se recouvrant alors du liquide qui a plus d'affinité pour la surface,
- b/ à séparer ensuite l'objet de ladite suspension afin d'obtenir l'objet avec une surface recouverte d'une mince couche dudit liquide,
- c/ à récupérer la suspension et à la séparer en deux phases distinctes :
- une première phase comportant essentiellement du corps gras,
- une deuxième phase comportant essentiellement du liquide de dégraissage,
- d/ à recycler cette deuxième phase à l'étape a/.
- a / to cover the layer of fatty substances with the degreasing liquid, possibly with a joint mechanical action, in particular ultrasound, in order to unhook the fatty substance from the surface by suspending it in the liquid, the surface of the object then covering itself with the liquid which has more affinity for the surface,
- b / then separating the object from said suspension in order to obtain the object with a surface covered with a thin layer of said liquid,
- c / recover the suspension and separate it into two distinct phases:
- a first phase essentially comprising fatty substances,
- a second phase essentially comprising degreasing liquid,
- d / to recycle this second phase in step a /.
Dans l'étape a/, la couche de corps gras est recouverte du liquide de dégraissage par tout moyen adapté et notamment par aspersion par jet ou spray ou encore par immersion de la surface de l'objet dans le liquide de dégraissage.In step a /, the layer of fatty substance is covered with the degreasing liquid by any suitable means and in particular by spraying with a jet or spray or else by immersion of the surface of the object in the degreasing liquid.
L'utilisation d'un jet sous pression provoque également une action mécanique facilitant le décrochement de la couche de corps gras recouvrant la surface de l'objet.The use of a pressurized jet also causes a mechanical action facilitating the release of the layer of fatty substance covering the surface of the object.
Il est possible aussi d'agiter chaque objet dans le liquide de dégraissage.It is also possible to agitate each object in the degreasing liquid.
Ce procédé présente de multiples avantages par rapport aux procédés connus de l'état de la technique.This method has multiple advantages over the known methods of the prior art.
Le liquide de dégraissage étant choisi de telle façon qu'il soit pratiquement immiscible ou seulement partiellement miscible avec le corps gras, il n'y a pas de phénomènes de dilution totale du corps gras par un solvant comme c'est le cas par exemple avec les solvants chlorés.The degreasing liquid being chosen in such a way that it is practically immiscible or only partially miscible with the fatty substance, there is no phenomenon of total dilution of the fatty substance by a solvent as is the case for example with chlorinated solvents.
Le corps gras est recueilli pratiquement non dilué ou très peu dilué, ce qui correspond à un rassemblement des différentes couches des corps gras des objets soumis au procédé selon l'invention.The fatty substance is collected practically undiluted or very little diluted, which corresponds to a collection of the different layers of the fatty substances of the objects subjected to the process according to the invention.
Le liquide de dégraissage, formant une deuxième phase distincte de celle formant le corps gras rassemblé, est recyclé avec un excellent rendement de récupération.The degreasing liquid, forming a second phase distinct from that forming the combined fatty substance, is recycled with an excellent recovery yield.
Comme le corps gras est pratiquement immiscible avec le liquide de dégraissage, ou y est très peu soluble, ce liquide ne contient dissous à l'état d'équilibre qu'un faible pourcentage en poids de corps gras. Il n'y a donc pas de pollution significative du liquide de dégraissage par le corps gras.As the fatty substance is practically immiscible with, or very sparingly soluble in, the degreasing liquid, this liquid contains dissolved at equilibrium only a small percentage by weight of fatty substance. There is therefore no significant pollution of the degreasing liquid by the fatty substance.
Le liquide de dégraissage peut ne pas comporter d'agent tensio-actif. Lorsque le liquide de dégraissage ne comporte pas de surfactant, cela présente un avantage de simplification de la formulation de ce même liquide.The degreasing liquid may not contain a surfactant. When the degreasing liquid does not contain a surfactant, this has the advantage of simplifying the formulation of this same liquid.
Avantageusement, le liquide de dégraissage ne comporte pas d'atome d'halogène organique. Par halogène organique, on entend un halogène entrant dans la formule chimique d'un composé organique. Ainsi, le procédé évite toutes les législations contraignantes actuelles et futures sur l'utilisation des produits organohalogénés.Advantageously, the degreasing liquid does not contain an organic halogen atom. By organic halogen is meant a halogen entering the chemical formula of an organic compound. Thus, the process avoids all current and future binding legislation on the use of organohalogenated products.
Avantageusement, le liquide de dégraissage comporte de l'alcool benzylique.Advantageously, the degreasing liquid comprises benzyl alcohol.
De manière toute préférée, le liquide de dégraissage comporte du diacétone-alcool. Le liquide peut être du diacétone-alcool pur ou contenir des additifs, notamment une faible quantité en pourcentage en poids de méthanol ou d'eau par rapport au poids total du liquide ou encore des esters mono- et/ou di-méthyl phosphorique.Most preferably, the degreasing liquid comprises diacetone alcohol. The liquid can be pure diacetone alcohol or contain additives, in particular a small amount in percentage by weight of methanol or water relative to the total weight of the liquid or alternatively mono- and / or di-methyl phosphoric esters.
De préférence, le liquide de dégraissage a une tension d'adhésion égale ou supérieure à 30 x 10⁻³ N/m ; cette tension d'adhésion est en effet généralement supérieure à celle d'un corps gras sur une surface métallique.Preferably, the degreasing liquid has an adhesion tension equal to or greater than 30 x 10⁻³ N / m; this adhesion tension is in fact generally greater than that of a fatty substance on a metal surface.
Les corps gras susceptibles d'être traités par le procédé peuvent être de toute sorte notamment d'origine animale, végétale, minérale ou encore de synthèse.The fatty substances capable of being treated by the process can be of any kind, in particular of animal, vegetable, mineral or even synthetic origin.
De préférence, chaque objet est choisi de façon que sa surface comporte des groupes polaires hydrophiles. Ceci facilite le départ de la couche de corps gras ayant un caractère lipophile marqué.Preferably, each object is chosen so that its surface has hydrophilic polar groups. This facilitates the departure of the layer of fatty substances having a marked lipophilic character.
Avantageusement, la surface à nettoyer est métallique, mais elle peut être également en un verre minéral ou en céramique, ou encore en un polymère organique.Advantageously, the surface to be cleaned is metallic, but it can also be made of mineral glass or ceramic, or even an organic polymer.
Un autre avantage du procédé réside dans le fait qu'à l'étape a/, le liquide de dégraissage peut être maintenu à une température voisine de la température ambiante, par exemple dans une gamme comprise entre 15°C et 40°C.Another advantage of the process lies in the fact that in step a /, the degreasing liquid can be maintained at a temperature close to room temperature, for example in a range between 15 ° C and 40 ° C.
Par contre, il est possible à l'étape c/, pour faciliter la séparation des deux phases de prévoir un refroidissement de la suspension pour diminuer encore, si de besoin, la très faible solubilité du corps gras dans le liquide de dégraissage et la très faible solubilité du liquide de dégraissage dans le corps gras.On the other hand, it is possible in step c /, to facilitate the separation of the two phases, to provide cooling of the suspension to further reduce, if necessary, the very low solubility of the fatty substance in the degreasing liquid and the very poor solubility of the degreasing liquid in the fatty substance.
Il est possible également de solidifier par refroidissement la première phase comportant essentiellement du corps gras pour faciliter sa récupération en tant que déchets.It is also possible to solidify by cooling the first phase essentially comprising fatty substance to facilitate its recovery as waste.
Avantageusement, le liquide de dégraissage est choisi de façon à ce qu'il soit évaporable à une température inférieure ou égale à 100°C sous la pression normale. Ceci permet qu'après l'étape b/, on évapore la mince couche dudit liquide recouvrant la surface de l'objet.Advantageously, the degreasing liquid is chosen so that it can be evaporated at a temperature less than or equal to 100 ° C. under normal pressure. This allows that after step b /, the thin layer of said liquid is evaporated covering the surface of the object.
De préférence, le liquide de dégraissage est choisi pour être miscible avec un solvant évaporable à une température inférieure ou égale à 100°C sous pression normale.Preferably, the degreasing liquid is chosen to be miscible with an evaporable solvent at a temperature less than or equal to 100 ° C. under normal pressure.
Ainsi le diacétone-alcool (DA) ou 4-hydroxy-4-méthyl pentanone-2 qui est, dans le procédé selon l'invention, un des liquides de dégraissage préférés, est miscible avec les alcools, les esters et l'eau.Thus diacetone alcohol (DA) or 4-hydroxy-4-methyl pentanone-2 which is, in the process according to the invention, one of the preferred degreasing liquids, is miscible with alcohols, esters and water.
De plus, le diacétone-alcool a une tension de vapeur très faible (133 Pa à 20°C), 100 fois plus faible que celle du solvant chloré T 111, un point éclair de +62°C (en coupe fermée), une bonne stabilité en milieu neutre, à température ambiante et en présence de métaux.In addition, diacetone alcohol has a very low vapor pressure (133 Pa at 20 ° C), 100 times lower than that of the chlorinated solvent T 111, a flash point of + 62 ° C (in closed cup), a good stability in neutral medium, at room temperature and in the presence of metals.
D'une manière préférée, le solvant évaporable est choisi parmi l'eau, l'acétone, le méthanol, l'éthanol ou un de leurs mélanges.Preferably, the evaporable solvent is chosen from water, acetone, methanol, ethanol or one of their mixtures.
Avantageusement, après l'étape b/, la surface de l'objet recouverte d'une mince couche de liquide de dégraissage est lavée avec le solvant évaporable, ce qui a pour effet d'éliminer cette couche de liquide et de la remplacer momentanément par une couche de solvant. La surface est ensuite séchée ce qui donne une surface sans corps gras.Advantageously, after step b /, the surface of the object covered with a thin layer of degreasing liquid is washed with the evaporable solvent, which has the effect of eliminating this layer of liquid and temporarily replacing it with a layer of solvent. The surface is then dried which gives a surface without fatty substance.
A l'étape c/ du procédé, il est obtenu une deuxième phase comportant essentiellement du liquide de dégraissage. Le corps gras même s'il est pratiquement immiscible avec ce liquide peut s'y dissoudre très faiblement. Avant de procéder à l'étape d/ de recyclage de cette deuxième phase, on préfère la purifier sur une matière pulvérulente à adsorption sélective, notamment charbon actif, afin de diminuer la teneur en corps gras voire éliminer totalement le corps gras dissous dans cette deuxième phase et obtenir du liquide de dégraissage ayant sensiblement une composition identique à celle qu'il avait avant tout dégraissage.In step c / of the process, a second phase is obtained essentially comprising degreasing liquid. The fatty substance, even if it is practically immiscible with this liquid, can dissolve therein very slightly. Before proceeding to step d / of recycling this second phase, it is preferable to purify it on a pulverulent material with selective adsorption, in particular activated carbon, in order to reduce the fatty substance content or even completely eliminate the fatty substance dissolved in this second phase and obtain degreasing liquid having substantially a composition identical to that which it had before any degreasing.
Cette purification peut également être faite par rectification.This purification can also be done by rectification.
L'étape c/ peut être réalisée par décantation. On obtient alors deux phases distinctes, l'une de ces phases recouvrant l'autre, l'ensemble étant contenu dans un récipient adapté.Step c / can be carried out by decantation. Two distinct phases are then obtained, one of these phases covering the other, the assembly being contained in a suitable container.
Dans le cas où la première phase à base de corps gras est surnageante au-dessus de la deuxième phase à base de liquide de dégraissage, il a été trouvé d'une manière surprenante que le dégraissage de chaque objet pouvait être réalisé par immersion de chaque objet dans la deuxième phase en passant par la première puis en extrayant chaque objet en sens inverse, en passant en dernier lieu par la première phase à base de corps gras. En effet, le corps gras roule ou glisse sur la mince couche de liquide de dégraissage recouvrant la surface de l'objet.In the case where the first phase based on fatty substances is supernatant above the second phase based on degreasing liquid, it has been surprisingly found that the degreasing of each object could be carried out by immersion of each object in the second phase passing through the first then extracting each object in the opposite direction, passing last through the first phase based on fatty substances. Indeed, the fatty substance rolls or slides on the thin layer of degreasing liquid covering the surface of the object.
En plus de la description précédente, l'invention sera mieux comprise à l'aide des exemples suivants dans lesquels l'exemple 7 est donné en référence à la figure unique du dessin schématique annexé.In addition to the preceding description, the invention will be better understood with the aid of the following examples in which Example 7 is given with reference to the single figure of the appended schematic drawing.
Deux procédures différentes ont été utilisées pour évaluer l'efficacité du dégraissage.Two different procedures were used to assess the effectiveness of degreasing.
Une plaque d'acier inoxydable NM 22S enduite d'huile de vaseline (huile totalement aliphatique) est trempée pendant 15 min. dans le solvant testé à température ambiante et sans utiliser d'ultra-sons. Afin d'écourter le séchage, la plaque est rapidement rincée au méthanol (cet alcool est un mauvais dégraissant), puis séchée à température ambiante. Dix gouttes d'eau sont réparties sur les deux faces de la plaque, ce qui donne au total 20 mesures d'angle de contact déterminées au goniomètre ( Cet angle est déterminé selon "Testing Surfaces for Cleanliness ,W.C. Jones, Metal Finishing, October 1985, p. 13").A NM 22S stainless steel plate coated with petroleum jelly oil (fully aliphatic oil) is quenched for 15 min. in the solvent tested at room temperature and without using ultrasound. In order to shorten the drying, the plate is quickly rinsed with methanol (this alcohol is a bad degreaser), then dried at room temperature. Ten drops of water are distributed on the two sides of the plate, which gives a total of 20 contact angle measurements determined with the goniometer (This angle is determined according to "Testing Surfaces for Cleanliness, WC Jones, Metal Finishing, October 1985 , p. 13 ").
La performance du dégraissage s'évalue par le calcul de la moyenne. L'écart-type des mesures donne une idée de l'homogénéité du dégraissage. Cette procédure statique par simple trempage sans utiliser d'ultra-sons a pour intérêt d'évaluer uniquement l'aptitude d'un solvant déterminé. L'utilisation d'ultra-sons, d'une agitation, d'une aspersion, d'une élévation de température sont autant de facteurs permettant d'accroître l'efficacité du dégraissage.The degreasing performance is evaluated by calculating the average. The standard deviation of the measurements gives a idea of the homogeneity of degreasing. This static procedure by simple soaking without using ultrasound has the advantage of only evaluating the suitability of a determined solvent. The use of ultrasound, agitation, sprinkling, a rise in temperature are all factors that increase the effectiveness of degreasing.
Un mélange d'huiles polaires et apolaire a été utilisé en remplacement de l'huile de vaseline ci-dessus. Le mélange est constitué de 50% en volume d'huile de vaseline, 25% d'huile ELF Aleda EE 40 (huile minérale phosphochlorée), 25% en volume d'huile Etirelf BFE 53 (huile entièrement sans chlore). Une plaque métallique est dégraissée en suivant la procédure ci-dessus. L'évaluation du dégraissage en utilisant ce mélange de 3 huiles a été faite par observation de l'étalement de l'eau sur la plaque. Un système de notation de 0 à 3 a été utilisé :
note = 3 : le mouillage de la surface (acier, inox ou aluminium) est très bon.
note = 2 : l'eau s'étale assez bien mais ensuite, on observe un certain retrait
note = 1 : le mouillage n'est que partiel
note = 0 : l'eau ne mouille pas la surface. C'est le cas d'une surface enduite du mélange des 3 huiles.A mixture of polar and non-polar oils was used to replace the above petroleum jelly oil. The mixture consists of 50% by volume of vaseline oil, 25% of ELF Aleda EE 40 oil (phosphochlorinated mineral oil), 25% by volume of Etirelf BFE 53 oil (completely chlorine-free oil). A metal plate is degreased by following the above procedure. The degreasing evaluation using this mixture of 3 oils was made by observation of the spreading of the water on the plate. A grading system from 0 to 3 was used:
note = 3: the wetting of the surface (steel, stainless steel or aluminum) is very good.
note = 2: the water spreads fairly well but then, we observe a certain shrinkage
note = 1: the anchorage is only partial
note = 0: the water does not wet the surface. This is the case for a surface coated with the mixture of 3 oils.
Suivant cette seconde procédure, les tests ont été effectués à plus grande échelle (bains de 10 litres). Les ultra-sons ont parfois été utilisés. Des additifs au diacétone-alcool ont parfois été ajoutés.Following this second procedure, the tests were carried out on a larger scale (10 liter baths). Ultrasound has sometimes been used. Diacetone alcohol additives have sometimes been added.
Les tensions d'adhésions (TA) ont été déterminées à 20°C, pour l'huile de vaseline et les différents solvants indiqués dans les exemples ci-après, et sont exprimées en milli-Newton par mètre.The adhesion tensions (TA) were determined at 20 ° C, for petroleum jelly oil and the various solvents indicated in the examples below, and are expressed in milli-Newton per meter.
En utilisant la première procédure, il a été comparé divers solvants oxygénés aux solvants dégraissants halogénés classiques.
- plaque d'acier enduite de vaseline (TA = 30) : = 90°
- plaque après 15 min. de dégraissage au T 111 (trichloroéthane, TA = 25 ) : = 52° ± 11°
- plaque après 15 min. de dégraissage au trichloroéthylène (TA = 26 ) : = 48° ± 10°
- plaque après 15 min. de dégraissage au trifluorotrichloroéthane F 113 : = 57° ± 4°
- plaque après 15 min. de dégraissage au methanol (TA = 23 ) : = 69° ± 9°
- plaque après 15 min. de dégraissage au méthylisobutylcarbinol ( TA = 23 ) : = 62° ± 8°
- plaque après 15 min. de dégraissage à l'éthylamylcétone ( TA = 28 ) : = 72° ± 6°
- plaque après 15 min. de dégraissage à la méthylisobutylcétone ( TA = 24 ) : = 68° ± 6°
- plaque après 15 min. de dégraissage au diacétone-alcool ( TA = 31 ) : = 56° ± 6°
- plaque après 15 min. de dégraissage à la N-méthylpyrrolidone ( TA = 36 ) : = 72° ± 8°
- plaque après 15 min. de dégraissage au diméthylsulfoxyde ( TA = 34 ) : = 66° ± 5°
- plaque après 15 min. de dégraissage à l'alcool benzylique ( TA = 39,5 ) : = 60° ± 5°
- Vaseline-coated steel plate (TA = 30): = 90 °
- plate after 15 min. degreasing with T 111 (trichloroethane, TA = 25): = 52 ° ± 11 °
- plate after 15 min. degreasing with trichlorethylene (TA = 26): = 48 ° ± 10 °
- plate after 15 min. degreasing with trifluorotrichloroethane F 113: = 57 ° ± 4 °
- plate after 15 min. methanol degreasing (TA = 23): = 69 ° ± 9 °
- plate after 15 min. degreasing with methylisobutylcarbinol (TA = 23): = 62 ° ± 8 °
- plate after 15 min. degreasing with ethylamyl ketone (TA = 28): = 72 ° ± 6 °
- plate after 15 min. degreasing with methyl isobutyl ketone (TA = 24): = 68 ° ± 6 °
- plate after 15 min. of diacetone-alcohol degreasing (TA = 31): = 56 ° ± 6 °
- plate after 15 min. degreasing with N-methylpyrrolidone (TA = 36): = 72 ° ± 8 °
- plate after 15 min. degreasing with dimethyl sulfoxide (TA = 34): = 66 ° ± 5 °
- plate after 15 min. degreasing with benzyl alcohol (TA = 39.5): = 60 ° ± 5 °
Cet exemple permet bien de retrouver les très bonnes propriétés dégraissantes des solvants halogénés (angle de contact de l'eau inférieur à 60°). De façon tout à fait inattendue, le diacétone-alcool donne un très bon dégraissage à température ambiante, avec une bonne homogénéité des mesures angulaires et avec une efficacité comparable aux solvants halogénés. L'alcool benzylique a donné de bons résultats, cependant inférieurs à ceux obtenus par l'utilisation du diacétone-alcool. Ces deux solvants agissent, en raison de leurs tensions d'adhésions supérieures à 30, par un mécanisme essentiellement de détergence et non de solubilisation comme c'est le cas pour les solvants halogénés.This example clearly shows the very good degreasing properties of halogenated solvents (contact angle of water less than 60 °). Quite unexpectedly, the diacetone alcohol gives very good degreasing at room temperature, with good homogeneity of angular measurements and with an efficiency comparable to halogenated solvents. Benzyl alcohol has given good results, however inferior to those obtained by the use of diacetone alcohol. These two solvents act, because of their adhesion tensions greater than 30, by a mechanism essentially of detergency and not of solubilization as is the case for halogenated solvents.
Par contre la N-méthylpyrrolidone pure et le diméthylsulfoxyde pur, bien que thermodynamiquement aptes à détacher l'huile de la surface, n'ont pas conduit à de bonnes performances de dégraissage. Cependant ces deux solvants peuvent faire partie chacun d'un liquide de dégraissage pour augmenter sa polarité et adapter ainsi sa tension d'adhésion à la tension d'adhésion du corps gras sur l'objet à dégraisser.On the other hand, pure N-methylpyrrolidone and pure dimethylsulfoxide, although thermodynamically capable of detaching the oil from the surface, have not led to good degreasing performance. However, these two solvents can each be part of a degreasing liquid to increase its polarity and thus adapt its adhesion tension to the adhesion tension of the fatty substance on the object to be degreased.
L'évaluation de l'efficacité du dégraissage a été la même que dans l'exemple 1. Les tests avec le diacétonealcool ont été effectués suivant la première procédure (trempage 15 min. dans le solvant à température ambiante). Les performances du diacétone-alcool ont été comparées à celles du trichloréthane T 111 utilisé à chaud.
- plaque d'acier enduite d'huile de vaseline : = 90°
- plaque après 15 min. de dégraissage au DA : = 56° ± 6°
- plaque après 15 min. de dégraissage au DA additivé de 3% de méthanol(% en poids par rapport au poids de DA ) : = 52° ± 2,5°
- plaque après 7 min. de dégraissage au T 111 à ébullition : = 61° ± 2,5°
- plaque après 7 min. de dégraissage au T 111 vapeur : = 63° ± 4,5°
- plaque après 3 min. de dégraissage au T 111 à ébullition, suivi d'un trempage d'une min. dans T 111 à température ambiante, suivi de 3 min. de dégraissage au T 111 vapeur : = 54° ± 2,5°
- steel plate coated with vaseline oil: = 90 °
- plate after 15 min. degreasing at DA: = 56 ° ± 6 °
- plate after 15 min. degreasing with DA additive of 3% methanol (% by weight relative to the weight of DA): = 52 ° ± 2.5 °
- plate after 7 min. degreasing at T 111 at boiling point: = 61 ° ± 2.5 °
- plate after 7 min. degreasing with T 111 steam: = 63 ° ± 4.5 °
- plate after 3 min. degreasing with T 111 at boiling point, followed by soaking for one min. in T 111 at room temperature, followed by 3 min. degreasing with T 111 steam: = 54 ° ± 2.5 °
Le diacétone-alcool est plus performant que le T 111 à ébullition ou le T 111 en phase vapeur, ce qui est particulièrement remarquable puisque le DA est utilisé à température ambiante. Le diacétone-alcool additivé de 3% (p/p) de méthanol et utilisé à température ambiante, est aussi efficace qu'un cycle trempage T 111 ébullition., trempage T 111, à température ambiante, rinçage T 111 en phase vapeur. Ce cycle est couramment utilisé dans les machines de dégraissage. Il est d'ailleurs beaucoup plus performant qu'une seule des 3 opérations.Diacetone alcohol performs better than T 111 at boiling point or T 111 in the vapor phase, which is particularly remarkable since DA is used at room temperature. The diacetone alcohol additive with 3% (w / w) of methanol and used at room temperature is as effective as a boiling T 111 boiling cycle, T 111 soaking cycle at room temperature, T 111 rinsing in the vapor phase. This cycle is commonly used in degreasing machines. It is also much more efficient than just one of the 3 operations.
En utilisant la première procédure, le diacétonealcool a été comparé à une lessive aqueuse, ainsi qu'à de nouveaux substituts à base d'éthers de propylène glycol ou de leurs mélanges avec des coupes pétrolières.
- plaque d'acier enduite d'huile de vaseline : = 90°
- plaque après 15 min. de dégraissage au DA : = 56° ± 6°
- plaque après 15 min. de dégraissage dans une lessive aqueuse GL 1740 (à 50°C) : = 56°,5 ± 10°
- plaque après 15 min. de dégraissage au 2-méthoxy-propanol-1 : = 61° ± 7,5°
- plaque après 15 min. de dégraissage dans un mélange 2-méthoxy-propanol-l et coupe pétrolière en C₈-C₁₁ : = 63° ± 10°
- steel plate coated with vaseline oil: = 90 °
- plate after 15 min. degreasing at DA: = 56 ° ± 6 °
- plate after 15 min. degreasing in an aqueous detergent GL 1740 (at 50 ° C): = 56 °, 5 ± 10 °
- plate after 15 min. degreasing with 2-methoxy-propanol-1: = 61 ° ± 7.5 °
- plate after 15 min. degreasing in a 2-methoxy-propanol-l mixture and C coupe-C₁₁ petroleum cut: = 63 ° ± 10 °
Malgré les bons résultats qu'elle donne, l'utilisation d'une lessive aqueuse nécessite un chauffage (50°C) ainsi qu'un rinçage important à l'eau distillée en raison d'importants dépôts de sels.Despite the good results it gives, the use of an aqueous detergent requires heating (50 ° C) as well as an important rinsing with distilled water due to significant deposits of salts.
Le diacétone-alcool, même non additivé de méthanol, est plus efficace que les dégraissants à base de 2-méthoxy-propanol-1.Diacetone alcohol, even without methanol additive, is more effective than degreasers based on 2-methoxy-propanol-1.
Dans cet exemple, nous avons utilisé un mélange de 3 huiles polaires et apolaire. Le mélange a servi à enduire les plaques d'acier mais également à polluer le bain de dégraissage. Il est constitué de 50% en volume d'huile de vaseline (d = 0,86), de 25% en volume d'huile Aleda EE 40 (d = 0,896) et de 25% en volume d'huile Etirelf BFE 53 (d = 0,935). Les deux premières huiles sont insolubles dans le diacétone-alcool. La troisième est soluble à 60% (en volume par rapport au volume de DA) dans le diacétone-alcool. On estime que le mélange des 3 huiles est soluble à seulement 20% volume/volume dans le diacétone-alcool. Cette faible solubilité dans un cas très défavorable où l'on a des huiles très polaires permet donc une diminution considérable de la pollution des bains de dégraissage.In this example, we have used a mixture of 3 polar and nonpolar oils. The mixture was used to coat the steel plates but also to pollute the degreasing bath. It consists of 50% by volume of petroleum jelly oil (d = 0.86), 25% by volume of Aleda EE 40 oil (d = 0.896) and 25% by volume of Etirelf BFE 53 oil ( d = 0.935). The first two oils are insoluble in diacetone alcohol. The third is soluble at 60% (by volume relative to the volume of DA) in diacetone alcohol. It is estimated that the mixture of the 3 oils is soluble at only 20% volume / volume in diacetone alcohol. This low solubility in a very unfavorable case where there are very polar oils therefore allows a considerable reduction in the pollution of the degreasing baths.
Des tests utilisant la seconde procédure ont été effectués avec le DA.Tests using the second procedure were performed with the DA.
- plaque d'acier enduite d'huile de vaseline : note = 0steel plate coated with vaseline oil: note = 0
- après 15 min. de dégraissage au DA sans ultra-sons : note = 1,5after 15 min. degreasing at DA without ultrasound: note = 1.5
- après 5 min. de dégraissage au DA avec ultra-sons : note = 2after 5 min. degreasing at DA with ultrasound: note = 2
- après 10 min. de dégraissage au DA avec ultra-sons : note = 2,5after 10 min. degreasing at DA with ultrasound: note = 2.5
- après 15 min. de dégraissage au DA avec ultra-sons : note = 3after 15 min. degreasing at DA with ultrasound: note = 3
- plaque d'acier enduite du mélange des 3 huiles : note = 0steel plate coated with the mixture of 3 oils: note = 0
- après 15 min. de dégraissage au DA avec ultra-sons : note = 2-2,5after 15 min. degreasing at DA with ultrasound: note = 2-2.5
A une échelle plus importante (plaques d'acier de 10 cm² et bains de 10 l), le diacétone-alcool conduit à des résultats très performants aussi bien avec l'huile de vaseline qu'avec un mélange polaire de 3 huiles.On a larger scale (10 cm² steel plates and 10 l baths), diacetone-alcohol leads to very effective results both with petroleum jelly oil and with a polar mixture of 3 oils.
- plaque d'acier enduite du mélange des 3 huiles : note = 0steel plate coated with the mixture of 3 oils: note = 0
- après 15 min. de dégraissage au DA pollué par 3,5% (v/v) du mélange des 3 huiles et l'application d'ultra-sons : note = 0after 15 min. degreasing with DA polluted by 3.5% (v / v) of the mixture of the 3 oils and the application of ultrasound: note = 0
- après 15 min. de dégraissage au DA additivé de 3% de MeOH (poids/poids) : note = 2after 15 min. degreasing with DA additive of 3% MeOH (weight / weight): score = 2
- après 15 min. de dégraissage au DA additivé de 5% de méthyl ester phosphorique (en poids par rapport au poids de DA ) neutralisé par la triéthanolamine et 5% d'eau : note = 2after 15 min. degreasing with DA additive 5% methyl phosphoric ester (by weight relative to the weight of DA) neutralized by triethanolamine and 5% water: note = 2
En additivant le diacétone-alcool de méthanol ou de méthyl ester phosphorique, on arrive encore à un bon dégraissage même lorsque le bain est pollué par une teneur de 3,5% en volume du mélange des 3 huiles (Ce qui équivaut au dégraissage de 3500 plaques).By adding the diacetone alcohol of methanol or methyl phosphoric ester, we still get a good degreasing even when the bath is polluted by a content of 3.5% by volume of the mixture of the 3 oils (This is equivalent to the degreasing of 3500 plates).
Les plaques d'acier inoxydables NM 22S ont été enduites par une huile choisie parmi trois huiles différentes, puis dégraissées avec une composition liquide comprenant, en pourcentages en poids, 89% de DA, 10% d'eau et 1% d'un mélange 50/50 en poids de mono- et di-méthyl ester de l'acide phosphorique, neutralisé par de la triéthanolamine.The NM 22S stainless steel plates were coated with an oil chosen from three different oils, then degreased with a liquid composition comprising, in percentages by weight, 89% of DA, 10% of water and 1% of a mixture 50/50 by weight of mono- and di-methyl ester of phosphoric acid, neutralized with triethanolamine.
Le dégraissage est pratiqué pendant 5 minutes avec ultrasons, selon la première procédure, mais l'évaluation du dégraissage est faites par l'observation de l'étalement de l'eau sur la plaque de manière analogue à l'exemple 4. Les résultats sont les suivants:
- huile de vaseline : note = 2 - 3
- mélange des 3 huiles : note = 2 - 3
- huile MAGNA BDX 68
( CASTROL ) : note = 0
- vaseline oil: score = 2 - 3
- mixture of the 3 oils: note = 2 - 3
- MAGNA BDX 68 oil
(CASTROL): score = 0
Le dégraissage est pratiqué d'une manière analogue à l'exemple 5, mais avec un liquide de dégraissage constitué de 50% en poids de DA et 50% en poids de Diméthylsulfoxyde:
- huile MAGNA BDX 68 : note = 2 - 3Degreasing is carried out in a manner analogous to Example 5, but with a degreasing liquid consisting of 50% by weight of DA and 50% by weight of Dimethylsulfoxide:
- MAGNA BDX 68 oil: note = 2 - 3
Cet exemple décrit, en référence à la figure unique, un prototype de machine de dégraissage 1 à deux bains utilisant le diacétone-alcool (DA). Les tests d'évaluation du dégraissage sont effectués suivant la seconde procédure.This example describes, with reference to the single figure, a prototype of a degreasing
Cette machine 1 comporte une première cuve 2 partiellement remplie du premier bain qui se présente sous la forme d'une première phase d'huile 6 recouvrant une deuxième phase 5 comportant essentiellement du diacétonealcool (DA).This
La phase surnageante 6 vient déborder dans le décanteur 4 en formant une colonne d'huile 7 dont la hauteur dans le décanteur augmente lors du nettoyage successif des objets.The supernatant phase 6 overflows into the decanter 4 by forming an
Cette colonne d'huile 7 surnage au-dessus d'une couche 8 de DA en provenance du débordement de la cuve 2 ou de la finition de la décantation des phases 5, 6.This column of
Une canalisation 9, équipée d'une pompe 10 et d'une vanne 11 à trois voies, relie le bas du décanteur 4 au fond de la cuve 2.A
Cette canalisation et sa pompe permettent de recycler la couche 8 de DA dans la deuxième phase 5 de la cuve 2 ou de diriger l'huile de la colonne 7 vers une canalisation 12 de récupération de l'huile pour son traitement ultérieur comme déchet.This pipe and its pump make it possible to recycle the
Cette machine 1 comporte également une seconde cuve 3 partiellement remplie d'un bain 13 de DA qui ne reçoit les objets ou pièces à dégraisser qu'après leur passage successif dans les phases 5 et 6 de la première cuve 2.This
Le trajet de dégraissage, par immersion des objets, est matérialisé par la ligne pointillée 14 pour un objet 15.The degreasing path, by immersion of the objects, is shown by the dotted
Le premier bain permet d'enlever la majeure partie de l'huile. Celle-ci vient décanter à la surface du DA et se retrouve dans la phase supérieure du décanteur 4. Une bonne partie de la pollution du premier bain est ainsi éliminée. Toutefois, certaines huiles polaires sont solubles dans le DA. Pour avoir un très bon dégraissage, l'installation est complétée par le second bain 13 de DA propre qui sert à la finition du dégraissage et dont la durée de vie est très élevée.The first bath removes most of the oil. This settles on the surface of the DA and is found in the upper phase of the settling tank 4. A good part of the pollution of the first bath is thus eliminated. However, some polar oils are soluble in DA. To have a very good degreasing, the installation is completed by the
Le premier bain de DA est pollué par 3,5% en volume du mélange des 3 huiles.
- Dégraissage 10 min. seulement dans le premier bain : note = 0,5
- Dégraissage 5 min. (premier bain) + 5 min. (deuxième bain) : note = 2,5
- Degreasing 10 min. only in the first bath: note = 0.5
- Degreasing 5 min. (first bath) + 5 min. (second bath): note = 2.5
Ce procédé de dégraissage à température ambiante est donc particulièrement efficace. De plus, il entraîne une pollution très lente des bains de dégraissage. Dans des conditions extrêmes de pollution, il s'avère encore performant.This degreasing process at room temperature is therefore particularly effective. In addition, it causes very slow pollution of the degreasing baths. In extreme pollution conditions, it is still effective.
Claims (20)
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Application Number | Priority Date | Filing Date | Title |
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FR9205983 | 1992-05-18 | ||
FR9205983A FR2691168B1 (en) | 1992-05-18 | 1992-05-18 | Method for degreasing a plurality of objects. |
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EP0571246A1 true EP0571246A1 (en) | 1993-11-24 |
EP0571246B1 EP0571246B1 (en) | 1995-06-28 |
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EP93401217A Expired - Lifetime EP0571246B1 (en) | 1992-05-18 | 1993-05-13 | Process for degreasing of a plurality of objects |
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EP (1) | EP0571246B1 (en) |
AT (1) | ATE124302T1 (en) |
DE (1) | DE69300217T2 (en) |
ES (1) | ES2075767T3 (en) |
FI (1) | FI100999B (en) |
FR (1) | FR2691168B1 (en) |
NO (1) | NO307573B1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0662529A1 (en) * | 1994-01-11 | 1995-07-12 | Mitsubishi Chemical Corporation | Degreasing cleaner and method for cleaning oil-deposited material |
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DE10050315C2 (en) * | 2000-10-10 | 2003-08-21 | Uhde Gmbh | Process for dissolving salts in 1,2-dichloroethane by means of ultrasound and device for carrying out the process |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2104104A (en) * | 1981-08-14 | 1983-03-02 | Protective Finishing Group Lim | Cleaning of chemically treated articles |
FR2531805A1 (en) * | 1981-02-19 | 1984-02-17 | Videocolor Sa | Removing protective plastic films from CRT screen support |
EP0360866A1 (en) * | 1988-03-29 | 1990-04-04 | Institut Khimii Nefti Sibirskogo Otdelenia Akademii Nauk Sssr | Method and installation for cleaning parts |
-
1992
- 1992-05-18 FR FR9205983A patent/FR2691168B1/en not_active Expired - Fee Related
-
1993
- 1993-05-13 ES ES93401217T patent/ES2075767T3/en not_active Expired - Lifetime
- 1993-05-13 EP EP93401217A patent/EP0571246B1/en not_active Expired - Lifetime
- 1993-05-13 AT AT93401217T patent/ATE124302T1/en not_active IP Right Cessation
- 1993-05-13 DE DE69300217T patent/DE69300217T2/en not_active Expired - Fee Related
- 1993-05-14 NO NO931761A patent/NO307573B1/en unknown
- 1993-05-17 FI FI932234A patent/FI100999B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2531805A1 (en) * | 1981-02-19 | 1984-02-17 | Videocolor Sa | Removing protective plastic films from CRT screen support |
GB2104104A (en) * | 1981-08-14 | 1983-03-02 | Protective Finishing Group Lim | Cleaning of chemically treated articles |
EP0360866A1 (en) * | 1988-03-29 | 1990-04-04 | Institut Khimii Nefti Sibirskogo Otdelenia Akademii Nauk Sssr | Method and installation for cleaning parts |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0662529A1 (en) * | 1994-01-11 | 1995-07-12 | Mitsubishi Chemical Corporation | Degreasing cleaner and method for cleaning oil-deposited material |
US5674827A (en) * | 1994-01-11 | 1997-10-07 | Mitsubishi Chemical Corporation | Degreasing cleaner and method for cleaning oil-deposited material |
Also Published As
Publication number | Publication date |
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FR2691168A1 (en) | 1993-11-19 |
NO931761L (en) | 1993-11-19 |
FR2691168B1 (en) | 1995-01-20 |
ES2075767T3 (en) | 1995-10-01 |
FI100999B (en) | 1998-03-31 |
NO931761D0 (en) | 1993-05-14 |
FI932234A (en) | 1993-11-19 |
FI932234A0 (en) | 1993-05-17 |
EP0571246B1 (en) | 1995-06-28 |
DE69300217T2 (en) | 1995-12-21 |
DE69300217D1 (en) | 1995-08-03 |
NO307573B1 (en) | 2000-04-25 |
ATE124302T1 (en) | 1995-07-15 |
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