EP0571246B1 - Procédé de dégraissage d'une pluralité d'objets - Google Patents

Procédé de dégraissage d'une pluralité d'objets Download PDF

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Publication number
EP0571246B1
EP0571246B1 EP93401217A EP93401217A EP0571246B1 EP 0571246 B1 EP0571246 B1 EP 0571246B1 EP 93401217 A EP93401217 A EP 93401217A EP 93401217 A EP93401217 A EP 93401217A EP 0571246 B1 EP0571246 B1 EP 0571246B1
Authority
EP
European Patent Office
Prior art keywords
degreasing
process according
liquid
article
phase
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.)
Expired - Lifetime
Application number
EP93401217A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0571246A1 (fr
Inventor
Jean-Pierre Lallier
Daniel Bignon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0571246A1 publication Critical patent/EP0571246A1/fr
Application granted granted Critical
Publication of EP0571246B1 publication Critical patent/EP0571246B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 precisely, 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 a precious metal such as gold or platinum. It can also be mineral glass, ceramic or 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 eliminated in accordance with the legislation in force - (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 can be lower.
  • the energy considered above covers the production of the chemical substances used, cleaning itself 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 detachment of the layer of fatty substance covering the surface of the object.
  • This method has multiple advantages over the methods known from the prior art.
  • 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 may be pure diacetone alcohol or contain additives, in particular a small percentage by weight of methanol or water relative to the total weight of the liquid or alternatively of 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 reverse, passing lastly 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.
  • 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, stirring, sprinkling, a rise in temperature are all factors that increase the effectiveness of degreasing.
  • a mixture of polar and nonpolar 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.
  • Example 2 The evaluation of the degreasing efficiency was the same as in Example 1.
  • the tests with diacetonalcohol were carried out according to the first procedure (soaking 15 min. In solvent at room temperature). The performances of diacetone alcohol were compared to those of trichloroethane T 111 used hot.
  • - steel plate coated with vaseline oil 90 ° - plate after 15 min.
  • degreasing at DA 56 ° ⁇ 6 ° - plate after 15 min.
  • degreasing with DA additive with 3% methanol (% by weight relative to the weight of DA) 52 ° ⁇ 2.5 ° - plate after 7 min.
  • degreasing with T 111 at boiling point 61 ° ⁇ 2.5 ° - plate after 7 min.
  • 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 additivated with 3% (w / w) of methanol and used at room temperature is as effective as a boiling T 111 boiling., 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.
  • diacetonalcohol was compared to an aqueous detergent, as well as to new substitutes based on propylene glycol ethers or their mixtures with petroleum fractions.
  • 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.
  • Degreasing is carried out for 5 minutes with ultrasound, according to the first procedure, but the evaluation of the degreasing is made by observing the spreading of the water on the plate in a manner analogous to example 4.
  • 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 comprises 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.
  • the first DA bath is polluted with 3.5% by volume of the mixture of the 3 oils.
  • - Degreasing 10 min. only in the first bath note 0.5
  • - Degreasing 5 min. (first bath) + 5 min. (second bath) note 2.5
  • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Control Of Vending Devices And Auxiliary Devices For Vending Devices (AREA)
  • Management, Administration, Business Operations System, And Electronic Commerce (AREA)
EP93401217A 1992-05-18 1993-05-13 Procédé de dégraissage d'une pluralité d'objets Expired - Lifetime EP0571246B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9205983 1992-05-18
FR9205983A FR2691168B1 (fr) 1992-05-18 1992-05-18 Procédé de dégraissage d'une pluralité d'objets.

Publications (2)

Publication Number Publication Date
EP0571246A1 EP0571246A1 (fr) 1993-11-24
EP0571246B1 true EP0571246B1 (fr) 1995-06-28

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ID=9429869

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93401217A Expired - Lifetime EP0571246B1 (fr) 1992-05-18 1993-05-13 Procédé de dégraissage d'une pluralité d'objets

Country Status (7)

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EP (1) EP0571246B1 (es)
AT (1) ATE124302T1 (es)
DE (1) DE69300217T2 (es)
ES (1) ES2075767T3 (es)
FI (1) FI100999B (es)
FR (1) FR2691168B1 (es)
NO (1) NO307573B1 (es)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW324029B (en) * 1994-01-11 1998-01-01 Mitsubishi Chem Corp De-oiling cleaner composition
DE10050315C2 (de) * 2000-10-10 2003-08-21 Uhde Gmbh Verfahren zur Auflösung von Salzen in 1,2-Dichlorethan mittels Ultraschall und Vorrichtung zur Durchführung des Verfahrens

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3106181A1 (de) * 1981-02-19 1982-09-02 Videocolor GmbH, 7900 Ulm Verfahren zur entfernung von folien und folienresten von schirmtraegern fuer kathodenstrahlroehren
GB2104104A (en) * 1981-08-14 1983-03-02 Protective Finishing Group Lim Cleaning of chemically treated articles
BR8807552A (pt) * 1988-03-29 1990-05-22 Inst Khim Nefti Sib Otdel Akad Processo e aparelho para limpar pecas de trabalho

Also Published As

Publication number Publication date
FR2691168B1 (fr) 1995-01-20
FI100999B (fi) 1998-03-31
FR2691168A1 (fr) 1993-11-19
NO307573B1 (no) 2000-04-25
ES2075767T3 (es) 1995-10-01
FI932234A0 (fi) 1993-05-17
EP0571246A1 (fr) 1993-11-24
DE69300217T2 (de) 1995-12-21
NO931761L (no) 1993-11-19
DE69300217D1 (de) 1995-08-03
FI932234A (fi) 1993-11-19
NO931761D0 (no) 1993-05-14
ATE124302T1 (de) 1995-07-15

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