WO1995002712A2 - Use of carboxylic acids in agents for the treatment of metal surfaces - Google Patents

Use of carboxylic acids in agents for the treatment of metal surfaces Download PDF

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Publication number
WO1995002712A2
WO1995002712A2 PCT/EP1994/002227 EP9402227W WO9502712A2 WO 1995002712 A2 WO1995002712 A2 WO 1995002712A2 EP 9402227 W EP9402227 W EP 9402227W WO 9502712 A2 WO9502712 A2 WO 9502712A2
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WO
WIPO (PCT)
Prior art keywords
carboxylic acids
acids
agents
salts
acid
Prior art date
Application number
PCT/EP1994/002227
Other languages
German (de)
French (fr)
Other versions
WO1995002712A3 (en
Inventor
Jürgen Geke
Bernd Stedry
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1995002712A2 publication Critical patent/WO1995002712A2/en
Publication of WO1995002712A3 publication Critical patent/WO1995002712A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B01D61/146—Ultrafiltration comprising multiple ultrafiltration steps
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/14—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/32—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/34—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/50—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/52—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/60—Tall oil acids
    • C—CHEMISTRY; METALLURGY
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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    • C10M133/32—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a nitrogen-to-oxygen bond containing a nitro group
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    • C10M135/10—Sulfonic acids or derivatives thereof
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    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/06—Working-up used lubricants to recover useful products ; Cleaning by ultrafiltration or osmosis
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
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    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

  • the present invention relates to the use of carboxylic acids or their salts as essential corrosion protection components in agents for treating metal surfaces, and to a process for the preparation of such agents and for the recovery of the carboxylic acids.
  • Metal surface treatment agents for example cooling lubricants, slide abrasives or grinding water additives, industrial cleaners such as the so-called “neutral cleaners", anti-corrosion agents such as oil-based anti-corrosion emulsions and oil-free formulations generally contain a number of different components, Additives and auxiliaries that are adapted to the respective treatment purpose.
  • a number of metal surface treatment agents include O / W emulsions based on mineral oils.
  • the object of the present invention is now to provide metal surface treatment agents of the type mentioned above, which, in contrast to the current state of the art, are designed on a common active substance basis, which technically and economically sensible processing of Means after use and reuse of essential ingredients.
  • the object of the present invention is to reduce the ecological effects of the previously customary disposal of metal surface treatment agents after use, in that optimal recovery of the raw material reserves can be ensured by recovery of these active ingredients and a closed active ingredient cycle at least in the main component arises.
  • the metal surface treatment agents designed in this way can be used for various types of surface treatment, for example for cleaning, passivation and / or lubrication, of metal surfaces.
  • the usability of carboxylic acids in some metal surface treatment agents is known in the prior art, for example from DE-A-3223940 or DE-A-3933 137. However, only the use of carboxylic acids in specific metal surfaces is described here -Treatment agents described. The opposite lies
  • the present invention is based on the general concept of generally using carboxylic acids or their salts in a large number of different metal surface treatment agents in the above-mentioned manner as a common active ingredient base, ie as a corrosion protection component, and recovering the carboxylic acids after use of the agents, where it is then possible to use the carboxylic acids or mixtures again in freshly prepared or already in use metal surface treatment agents.
  • the carboxylic acids or their salts are selected from: (a) aliphatic, saturated or unsaturated, straight-chain or branched mono- and dicarboxylic acids having 6 to 22 carbon atoms, preferably having 6 to 14 carbon atoms, (b) aromatic mono- and dicarboxylic acids, preferably substituted and unsubstituted benzene mono- and benzenedicarboxylic acids and substituted and unsubstituted arylsulfonyla inocarboxylic acids,
  • Aliphatic, saturated or unsaturated, straight-chain or branched mono- and dicarboxylic acids are available in various forms in the trade.
  • the use of naturally renewable raw materials or substances based on renewable raw materials is particularly preferred from an ecological point of view.
  • carboxylic acid mixtures with different structures and lengths of the chain of the alkyl radical.
  • mono- or polyunsaturated carboxylic acids can also be used.
  • the aliphatic monocarboxylic acids are selected from natural or synthetic, saturated, straight-chain or branched monocarboxylic acids having 6 to 9 carbon atoms.
  • Particularly preferred monocarboxylic acids are: heptanoic acid (enanthic acid), octanoic acid and isononanoic acid.
  • These carboxylic acids can advantageously be used in all metal surface treatment agents as corrosion protection components; furthermore, they can be economically recovered in the sense of the present invention and then used to formulate new products or returned to a metal surface treatment agent in use.
  • the dicarboxylic acids to be used in the context of the invention are preferably selected from aliphatic, saturated, straight-chain, ⁇ , G -dicarboxylic acids having 6 to 10 carbon atoms.
  • adipic acid and sebacic acid can be mentioned here, which can be used as a corrosion protection component in the sense of the present invention.
  • the aromatic mono- and dicarboxylic acids to be used according to the invention are preferably selected from benzene mono- and benzenedicarboxylic acids, which optionally have one or more substituents selected from alkyl radicals having 1 to 3 carbon atoms, nitro, amino, Methoxy and sulfonic acid groups have.
  • the following are to be mentioned in particular: benzoic acid, 3-nitrobenzoic acid, 4-aminobenzoic acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the aromatic carboxylic acids to be used according to the invention also include those in which the carboxyl group is not bonded directly to the benzene nucleus.
  • cinnamic acid which is used in particular in combination with the 4-aminobenzoic acid mentioned above.
  • Alkylbenzoylacrylic acids which have saturated, straight-chain or branched alkyl radicals having 8 to 18 carbon atoms are also among the carboxylic acids to be used according to the invention as a corrosion protection component. Such acids are described, for example, in DE-A-3600401 and DE-A-39 33 137. Of this type of carboxylic acid, 3- (p-dodecylbenzoyl) acrylic acid is preferably used according to the invention. Substituted or unsubstituted benzoylalanines may also be mentioned as the corrosion protection component to be used according to the invention.
  • Such acids can have alkyl or hydroxyalkyl substituents on the benzene nucleus and on the N atom. They are described for example in DE-A-34 16 120 and DE-A-35 21 116. Of this type of carboxylic acid, 3- (p-methylbenzoyl) N- (l, l-dimethylethanol) alanine is preferably used according to the invention. Preferred in the sense of lying invention is also the use in particular of substituted or unsubstituted arylsulfonylaminocarboxylic acids as a corrosion protection component. Such acids are described, for example, in DE-B-12 98 672 and DE-A-33 30 223.
  • benzenesulfonylamino-carboxylic acids which are optionally substituted on the N atom by an alkyl radical having 1 to 3 C atoms are preferably used; benzenesulfonyl-N-methylaminocaproic acid should be mentioned in particular here.
  • the carboxylic acids to be used in the sense of the present invention can be used not only in the form of the free acids, but also in the same way in the form of their alkali metal, ammonium, A in and alkanolamine salts. Salts which do not lead to poorly soluble precipitates in the treatment baths and in particular on the surfaces to be treated are preferably used here. Suitable alkanolamine salts are, in particular, corresponding monoethanol or triethanolamine salts. Since such compounds are now classified as toxicologically unsafe, their use within the scope of the invention is generally of less interest. For the purposes of the invention, particular preference is given to the use of sodium or potassium salts of the carboxylic acids mentioned, where appropriate the use of corresponding potassium salts - with a view to their better solubility in water - is given priority, depending on the circumstances.
  • Metal surface treatment agents in the sense of the present invention are, for example, cooling lubricants, slide abrasives, grinding water additives, industrial cleaners, such as the so-called “neutral cleaners”, corrosion protection agents, such as oil-based corrosion protection emulsions or oil-free formulations. According to the invention Cooling lubricants, cleaning agents and anti-corrosion agents are preferred.
  • Cooling lubricants are generally understood to mean formulations which are used in metal cutting and metal forming to cool and lubricate the materials.
  • the most important machining processes which are affected by this are referred to as milling, turning, drilling and grinding (machining operations) as well as rolling, deep drawing and cold extrusion (non-cutting
  • KQhl lubricants contain - in addition to the carboxylic acids or their salts to be used according to the invention - also mineral oils or synthetic oils, for example ester oils or dialkyl ethers, as the oil phase and optionally anionic and / or nonionic surfactants or emulsifiers, solubilizers, EP additives, anti-fog additives, defoamers, biocides and other tools.
  • neutral cleaners are generally based on aqueous concentrates which have a pH in the range from 8 to 9.5. They are generally used as dilute (0.5 to 2% by weight) aqueous solutions for degreasing metal surfaces in a foam-free spraying process. Such neutral cleaners dry spot-free on the metal surfaces and thereby produce a temporary, transparent rust protection film which protects the treated metal parts against corrosive influences when stored in between.
  • neutral cleaners contain - in addition to the carboxylic acids or their salts to be used according to the invention as a corrosion protection component - nonionic and / or cationic surfactants, organic and / or inorganic builders, foam inhibitors, biocides and solubilizers.
  • Corrosion protection agents within the meaning of the present invention are both oil-free formulations based on water and oil-containing formulations, ie those based on oil. They serve to temporarily protect metallic workpieces from atmospheric, corrosive influences.
  • the oil-containing formulations can be present both as water-free or water-containing oil-based concentrates or as oil-in-water emulsion concentrates (O / W concentrate).
  • the O / W emulsion concentrates also include so-called phase inversion temperature emulsions (PIT emulsions), as described in DE-A-3933 137 cited above.
  • Mineral oils or synthetic oils, for example ester oils or dialkyl ethers are in turn suitable as the oil base for such oil-containing corrosion protection agents.
  • corrosion protection emulsions contain at least one emulsifier component.
  • An essential component of all these corrosion protection agents are the carboxylic acids or their salts to be used according to the invention.
  • Both the oil-based concentrates and the O / W emulsion concentrates are diluted with water for use and are then in the form of O / W emulsions. To stabilize such emulsions during an application process, it is generally advantageous to add emulsifiers to them.
  • emulsifiers examples include: saturated or unsaturated fatty alcohols with 12 to 22 carbon atoms, addition products of 2 to 20 moles of ethylene oxide with saturated or unsaturated fatty alcohols with 6 to 22 carbon atoms, fatty alcohol / polyethylene glycol mixed ether, glycerol partial esters of saturated or unsaturated fatty acids with 12 to 22 carbon atoms or anionic emulsifiers, preferably sodium salts of C 1 -C 8 -alkyl-benzenesulfonic acids.
  • Such emulsifiers can be added to the O / W application emulsions either directly or in the form of aqueous solutions.
  • oil-free water-based formulations mentioned above as anti-corrosion agents generally only contain the carboxylic acids or their salts to be used according to the invention in aqueous solution.
  • Such formulations are used either directly for the treatment of metallic workpieces as corrosion protection agents or also as additives to the above-mentioned O / W application emulsions or cooling lubricants during an application process to improve the corrosion protection.
  • the metal surface treatment agents for the purposes of the present invention are generally prepared in the form of concentrates and diluted with water before use, so that use takes place in an aqueous environment.
  • Such metal surface treatment agents can have different pH values which are adapted to the respective application.
  • the possibilities for adjusting the pH are sufficiently familiar to the person skilled in the art.
  • the metal surface treatment agents to be used according to the invention are generally designed in such a way that they contain - in addition to the carboxylic acids or their salts to be used as a corrosion protection component - product-specific components for the respective application.
  • the optimum here lies in the use according to the invention of a single carboxylic acid type, for example the use of homologous carboxylic acids, such as saturated or unsaturated fatty acids, the carboxylic acid type not being limited to a carboxylic acid of defined chain length with a constant amount and position of the double bonds.
  • certain boiling cuts of native or synthetic carboxylic acids can be used advantageously are used as they are known from the production of carboxylic acids, especially fatty acids, on an industrial scale.
  • the economic efficiency and the achievable relief for the environment increase to the extent that the diversity of the carboxylic acid component used is reduced.
  • the preparation method according to the invention offers the possibility of recovering and recycling the essential corrosion protection component in the sense of reuse in corresponding metal surface treatment agents.
  • the intended use of the metal surface treatment agent entails an accumulation of impurities, for example fats, solvents, extraneous oils and other dirt, in the same.
  • impurities for example fats, solvents, extraneous oils and other dirt.
  • the preparation of the agents mentioned according to the invention also enables such impurities to be separated off and the carboxylic acids used as the corrosion protection component to be recovered.
  • the treatment of the metal surface treatment agents takes place from an aqueous environment and the recovery of the carboxylic acids in a multi-stage separation process which comprises the following steps: (i) Use of at least one membrane separation process selected from microfiltration, ultrafiltration, nanofiltration and reverse osmosis, in particular ultrafiltration, for separating off an aqueous solution which contains the carboxylic acids or their salts, (ii) adjusting the pH of the aqueous solution obtained in step (i) to values in the range from 0 to 6, preferably in the range from 2 to 4, (iii) use of at least one of the membrane separation processes mentioned in step (i), in particular ultrafiltration, and / or at least one separator separation process onto the aqueous solution acidified according to step (ii) to separate the non-dissociated carboxylic acids, (iiii) optionally refining the carboxylic acids separated in step (iii).
  • a multi-stage separation process which comprises the following steps: (i) Use of at least one membrane separation process selected
  • the hydrophobic ingredients, preferably the oil components, and corresponding impurities in the metal surface treatment agent are separated from the aqueous solutions which contain the carboxylic acids or their salts.
  • the selection of the membrane separation process used and the separability of the membrane used in each case play a certain role.
  • the person skilled in the art will select a suitable membrane separation process.
  • ultrafiltration is sufficient as the membrane separation process. If metal surface treatment agents which are in the form of O / W emulsions are used for the treatment, it may be advantageous to add emulsifiers to them before carrying out step (i). Suitable emulsifiers have already been mentioned above in connection with oil-containing corrosion protection agents. If an ultrafiltration process is used, this measure requires better oil separation.
  • the pH of the aqueous solutions separated off as permeate in step (i) is adjusted in the subsequent step (ii) to values in the range from 0 to 6, preferably in the range from 2 to 5 and in particular in the range from 2 to 4.
  • the carboxylic acids to be used according to the invention can be used, but also mineral acids, for example sulfuric acid, can also be used.
  • the acidified aqueous solutions are again subjected to a membrane separation process - as in step (i).
  • a separator separation process for example using a separator or a centrifuge, can also be used here. According to the invention, the use of ultrafiltration as the separation process is preferred.
  • the non-dissociated carboxylic acids are separated from the dissociated, other anionic constituents of the aqueous solution used in each case.
  • step (iii) The carboxylic acids separated off as retentate in step (iii) can, if desired, be subjected to a further refining, for example distillation or thin-layer evaporation, in step (iiii).
  • carboxylic acids obtained in step (iii) and / or (iiii) can then be used again in the sense of the invention as an essential corrosion protection component in such agents for treating metal surfaces. If desired, they are first converted into the corresponding salts by neutralization.
  • the present invention is based on a recycling concept which makes it possible to recover and recycle the carboxylic acids used as corrosion protection components in such metal surface treatment agents.
  • the present invention comprises a process for the preparation of agents for the treatment of metal surfaces which contain carboxylic acids or their salts as an essential corrosion protection component, in a multi-stage process Separation process which comprises the steps characterized in more detail above.
  • the method according to the invention enables waste water-free treatment of the metal surface treatment agents used.
  • Examples 1 to 4 below show formulations for metal surface treatment agents which, for the purposes of the present invention, contain carboxylic acids or their salts as essential corrosion protection components.
  • the abbreviation "EO” stands for ethylene oxide.
  • the following example 5 shows the preparation of the above formulations according to examples 1 to 4 for the recovery of the carboxylic acids in the sense according to the invention.
  • the metal surface treatment agent formulations mentioned above were subjected to the multi-stage preparation using a membrane separation process, partly individually, partly in a mixture (cf. the table below).
  • the formulations were first diluted with water; the respective The use concentration of the individual formulations can be seen from the table (batch solution, conc.).
  • the preparation took place in the following steps:
  • step (i) The permeates obtained in step (i) were adjusted to pH values in the range between 2 and 5.5 using sulfuric acid (table, permeate 1 after acidification).
  • step (ii) The permeates acidified according to step (ii) were again subjected to ultrafiltration analogous to step (i). The result was retentates which now almost exclusively contained the carboxylic acids.
  • Formulation batch solution permeate 1 permeate 1 permeate 2 according to conc. PH COD COD after acidification COD example [g / 1] [mg0 2 / l] [mg0 2 / L] pH [mg0 2 / l]

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Abstract

The invention concerns the use of carboxylic acids or their salts as the basic corrosion-protection component of agents for the treatment of metal surfaces, as well as a method of separating such agents from an aqueous medium after use in accordance with specified procedures, recovering the carboxylic acids and, optionally, recycling them in a suitable agent.

Description

Verwendung von Carbonsäuren in Mitteln zum Behandeln von Metalloberflachen Use of carboxylic acids in agents for treating metal surfaces
Die vorliegende Erfindung betrifft die Verwendung von Carbonsäuren oder deren Salzen als essentielle Korrosionsschutzkomponente in Mitteln zum Behandeln von MetallOberflächen sowie ein Verfahren zur Aufbereitung derartiger Mittel und zur Wiedergewinnung der Carbon¬ säuren.The present invention relates to the use of carboxylic acids or their salts as essential corrosion protection components in agents for treating metal surfaces, and to a process for the preparation of such agents and for the recovery of the carboxylic acids.
Metalloberflächen-Behandlungsmittel, beispielsweise Kuhlschmier¬ stoffe, Gleitschleifmittel oder Schleifwasserzusätze, Industrie¬ reiniger wie die sogenannten "Neutralreiniger", Korrosionsschutz¬ mittel wie Korrosionsschutzemulsionen auf Öl-Basis und ölfreie For¬ mulierungen, enthalten in der Regel eine Reihe von verschiedenar¬ tigen Bestandteilen, Zusatzstoffen und Hilfsstoffen, die dem jewei¬ ligen Behandlungszweck angepaßt sind. So umfassen eine Reihe von Metalloberflächen-Behandlungsmittel O/W-Emulsionen auf der Basis von Mineralölen.Metal surface treatment agents, for example cooling lubricants, slide abrasives or grinding water additives, industrial cleaners such as the so-called "neutral cleaners", anti-corrosion agents such as oil-based anti-corrosion emulsions and oil-free formulations generally contain a number of different components, Additives and auxiliaries that are adapted to the respective treatment purpose. For example, a number of metal surface treatment agents include O / W emulsions based on mineral oils.
Üblicherweise ist es erforderlich, Metalloberflächen-Behandlungs- mittel nach deren bestimmungsgemäßer Anwendung zu entsorgen. Eine Aufarbeitung und Rückgewinnung der einzelnen Bestandteile der Mit¬ tel ist meist wirtschaftlich uninteressant. In der Regel ist eine Aufarbeitung und Wiederverwendung der essentiellen Bestandteile nicht möglich. Ursache hierfür ist die Fülle der üblicherweise eingesetzten Wirkstoffe, Zusatzstoffe und Hilfsstoffe, die in den einzelnen Metalloberflächen-Behandlungsmitteln keine gemeinsame stoffliche Basis b lden.It is usually necessary to dispose of metal surface treatment agents after their intended use. Processing and recovery of the individual components of the agent is usually economically uninteresting. As a rule, it is not possible to process and reuse the essential components. The reason for this is the abundance of the commonly used active ingredients, additives and auxiliary substances, which in the individual metal surface treatment agents do not have a common material basis.
Die Aufgabe der vorliegenden Erfindung besteht nunmehr darin, Me- talloberflächen-Behandlungsmittel der obengenannten Art zur Ver¬ fügung zu stellen, die im Gegensatz zu dem derzeitigen Stand der Technik auf einer gemeinsamen Wirkstoff-Basis konzipiert sind, die eine technisch und wirtschaftlich sinnvolle Aufarbeitung der Mittel nach Gebrauch und die Wiederverwendung der essentiellen Wirkstoffe ermöglicht. Darüber hinaus besteht die Aufgabe der vorliegenden Er¬ findung darin, die ökologischen Auswirkungen der bisher üblichen Entsorgung von Metalloberflächen-Behandlungsmitteln nach Gebrauch dadurch zu vermindern,daß durch Wiedergewinnung dieser Wirkstoffe eine optimale Nutzung der Rohstoffreserven gewährleistet werden kann und ein geschlossener Wirkstoffkreislauf wenigstens der Haupt¬ komponente entsteht. Die so konzipierten Metalloberflächen-Be¬ handlungsmittel können zu verschiedenen Arten der Oberflächenbe¬ handlung, beispielsweise zur Reinigung, Passivierung und/oder Schmierung, von Metalloberflächen eingesetzt werden.The object of the present invention is now to provide metal surface treatment agents of the type mentioned above, which, in contrast to the current state of the art, are designed on a common active substance basis, which technically and economically sensible processing of Means after use and reuse of essential ingredients. In addition, the object of the present invention is to reduce the ecological effects of the previously customary disposal of metal surface treatment agents after use, in that optimal recovery of the raw material reserves can be ensured by recovery of these active ingredients and a closed active ingredient cycle at least in the main component arises. The metal surface treatment agents designed in this way can be used for various types of surface treatment, for example for cleaning, passivation and / or lubrication, of metal surfaces.
Die vorgenannten Aufgaben werden gelöst durch die Verwendung von Carbonsäuren oder deren Salzen als essentielle Korrosionsschutz¬ komponente in Mitteln zum Behandeln von MetallOberflächen zur Auf¬ bereitung dieser Mittel aus einem wäßrigen Milieu nach deren be¬ stimmungsgemäßer Anwendung, Wiedergewinnung der Carbonsäuren und gegebenenfalls Rückführung derselben in ein entsprechendes Mittel.The above-mentioned objects are achieved by the use of carboxylic acids or their salts as essential corrosion protection components in agents for treating metal surfaces for the preparation of these agents from an aqueous environment after their intended use, recovery of the carboxylic acids and, if appropriate, recycling thereof appropriate means.
Zwar ist im Stand der Technik die Verwendbarkeit von Carbonsäuren in einigen Metalloberflächen-Behandlungsmitteln bekannt, so bei¬ spielsweise aus der DE-A-3223940 oder der DE-A-3933 137. Jedoch wird hier nur der Einsatz von Carbonsäuren in spezifischen Metall- oberflächen-Behandlungsmitteln beschrieben. Demgegenüber liegt der vorliegenden Erfindung das allgemeine Konzept zugrunde, Carbonsäu¬ ren oder deren Salze generell in einer Vielzahl von verschiedenen Metalloberflächen-BehandlungsmitteIn der obengenannten Art als ge¬ meinsame Wirkstoffbasis, d. h. als Korrosionsschutzkomponente, ein¬ zusetzen und die Carbonsäuren nach Gebrauch der Mittel wiederzuge¬ winnen, wobei es dann möglich ist, die Carbonsäuren oder Gemische erneut in frisch angesetzten oder bereits in Gebrauch befindlichen Metalloberflächen-Behandlungsmitteln einzusetzen.The usability of carboxylic acids in some metal surface treatment agents is known in the prior art, for example from DE-A-3223940 or DE-A-3933 137. However, only the use of carboxylic acids in specific metal surfaces is described here -Treatment agents described. The opposite lies The present invention is based on the general concept of generally using carboxylic acids or their salts in a large number of different metal surface treatment agents in the above-mentioned manner as a common active ingredient base, ie as a corrosion protection component, and recovering the carboxylic acids after use of the agents, where it is then possible to use the carboxylic acids or mixtures again in freshly prepared or already in use metal surface treatment agents.
Während im Stand der Technik auf dem hier vorliegenden Fachgebiet eine ganzheitliche Betrachtung bezüglich Ökologie, aber auch Öko¬ nomie praktisch nicht zu erkennen ist, und Recycling-Strategien sich lediglich auf die temporäre Verlängerung der Standzeiten in den einzelnen Teilbereichen der Technik konzentrieren, ist es mit Hilfe der vorliegenden Erfindung möglich, die Gewässerbelastung durch organische Rohstoffe zu reduzieren. Mit Hilfe der vorliegen¬ den Erfindung ist es im Idealfall möglich, den chemischen Sauer¬ stoffbedarf (CSB) und das Abwasservolumen auf dem Gebiet der Me¬ tallOberflächenbehandlung durch Rückführung der essentiellen Wirk¬ stoffe, d. h. der Carbonsäuren, auf Null zu reduzieren. Grundlage hierfür ist, daß die erfindungsgemäß eingesetzten Carbonsäuren während der Behandlung der jeweiligen MetallOberflächen in ihren chemischen Eigenschaften praktisch nicht verändert werden. Bedingt durch den natürlichen Verbrauch im Anwendungsprozeß ist es in der Regel jedoch erforderlich, eine mehr oder weniger große Menge an Carbonsäuren den Behandlungsmitteln neu zuzugeben.While in the state of the art a holistic view regarding ecology, but also economy, is practically not recognizable in the field at hand here, and recycling strategies concentrate only on the temporary extension of the service life in the individual sub-areas of technology, it is with With the help of the present invention it is possible to reduce the water pollution caused by organic raw materials. With the help of the present invention, it is ideally possible to reduce the chemical oxygen demand (COD) and the waste water volume in the field of metal surface treatment by recycling the essential active substances, ie. H. of carboxylic acids to reduce to zero. The basis for this is that the chemical properties of the carboxylic acids used according to the invention are practically unchanged during the treatment of the respective metal surfaces. Due to the natural consumption in the application process, however, it is usually necessary to add a more or less large amount of carboxylic acids to the treatment agents.
Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Carbonsäuren oder deren Salze ausgewählt aus: (a) aliphatisehen, gesättigten oder ungesättigten, geradkettigen oder verzweigten Mono- und Dicarbonsäuren mit 6 bis 22 C-Atomen, vorzugsweise mit 6 bis 14 C-Atomen, (b) aromatischen Mono- und Dicarbonsäuren, vorzugsweise substituierten und unsubstituierten Benzolmono- und Benzoldicarbonsäuren und substituierten und unsubstituierten Arylsulfonyla inocarbonsäuren,According to a preferred embodiment of the present invention, the carboxylic acids or their salts are selected from: (a) aliphatic, saturated or unsaturated, straight-chain or branched mono- and dicarboxylic acids having 6 to 22 carbon atoms, preferably having 6 to 14 carbon atoms, (b) aromatic mono- and dicarboxylic acids, preferably substituted and unsubstituted benzene mono- and benzenedicarboxylic acids and substituted and unsubstituted arylsulfonyla inocarboxylic acids,
(c) den wasserlöslichen Alkalimetall-, Ammonium-, Amin- und Alkanolaminsalzen der unter (a) und (b) genannten Säuren,(c) the water-soluble alkali metal, ammonium, amine and alkanolamine salts of the acids mentioned under (a) and (b),
(d) Gemischen der unter (a) bis (c) genannten Säuren und Salzen.(d) Mixtures of the acids and salts mentioned under (a) to (c).
Aliphatische, gesättigte oder ungesättigte, geradkettige oder ver¬ zweigte Mono- und Dicarbonsäuren sind in vielfältiger Form im Han¬ del erhältlich. Hierbei ist die Verwendung von natürlich nachwach¬ senden Rohstoffen oder Stoffen auf der Basis von nachwachsenden Rohstoffen aus ökologischer Sicht besonders bevorzugt. Neben den reinen Carbonsäuren können selbstverständlich auch Carbonsäurege¬ mische mit unterschiedlicher Struktur und Länge der Kette des Al- kylrestes eingesetzt werden. So sind neben den gesättigten alipha¬ tisehen Carbonsäuren auch einfach oder mehrfach ungesättigte Car¬ bonsäuren verwendbar.Aliphatic, saturated or unsaturated, straight-chain or branched mono- and dicarboxylic acids are available in various forms in the trade. The use of naturally renewable raw materials or substances based on renewable raw materials is particularly preferred from an ecological point of view. In addition to the pure carboxylic acids, it is of course also possible to use carboxylic acid mixtures with different structures and lengths of the chain of the alkyl radical. Thus, in addition to the saturated aliphatic carboxylic acids, mono- or polyunsaturated carboxylic acids can also be used.
Insbesondere sind die aliphatisehen Monocarbonsäuren ausgewählt aus natürlichen oder synthetischen, gesättigten, geradkettigen oder verzweigten Monocarbonsäuren mit 6 bis 9 C-Atomen. Besonders be¬ vorzugte Monocarbonsäuren sind: Heptansäure (Önanthsäure), Octan- säure und Isononansäure. Diese Carbonsäuren lassen sich in allen Metalloberflächen-BehandlungsmitteIn mit Vorteil als Korrosions¬ schutzkomponente einsetzen; sie können ferner im Sinne der vorlie¬ genden Erfindung in wirtschaftlicher Weise wiedergewonnen und dann zur Formulierung neuer Produkte verwendet oder in ein in Gebrauch befindliches Metalloberflächen-Behandlungsmittel rückgeführt wer¬ den. Die im Sinne der Erfindung zu verwendenden Dicarbonsäuren sind vor¬ zugsweise ausgewählt aus aliphatischen, gesättigten, geradkettigen, α,G -Dicarbonsäuren mit 6 bis 10 C-Atomen. Insbesondere sind hier¬ von Adipinsäure und Sebacinsäure zu nennen, die im Sinne der vor¬ liegenden Erfindung als Korrosionsschutzkomponente Verwendung fin¬ den können.In particular, the aliphatic monocarboxylic acids are selected from natural or synthetic, saturated, straight-chain or branched monocarboxylic acids having 6 to 9 carbon atoms. Particularly preferred monocarboxylic acids are: heptanoic acid (enanthic acid), octanoic acid and isononanoic acid. These carboxylic acids can advantageously be used in all metal surface treatment agents as corrosion protection components; furthermore, they can be economically recovered in the sense of the present invention and then used to formulate new products or returned to a metal surface treatment agent in use. The dicarboxylic acids to be used in the context of the invention are preferably selected from aliphatic, saturated, straight-chain, α, G -dicarboxylic acids having 6 to 10 carbon atoms. In particular, adipic acid and sebacic acid can be mentioned here, which can be used as a corrosion protection component in the sense of the present invention.
Die erfindungsgemäß zu verwendenden aromatischen Mono- und Dicar¬ bonsäuren sind vorzugsweise ausgewählt aus Benzolmono- und Benzol- dicarbonsäuren, die gegebenenfalls einen oder mehrere Substituen- ten, ausgewählt aus Alkylresten mit 1 bis 3 C-Atomen, Nitro-, Ami- no-, Methoxy- und Sulfonsäuregruppen, aufweisen. Hier sind insbe¬ sondere zu nennen: Benzoesäure, 3-Nitrobenzoesäure, 4-Aminobenzoe- säure, Phthalsäure, Isophthalsäure und Terephthalsäure. Zu den er¬ findungsgemäß zu verwendenden aromatischen Carbonsäuren zählen je¬ doch auch solche, bei denen die Carboxylgruppe nicht direkt an den Benzolkern gebunden ist. Beispielhaft sei hier die Zimtsäure ge¬ nannt, die insbesondere in Kombination mit der vorstehend erwähnten 4-Aminobenzoesäure eingesetzt wird. Auch AIkylbenzoylacrylsäuren, die gesättigte, geradkettige oder verzweigte Alkylreste mit 8 bis 18 C-Atomen aufweisen, zählen zu den erfindungsgemäß als Korrosions¬ schutzkomponente zu verwendenden Carbonsäuren. Derartige Säuren werden beispielsweise in den DE-A-3600401 und DE-A-39 33 137 be¬ schrieben. Von diesem Carbonsäuretyp wird erfindungsgemäß die 3-(p-Dodecylbenzoyl)-acrylsäure bevorzugt eingesetzt. Ferner sind als erfindungsgemäß zu verwendende Korrosionsschutzkomponente sub¬ stituierte oder unsubstituierte Benzoylalanine zu nennen. Derartige Säuren können am Benzolkern sowie am N-Atom Alkyl- bzw. Hydroxyal- kyl-substituenten aufweisen. Sie werden beispielsweise in den DE-A-34 16 120 und DE-A-35 21 116 beschrieben. Von diesem Carbon¬ säuretyp wird erfindungsgemäß 3-(p-Methylbenzoyl)N-(l,l-dimethyl- ethanol)-alanin bevorzugt eingesetzt. Bevorzugt im Sinne der vor- liegenden Erfindung ist ferner die Verwendung insbesondere von sub¬ stituierten oder unsubstituierten Arylsulfonyl-aminocarbonsäuren als Korrosionsschutzkomponente. Derartige Säuren werden beispiels¬ weise in den DE-B-12 98 672 und DE-A-33 30 223 beschrieben. Von diesem Carbonsäuretyp werden erfindungsgemäß Benzolsulfonyl-amino- carbonsäuren, die gegebenenfalls am N-Atom durch einen Alkylrest mit 1 bis 3 C-Atomen substituiert sind, bevorzugt eingesetzt; ins¬ besondere ist hier die Benzolsulfonyl-N-methyl- aminocapronsäure zu nennen.The aromatic mono- and dicarboxylic acids to be used according to the invention are preferably selected from benzene mono- and benzenedicarboxylic acids, which optionally have one or more substituents selected from alkyl radicals having 1 to 3 carbon atoms, nitro, amino, Methoxy and sulfonic acid groups have. The following are to be mentioned in particular: benzoic acid, 3-nitrobenzoic acid, 4-aminobenzoic acid, phthalic acid, isophthalic acid and terephthalic acid. However, the aromatic carboxylic acids to be used according to the invention also include those in which the carboxyl group is not bonded directly to the benzene nucleus. An example is cinnamic acid, which is used in particular in combination with the 4-aminobenzoic acid mentioned above. Alkylbenzoylacrylic acids which have saturated, straight-chain or branched alkyl radicals having 8 to 18 carbon atoms are also among the carboxylic acids to be used according to the invention as a corrosion protection component. Such acids are described, for example, in DE-A-3600401 and DE-A-39 33 137. Of this type of carboxylic acid, 3- (p-dodecylbenzoyl) acrylic acid is preferably used according to the invention. Substituted or unsubstituted benzoylalanines may also be mentioned as the corrosion protection component to be used according to the invention. Such acids can have alkyl or hydroxyalkyl substituents on the benzene nucleus and on the N atom. They are described for example in DE-A-34 16 120 and DE-A-35 21 116. Of this type of carboxylic acid, 3- (p-methylbenzoyl) N- (l, l-dimethylethanol) alanine is preferably used according to the invention. Preferred in the sense of lying invention is also the use in particular of substituted or unsubstituted arylsulfonylaminocarboxylic acids as a corrosion protection component. Such acids are described, for example, in DE-B-12 98 672 and DE-A-33 30 223. Of this type of carboxylic acid, benzenesulfonylamino-carboxylic acids which are optionally substituted on the N atom by an alkyl radical having 1 to 3 C atoms are preferably used; benzenesulfonyl-N-methylaminocaproic acid should be mentioned in particular here.
Die im Sinne der vorliegenden Erfindung zu verwendenden Carbonsäu¬ ren können nicht nur in Form der freien Säuren, sondern in gleicher Weise auch in Form ihrer Alkalimetall-, Ammonium-, A in- und Alka- nolaminsalze eingesetzt werden. Bevorzugt werden hierbei solche Salze eingesetzt, die nicht zu schwerlöslichen Niederschlägen in den Behandlungsbädern und insbesondere auf den zu behandelnden Ober¬ flächen führen. Als Alkanolaminsalze kommen insbesondere ent¬ sprechende Monoethanol- oder Triethanolaminsalze in Frage. Da derar¬ tige Verbindungen heutzutage jedoch als toxikologisch bedenklich eingestuft werden, ist deren Verwendung im Rahmen der Erfindung im allgemeinen von geringerem Interesse. Besonders bevorzugt im Sinne der Erfindung ist die Verwendung von Natrium- oder Kaliumsalzen der genannten Carbonsäuren, wobei gegebenenfalls der Verwendung ent¬ sprechender Kaliumsalze - im Hinblick auf deren bessere Wasserlös¬ lichkeit - je nach den Gegebenheiten eine Vorrangstellung einge¬ räumt wird.The carboxylic acids to be used in the sense of the present invention can be used not only in the form of the free acids, but also in the same way in the form of their alkali metal, ammonium, A in and alkanolamine salts. Salts which do not lead to poorly soluble precipitates in the treatment baths and in particular on the surfaces to be treated are preferably used here. Suitable alkanolamine salts are, in particular, corresponding monoethanol or triethanolamine salts. Since such compounds are now classified as toxicologically unsafe, their use within the scope of the invention is generally of less interest. For the purposes of the invention, particular preference is given to the use of sodium or potassium salts of the carboxylic acids mentioned, where appropriate the use of corresponding potassium salts - with a view to their better solubility in water - is given priority, depending on the circumstances.
Metalloberflächen-Behandlungsmittel im Sinne der vorliegenden Er¬ findung sind beispielsweise KühlSchmiermittel, Gleitschleifmittel, Schleifwasserzusätze, Industriereiniger, wie die sogenannten "Neu¬ tralreiniger", Korrosionsschutzmittel, wie Korrosionsschutzemulsi- onen auf Öl-Basis oder ölfreie Formulierungen. Erfindungsgemäß be- vorzugt sind hierbei Kühlschmiermittel, Reinigungsmittel und Kor¬ rosionsschutzmittel.Metal surface treatment agents in the sense of the present invention are, for example, cooling lubricants, slide abrasives, grinding water additives, industrial cleaners, such as the so-called "neutral cleaners", corrosion protection agents, such as oil-based corrosion protection emulsions or oil-free formulations. According to the invention Cooling lubricants, cleaning agents and anti-corrosion agents are preferred.
Unter KühlschmiermitteIn werden im allgemeinen Formulierungen ver¬ standen, die bei der MetallZerspanung und bei der MetallUmformung zum Kühlen und Schmieren der Werkstoffe verwendet werden. Die wich¬ tigsten Bearbeitungsverfahren, die hiervon betroffen sind, bezeich¬ net man als Fräsen, Drehen, Bohren und Schleifen (spangebende Bear¬ beitungen) sowie Walzen, Tiefziehen und Kaltfließpressen (spanloseCooling lubricants are generally understood to mean formulations which are used in metal cutting and metal forming to cool and lubricate the materials. The most important machining processes which are affected by this are referred to as milling, turning, drilling and grinding (machining operations) as well as rolling, deep drawing and cold extrusion (non-cutting
Verformungen). Derartige KQhlSchmiermittel enthalten - neben den erfindungsgemäß zu verwendenden Carbonsäuren oder deren Salzen - ferner Mineralöle oder synthetische Öle, beispielweise Esteröle oder Dialkylether, als Ölphase sowie gegebenenfalls anionische und/oder nichtionische Tenside oder Emulgatoren, Lösungsvermittler, EP-Zusätze, Antinebelzusätze, Entschäumer, Biozide und weitere Hilfsmittel.Deformations). Such KQhl lubricants contain - in addition to the carboxylic acids or their salts to be used according to the invention - also mineral oils or synthetic oils, for example ester oils or dialkyl ethers, as the oil phase and optionally anionic and / or nonionic surfactants or emulsifiers, solubilizers, EP additives, anti-fog additives, defoamers, biocides and other tools.
Die als "Neutralreiniger" bezeichneten Reinigungsmittel basieren in der Regel auf wäßrigen Konzentraten, die einen pH-Wert im Bereich von 8 bis 9,5 aufweisen. Sie werden in der Regel als verdünnte (0,5 bis 2 Gew.-%) wäßrige Lösungen zur Entfettung von MetallOberflächen im schaumfreien Spritzverfahren eingesetzt. Derartige Neutralrei¬ niger trocknen fleckenfrei auf den MetallOberflächen auf und er¬ zeugen hierbei einen temporären, transparenten Rostschutzfilm, der die behandelten Metallteile bei einer Zwisehenlagerung vor korro¬ siven Einflüssen schützt. Derartige Neutralreiniger enthalten - neben den erfindungsgemäß als Korrosionsschutzkomponente zu ver¬ wendenden Carbonsäuren oder deren Salzen - nichtionische und/oder kationische Tenside, organische und/oder anorganische Builder- stoffe, Schauminhibitoren, Biozide und Lösungsvermittler. Korrosionsschutzmittel im Sinne der vorliegenden Erfindung sind sowohl ölfreie Formulierungen auf Wasser-Basis sowie ölhaltige For¬ mulierungen, d. h. solche auf Öl-Basis. Sie dienen zum temporären Schutz metallischer Werkstücke vor atmosphärischen, korrosiven Ein¬ flüssen. Die ölhaltigen Formulierungen können sowohl als wasser¬ freie oder wasserhaltige Öl-basierte Konzentrate oder aber als Öl-in-Wasser-Emulsionskonzentrate (O/W-Konzentrat) vorliegen. Zu den O/W-Emulsionskonzentraten zählen insbesondere auch sogenann¬ te Phaseninversionstemperatur-Emulsionen (PIT-Emulsionen), wie sie in der vorstehend zitierten DE-A-3933 137 beschrieben werden. Als Öl-Basis für derartige ölhaltige Korrosionsschutzmittel kommen wiederum Mineralöle oder synthetische Öle, beispielsweise Esteröle oder Dialkylether, in Frage. Ferner enthalten derartige Korrosions¬ schutzemulsionen wenigstens eine Emulgatorkomponente. Ein wesent¬ licher Bestandteil all dieser Korrosionsschutzmittel sind die er¬ findungsgemäß zu verwendenden Carbonsäuren oder deren Salze. Sowohl die Öl-basierten Konzentrate als auch die O/W-Emulsionskonzentrate werden zur Anwendung mit Wasser verdünnt und liegen dann in Form von O/W-Emulsionen vor. Zur Stabilisierung derartiger Emulsionen während eines Anwendungsprozesses ist es in der Regel von Vorteil, diesen zusätzlich Emulgatoren zuzufügen. Als Emulgatoren kommen hier beispielsweise in Frage: Gesättigte oder ungesättigte Fettal¬ kohole mit 12 bis 22 C-Atomen, Anlagerungsprodukte von 2 bis 20 Mol Ethylenoxid an gesättigte oder ungesättigte Fettalkohole mit 6 bis 22 C-Atomen, Fettalkohol-polyethylenglykol-mischether, Glycerin- partialester von gesättigten oder ungesättigten Fettsäuren mit 12 bis 22 C-Atomen oder anionische Emulgatoren, vorzugsweise Natrium¬ salze von Cß-H-Alkyl-benzolsulfonsäuren. Derartige Emulgatoren können den O/W-Anwendungsemulsionen entweder direkt oder in Form wäßriger Lösungen zugefügt werden. Die als Korrosionsschutzmittel vorstehend erwähnten ölfreien For¬ mulierungen auf Wasser-Basis enthalten im allgemeinen lediglich die erfindungsgemäß zu verwendenden Carbonsäuren oder deren Salze in wäßriger Lösung. Derartige Formulierungen werden als Korrosions¬ schutzmittel entweder direkt zur Behandlung metallischer Werkstücke eingesetzt oder auch als Additiv den vorstehend erwähnten O/W-Anwendungsemulsionen oder KühlschmiermitteIn während eines An¬ wendungsprozesses zur Verbesserung des Korrosionsschutzes zuge¬ setzt.The cleaning agents referred to as "neutral cleaners" are generally based on aqueous concentrates which have a pH in the range from 8 to 9.5. They are generally used as dilute (0.5 to 2% by weight) aqueous solutions for degreasing metal surfaces in a foam-free spraying process. Such neutral cleaners dry spot-free on the metal surfaces and thereby produce a temporary, transparent rust protection film which protects the treated metal parts against corrosive influences when stored in between. Such neutral cleaners contain - in addition to the carboxylic acids or their salts to be used according to the invention as a corrosion protection component - nonionic and / or cationic surfactants, organic and / or inorganic builders, foam inhibitors, biocides and solubilizers. Corrosion protection agents within the meaning of the present invention are both oil-free formulations based on water and oil-containing formulations, ie those based on oil. They serve to temporarily protect metallic workpieces from atmospheric, corrosive influences. The oil-containing formulations can be present both as water-free or water-containing oil-based concentrates or as oil-in-water emulsion concentrates (O / W concentrate). The O / W emulsion concentrates also include so-called phase inversion temperature emulsions (PIT emulsions), as described in DE-A-3933 137 cited above. Mineral oils or synthetic oils, for example ester oils or dialkyl ethers, are in turn suitable as the oil base for such oil-containing corrosion protection agents. Furthermore, such corrosion protection emulsions contain at least one emulsifier component. An essential component of all these corrosion protection agents are the carboxylic acids or their salts to be used according to the invention. Both the oil-based concentrates and the O / W emulsion concentrates are diluted with water for use and are then in the form of O / W emulsions. To stabilize such emulsions during an application process, it is generally advantageous to add emulsifiers to them. Examples of suitable emulsifiers here are: saturated or unsaturated fatty alcohols with 12 to 22 carbon atoms, addition products of 2 to 20 moles of ethylene oxide with saturated or unsaturated fatty alcohols with 6 to 22 carbon atoms, fatty alcohol / polyethylene glycol mixed ether, glycerol partial esters of saturated or unsaturated fatty acids with 12 to 22 carbon atoms or anionic emulsifiers, preferably sodium salts of C 1 -C 8 -alkyl-benzenesulfonic acids. Such emulsifiers can be added to the O / W application emulsions either directly or in the form of aqueous solutions. The oil-free water-based formulations mentioned above as anti-corrosion agents generally only contain the carboxylic acids or their salts to be used according to the invention in aqueous solution. Such formulations are used either directly for the treatment of metallic workpieces as corrosion protection agents or also as additives to the above-mentioned O / W application emulsions or cooling lubricants during an application process to improve the corrosion protection.
Die Metalloberflächen-Behandlungsmittel im Sinne der vorliegenden Erfindung werden in der Regel in Form von Konzentraten zubereitet und vor ihrer Anwendung mit Wasser verdünnt, so daß die Anwendung in einem wäßrigen Milieu erfolgt. Hierbei können derartige Metall- oberflächen-Behandlungsmittel unterschiedliche pH-Werte aufweisen, die dem jeweiligen Anwendungszweck angepaßt sind. Die Möglichkeiten zur Einstellung des pH-Wertes sind dem Fachmann hinreichend geläu¬ fig.The metal surface treatment agents for the purposes of the present invention are generally prepared in the form of concentrates and diluted with water before use, so that use takes place in an aqueous environment. Such metal surface treatment agents can have different pH values which are adapted to the respective application. The possibilities for adjusting the pH are sufficiently familiar to the person skilled in the art.
Die erfindungsgemäß einzusetzenden Metalloberflächen-Behandlungs¬ mittel sind generell so konzipiert, daß sie - neben den als Korro¬ sionsschutzkomponente zu verwendenden Carbonsäuren oder deren Sal¬ zen - für den jeweiligen Anwendungszweck produktspezifische Kompo¬ nenten enthalten. Hierbei ist es im Sinne der Erfindung bevorzugt, die breite Vielfalt verwendbarer unterschiedlicher Carbonsäuretypen möglichst einzuschränken. Das Optimum liegt hier bei der erfindungs¬ gemäßen Verwendung eines einzigen Carbonsäuretyps, beispielsweise der Verwendung homologer Carbonsäuren, wie gesättigten oder unge¬ sättigten Fettsäuren, wobei der Carbonsäuretyp nicht auf eine Car¬ bonsäure definierter Kettenlänge mit konstanter Menge und Lage der Doppelbindungen beschränkt ist. So können in vorteilhafter Weise bestimmte Siedeschnitte von nativen oder synthetischen Carbonsäuren eingesetzt werden, wie sie aus der Herstellung von Carbonsäuren, insbesondere Fettsäuren, in technischem Maßstab bekannt sind. Die ökonomische Effizienz und die erzielbare Entlastung der Umwelt er¬ höht sich jedoch in dem Maße, wie die Vielfalt der eingesetzten Carbonsäurekomponente verringert wird. Generell bietet jedoch das erfindungsgemäße Aufbereitungsverfahren die Möglichkeit einer Rück¬ gewinnung und Kreislaufführung der essentiellen Korrosionsschutzkom¬ ponente im Sinne einer Wiederverwendung in entsprechenden Metall- oberf1ächen-Behand1ungmitte1n.The metal surface treatment agents to be used according to the invention are generally designed in such a way that they contain - in addition to the carboxylic acids or their salts to be used as a corrosion protection component - product-specific components for the respective application. In the context of the invention, it is preferred to limit the wide variety of usable different carboxylic acid types as far as possible. The optimum here lies in the use according to the invention of a single carboxylic acid type, for example the use of homologous carboxylic acids, such as saturated or unsaturated fatty acids, the carboxylic acid type not being limited to a carboxylic acid of defined chain length with a constant amount and position of the double bonds. For example, certain boiling cuts of native or synthetic carboxylic acids can be used advantageously are used as they are known from the production of carboxylic acids, especially fatty acids, on an industrial scale. However, the economic efficiency and the achievable relief for the environment increase to the extent that the diversity of the carboxylic acid component used is reduced. In general, however, the preparation method according to the invention offers the possibility of recovering and recycling the essential corrosion protection component in the sense of reuse in corresponding metal surface treatment agents.
Darüber hinaus bedingt die bestimmungsgemäße Anwendung der Metall¬ oberflächen-Behandlungsmittel eine Anreicherung von Verunreinigun¬ gen, beispielsweise von Fetten, Lösungsmitteln, Fremdölen und son¬ stigem Schmutz, in denselben. Die erfindungsgemäße Aufbereitung der genannten Mittel ermöglicht auch eine Abtrennung derartiger Verun¬ reinigungen und eine Wiedergewinnung der als Korrosionsschutzkom¬ ponente eingesetzten Carbonsäuren.In addition, the intended use of the metal surface treatment agent entails an accumulation of impurities, for example fats, solvents, extraneous oils and other dirt, in the same. The preparation of the agents mentioned according to the invention also enables such impurities to be separated off and the carboxylic acids used as the corrosion protection component to be recovered.
Im Sinne der vorliegenden Erfindung erfolgt die Aufbereitung der Metalloberflächen-Behandlungsmittel aus einem wäßrigen Milieu sowie die Wiedergewinnung der Carbonsäuren in einem mehrstufigen Trenn¬ verfahren, welches die folgenden Schritte umfaßt: (i) Anwendung mindestens eines Membrantrennverfahrens, ausgewählt aus Mikrofiltration, Ultrafiltration, Nanof ltration und Umkehrosmose, insbesondere Ultrafiltration, zur Abtrennung einer wäßrigen Lösung, welche die Carbonsäuren oder deren Salze enthält, (ii) Einstellen des pH-Wertes der im Schritt (i) gewonnenen wäßrigen Lösung auf Werte im Bereich von 0 bis 6, vorzugsweise im Bereich von 2 bis 4, (iii) Anwendung mindestens eines der im Schritt (i) genannten Membrantrennverfahren, insbesondere Ultrafiltration, und/ oder mindestens eines Separatortrennverfahrens auf die gemäß Schritt (ii) angesäuerte wäßrige Lösung zur Abtrennung der nicht-dissoziierten Carbonsäuren, (iiii) gegebenenfalls Raffination der im Schritt (iii) abgetrennten Carbonsäuren.For the purposes of the present invention, the treatment of the metal surface treatment agents takes place from an aqueous environment and the recovery of the carboxylic acids in a multi-stage separation process which comprises the following steps: (i) Use of at least one membrane separation process selected from microfiltration, ultrafiltration, nanofiltration and reverse osmosis, in particular ultrafiltration, for separating off an aqueous solution which contains the carboxylic acids or their salts, (ii) adjusting the pH of the aqueous solution obtained in step (i) to values in the range from 0 to 6, preferably in the range from 2 to 4, (iii) use of at least one of the membrane separation processes mentioned in step (i), in particular ultrafiltration, and / or at least one separator separation process onto the aqueous solution acidified according to step (ii) to separate the non-dissociated carboxylic acids, (iiii) optionally refining the carboxylic acids separated in step (iii).
Im ersten Schritt (i) werden die hydrophoben Inhaltsstoffe, vor¬ zugsweise die Ölko ponenten, und entsprechenden Verunreinigungen der Metalloberflächen-Behandlungsmittel von den wäßrigen Lösungen, die die Carbonsäuren oder deren Salze enthalten, abgetrennt. Hier¬ bei spielen natürlich die Auswahl des eingesetzten Membrantrenn¬ verfahrens und das Trennvermögen der jeweils eingesetzten Membran eine gewisse Rolle. Der Fachmann wird hier - in Abhängigkeit von dem jeweiligen Anwendungsfall - ein geeignetes Membrantrennverfah¬ ren auswählen. Im allgemeinen ist hierbei als Membrantrennverfahren jedoch eine Ultrafiltration ausreichend. Sofern hierbei Metallober¬ flächen-Behandlungsmittel zur Behandlung gelangen, die in Form von O/W-Emulsionen vorliegen, kann es von Vorteil sein, diesen vor der Durchführung des Schrittes (i) zusätzlich Emulgatoren zuzusetzen. Geeignete Emulgatoren wurden bereits vorstehend im Zusammenhang mit ölhaltigen Korrosionsschutzmitteln beispielhaft angeführt. Bei An¬ wendung insbesondere eines Ultrafiltrationsverfahrens bedingt diese Maßnahme eine bessere Ölseparierung.In the first step (i), the hydrophobic ingredients, preferably the oil components, and corresponding impurities in the metal surface treatment agent are separated from the aqueous solutions which contain the carboxylic acids or their salts. Here, of course, the selection of the membrane separation process used and the separability of the membrane used in each case play a certain role. Depending on the particular application, the person skilled in the art will select a suitable membrane separation process. In general, however, ultrafiltration is sufficient as the membrane separation process. If metal surface treatment agents which are in the form of O / W emulsions are used for the treatment, it may be advantageous to add emulsifiers to them before carrying out step (i). Suitable emulsifiers have already been mentioned above in connection with oil-containing corrosion protection agents. If an ultrafiltration process is used, this measure requires better oil separation.
Der pH-Wert der in Schritt (i) als Permeat abgetrennten wäßrigen Lösungen wird im nachfolgenden Schritt (ii) auf Werte im Bereich von 0 bis 6, vorzugsweise im Bereich von 2 bis 5 und insbesondere im Bereich von 2 bis 4, eingestellt. Hierzu können die erfindungsge¬ mäß zu verwendenden Carbonsäuren eingesetzt werden, daneben jedoch auch Mineralsäuren, beispielsweise Schwefelsäure. Im dritten Schritt (iii) werden die angesäuerten wäßrigen Lösungen erneut einem Membrantrennverfahren - wie auch in Schritt (i) - un¬ terworfen. Anstelle eines Membrantrennverfahrens oder zusätzlich zu diesem kann hier jedoch auch ein Separatortrennverfahren, bei¬ spielsweise Anwendung eines Separators oder einer Zentrifuge, ein¬ gesetzt werden. Erfindungsgemäß bevorzugt ist auch hier der Einsatz einer Ultrafiltration als Trennverfahren. In diesem Schritt (iii) erfolgt eine Abtrennung der nicht-dissoziierten Carbonsäuren von den dissoziierten, übrigen anionischen Inhaltsstoffen der jeweils eingesetzten wäßrigen Lösung.The pH of the aqueous solutions separated off as permeate in step (i) is adjusted in the subsequent step (ii) to values in the range from 0 to 6, preferably in the range from 2 to 5 and in particular in the range from 2 to 4. For this purpose, the carboxylic acids to be used according to the invention can be used, but also mineral acids, for example sulfuric acid, can also be used. In the third step (iii), the acidified aqueous solutions are again subjected to a membrane separation process - as in step (i). Instead of a membrane separation process or in addition to this, a separator separation process, for example using a separator or a centrifuge, can also be used here. According to the invention, the use of ultrafiltration as the separation process is preferred. In this step (iii), the non-dissociated carboxylic acids are separated from the dissociated, other anionic constituents of the aqueous solution used in each case.
Die in Schritt (iii) als Retentat abgetrennten Carbonsäuren können in einem Schritt (iiii) - sofern erwünscht - noch einer weiteren Raffination, beispielsweise einer Destillation oder Dünnschicht¬ verdampfung, unterworfen werden.The carboxylic acids separated off as retentate in step (iii) can, if desired, be subjected to a further refining, for example distillation or thin-layer evaporation, in step (iiii).
Die in Schritt (iii) und/oder (iiii) gewonnenen Carbonsäuren können dann im Sinne der Erfindung erneut als essentielle Korrosions¬ schutzkomponente in derartigen Mitteln zum Behandeln von Metall¬ oberflächen eingesetzt werden. Sofern erwünscht werden sie zuvor durch Neutralisation in die entsprechenden Salze überführt.The carboxylic acids obtained in step (iii) and / or (iiii) can then be used again in the sense of the invention as an essential corrosion protection component in such agents for treating metal surfaces. If desired, they are first converted into the corresponding salts by neutralization.
Basis der vorliegenden Erfindung ist ein Recycling-Konzept, welches die Wiedergewinnung und Rückführung der als Korrosionsschutzkom¬ ponente in derartigen Metalloberflächen-Behandlungsmitteln einge¬ setzten Carbonsäuren ermöglicht.The present invention is based on a recycling concept which makes it possible to recover and recycle the carboxylic acids used as corrosion protection components in such metal surface treatment agents.
In einer weiteren Ausführungsform umfaßt die vorliegende Erfindung ein Verfahren zur Aufbereitung von Mitteln zur Behandlung von Me¬ tallOberflächen, die als essentielle Korrosionsschutzkomponente Carbonsäuren oder deren Salze enthalten, in einem mehrstufigen Trennverfahren, welches die vorstehend näher charakterisierten Schritte umfaßt.In a further embodiment, the present invention comprises a process for the preparation of agents for the treatment of metal surfaces which contain carboxylic acids or their salts as an essential corrosion protection component, in a multi-stage process Separation process which comprises the steps characterized in more detail above.
Im Sinne einer vollständigen Aufbereitung der Metalloberflächen- Behandlungsmittel kann es zweckmäßig und erwünscht sein, auch die in Schritt (iii) als Permeat abgetrennten wäßrigen Lösungen, welche die dissoziierten, weiteren anionischen Inhaltsstoffe enthalten, erneut einem Membrantrennverfahren zu unterwerfen. Hierzu kommt insbesondere ein Umkehrosmose-Verfahren in Frage. Hierbei werden die verbliebenen Inhaltsstoffe der wäßrigen Lösungen vom Wasser ab¬ getrennt, so daß praktisch reines Wasser zurückbleibt. Somit ermög¬ licht das erfindungsgemäße Verfahren eine abwasserfreie Aufberei¬ tung der eingesetzten Metalloberflächen-Behandlungsmittel. In the sense of a complete preparation of the metal surface treatment agents, it may be expedient and desirable to subject the aqueous solutions, which were separated as permeate in step (iii) and which contain the dissociated further anionic ingredients, to a membrane separation process again. A reverse osmosis process is particularly suitable for this. The remaining ingredients of the aqueous solutions are separated from the water so that practically pure water remains. Thus, the method according to the invention enables waste water-free treatment of the metal surface treatment agents used.
BeispieleExamples
Die nachstehenden Beispiele 1 bis 4 zeigen Formulierungen für Me- talloberflächen-Behandlungsmittel, die im Sinne der vorliegenden Erfindung Carbonsäuren oder deren Salze als essentielle Korrosi¬ onsschutzkomponente enthalten. Die Abkürzung "EO" steht jeweils für Ethylenoxid.Examples 1 to 4 below show formulations for metal surface treatment agents which, for the purposes of the present invention, contain carboxylic acids or their salts as essential corrosion protection components. The abbreviation "EO" stands for ethylene oxide.
Beispiel 1: Reinigungsmittel (Neutralreiniger)Example 1: Detergent (neutral cleaner)
16 Gew.-% wäßrige KOH-Lösung (45 Gew.-%ig), 20 Gew.-% Isononansäure,16% by weight aqueous KOH solution (45% by weight), 20% by weight isononanoic acid,
3,5 Gew.-% Kokosamin + 12 EO (BK 1057, Handelsprodukt der Anmelderin)3.5% by weight coconut amine + 12 EO (BK 1057, commercial product of the applicant)
3,5 Gew.-% Ci2/l8~^etta^0h°1~P01ye^y^en9l -<01~bu^y''e^er (DEHYP0NR LT 104, Handelsprodukt der Anmelderin), Rest: Wasser3.5% by weight Ci2 / l8 ~ ^ etta ^ 0 h ° 1 ~ P 0 1y e ^ y ^ en 9l - <0 1 ~ b u ^ y ' ' e ^ er (DEHYP0N R LT 104, commercial product of Applicant), rest: water
Beispiel 2: KorrosionsschutzemulsionExample 2: Corrosion protection emulsion
37,7 Gew.-% Mineralöl, naphthenbasisch (Pionier1 4556, Handels¬ produkt der Fa. Hansen & Rosenthal, Hamburg), 2,1 Gew.-% Önanthsäure, 2,0 Gew.-% wäßrige KOH-Lösung (45 Gew.-%ig), 6,3 Gew.-% Polyoxyethylen-5-oleylcetylalkohol (EumulginR 05,37.7% by weight mineral oil, naphthenic (pioneer 1 4556, commercial product from Hansen & Rosenthal, Hamburg), 2.1% by weight oenanthic acid, 2.0% by weight aqueous KOH solution (45 % By weight), 6.3% by weight of polyoxyethylene-5-oleylcetyl alcohol (Eumulgin R 05,
Handelsprodukt der An elderin), 1,9 Gew.-% Glycerin-monooleat (RilanitR GM0, Handelsprodukt der Anmelderin) Rest: Wasser. Beispiel 3: KühlschmierstoffemulsionCommercial product from An elderin), 1.9% by weight glycerol monooleate (Rilanit R GM0, commercial product from the applicant) Rest: water. Example 3: Cooling lubricant emulsion
50,8 Gew.-% Mineralöl (Shell GravexR 915), 10,0 Gew.-% n-Octansäure,50.8% by weight mineral oil (Shell Gravex R 915), 10.0% by weight n-octanoic acid,
5,0 Gew.-% Tallölfettsäure,5.0% by weight tall oil fatty acid,
5,5 Gew.-% Polydiol 200,5.5% by weight of polydiol 200,
9,0 Gew.-% Oleylcetylalkohol + 2 E0 (EumulginR EP2, Handels¬ produkt der Anmelderin),9.0% by weight oleyl cetyl alcohol + 2 E0 (Eumulgin R EP2, commercial product of the applicant),
2,0 Gew.- Oleylcetylalkohol + 5 E0 (EumulginR EP5L, Handels¬ produkt der Anmelderin),2.0% by weight oleyl cetyl alcohol + 5 E0 (Eumulgin R EP5L, commercial product of the applicant),
8,7 Gew.-% C3ö-Dimerfettsäure mit Monomer-Anteilen (Empol 1022, Handelsprodukt der Henkel Corp., USA),8.7% by weight of C3ö dimer fatty acid with monomer fractions (Empol 1022, commercial product from Henkel Corp., USA),
3,0 Gew.-% vollentsalztes Wasser,3.0% by weight of fully demineralized water,
6,0 Gew.-% Kaliumhydroxid, fest (85 Gew.-%ig).6.0% by weight potassium hydroxide, solid (85% by weight).
Beispiel 4: KorrosionsschutzmittelExample 4: Corrosion protection agent
6,9 Gew.-% Kaliumhydroxid, fest (85 Gew.-%ig), 19,0 Gew.-% Önanthsäure, Rest: vollentsalztes Wasser.6.9% by weight of potassium hydroxide, solid (85% by weight), 19.0% by weight of enanthic acid, remainder: demineralized water.
Im folgendem Beispiel 5 wird die Aufbereitung der vorstehenden For¬ mulierungen gemäß Beispielen 1 bis 4 zur Wiedergewinnung der Car¬ bonsäuren im erfindungsgemäßen Sinne aufgezeigt.The following example 5 shows the preparation of the above formulations according to examples 1 to 4 for the recovery of the carboxylic acids in the sense according to the invention.
Beispiel 5:Example 5:
Die vorstehend angeführten Metalloberflächen-Behandlungsmittelfor- mulierungen wurden - zum Teil einzeln, zum Teil im Gemisch (vgl. die nachstehende Tabelle) - der mehrstufigen Aufbereitung unter Verwendung eines MembrantrennVerfahrens unterworfen. Hierzu wurden die Formulierungen zunächst mit Wasser verdünnt; die jeweilige Einsatzkonzentration der einzelnen Formulierungen ist aus der Ta¬ belle ersichtlich (Ansatzlösung, Konz.). Die Aufbereitung erfolgte in folgenden Schritten:The metal surface treatment agent formulations mentioned above were subjected to the multi-stage preparation using a membrane separation process, partly individually, partly in a mixture (cf. the table below). For this purpose, the formulations were first diluted with water; the respective The use concentration of the individual formulations can be seen from the table (batch solution, conc.). The preparation took place in the following steps:
Schritt (i):Step (i):
Die jeweiligen Ansatzlösungen wurden - bei den sich nach Verdünnen mit Wasser einstellenden pH-Werten (Tabelle, Ansatzlösung, pH) - einer Ultrafiltration über eine handelsübliche Membran (Material: Polyvinylidendifluorid; Trenngrenze: 20000 Dalton) unterworfen. Es resultierten wäßrige Permeate, die die Carbonsäuren bzw. deren Sal¬ ze enthielten (Tabelle, Permeat 1).The respective batch solutions were subjected to ultrafiltration over a commercially available membrane (material: polyvinylidene difluoride; separation limit: 20,000 daltons) at the pH values which set after dilution with water (table, batch solution, pH). The result was aqueous permeates which contained the carboxylic acids or their salts (table, permeate 1).
Schritt (ii):Step (ii):
Die in Schritt (i) jeweils gewonnenen Permeate wurden mit Schwefel¬ säure auf pH-Werte im Bereich zwischen 2 und 5,5 eingestellt (Ta¬ belle, Permeat 1 nach Ansäuern).The permeates obtained in step (i) were adjusted to pH values in the range between 2 and 5.5 using sulfuric acid (table, permeate 1 after acidification).
Schritt (iii)Step (iii)
Die gemäß Schritt (ii) angesäuerten Permeate wurden erneut einer Ultrafiltration analog Schritt (i) unterworfen. Es resultierten Retentate, die nunmehr fast ausschließlich die Carbonsäuren ent¬ hielten.The permeates acidified according to step (ii) were again subjected to ultrafiltration analogous to step (i). The result was retentates which now almost exclusively contained the carboxylic acids.
Der Erfolg der durchgeführten Aufbereitung der Formulierungen, der Abtrennung der übrigen Inhaltsstoffe von den Carbonsäuren und somit deren Rückgewinnung wurde durch Bestimmung des Chemischen Sauer¬ stoffbedarfs (CSB) - sowohl bei den Ansatzlösungen, als auch bei Permeat 1 aus Schritt (i) und Permeat 2 aus Schritt (iii) - ver¬ folgt. Hierbei erfolgte die Bestimmung der CSB-Werte nach dem Dr.Lange-Küvetten-Test. Aus den in der nachstehenden Tabelle aufgelisteten CSB-Werten ist folgendes ersichtlich: Je geringer die CSB-Werte der Permeate sind, desto größer ist der Anteil der Inhaltsstoffe der jeweiligen An¬ satzlösungen, der bei den Ultrafiltrationen abgetrennt wurde. Durch Einstellen unterschiedlicher pH-Werte im Schritt (ii) (Ansäuern) vor der zweiten Ultrafiltration läßt sich die Permeabilität ein¬ zelner Inhaltsstoffe beeinflussen und somit die Abtrennung und Wiedergewinnung der Carbonsäuren sicherstellen. The success of the preparation of the formulations, the separation of the other constituents from the carboxylic acids and thus their recovery was determined by determining the chemical oxygen requirement (COD) - both for the batch solutions and for permeate 1 from step (i) and permeate 2 from step (iii) - follows. The COD values were determined using the Dr. Lange cuvette test. The following can be seen from the COD values listed in the table below: The lower the COD values of the permeates, the greater the proportion of the constituents of the respective batch solutions which was separated off in the ultrafiltration. By setting different pH values in step (ii) (acidification) before the second ultrafiltration, the permeability of individual ingredients can be influenced and thus the separation and recovery of the carboxylic acids can be ensured.
Tabelletable
Formulierung Ansatzlösung Permeat 1 Permeat 1 Permeat 2 gemäß Konz. pH CSB CSB nach Ansäuern CSB Beispiel [g/1] [mg02/l] [mg02/L] pH [mg02/l]Formulation batch solution permeate 1 permeate 1 permeate 2 according to conc. PH COD COD after acidification COD example [g / 1] [mg0 2 / l] [mg0 2 / L] pH [mg0 2 / l]
20 9,1 21 100 14800 2,4 440020 9.1 21 100 14 800 2.4 4400
40 7,2 67000 14800 2,3 560040 7.2 67000 14800 2.3 5600
20 8,0 54000 13400 2,3 520020 8.0 54000 13400 2.3 5200
2 20 und 8,1 71 500 21900 5,5 93002 20 and 8.1 71 500 21 900 5.5 9300
4 54 5
1 20 und1 20 and
2 5 8,0 53000 16000 2,5 4400 und2 5 8.0 53000 16000 2.5 4400 and
3 10 3 10

Claims

P A T E N T A N S P R Ü C H E PATENT CLAIMS
1. Verwendung von Carbonsäuren oder deren Salzen als essentielle Korrosionsschutzkomponente in Mitteln zum Behandeln von Metall¬ oberflächen zur Aufbereitung dieser Mittel aus einem wäßrigen Milieu nach deren bestimmungsgemäßer Anwendung, Wiederrge- winnung der Carbonsäuren und gegebenenfalls Rückführung der¬ selben in ein entsprechendes Mittel.1. Use of carboxylic acids or their salts as an essential corrosion protection component in agents for treating metal surfaces for the preparation of these agents from an aqueous medium after their intended use, recovery of the carboxylic acids and, if appropriate, recycling of the same to an appropriate agent.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Carbonsäuren oder deren Salze ausgewählt sind aus:2. Use according to claim 1, characterized in that the carboxylic acids or their salts are selected from:
(a) aliphatischen, gesättigten oder ungesättigten, geradkettigen oder verzweigten Mono- und Dicarbonsäuren mit 6 bis 22 C-Atomen, vorzugsweise mit 6 bis 14 C-Atomen,(a) aliphatic, saturated or unsaturated, straight-chain or branched mono- and dicarboxylic acids with 6 to 22 C atoms, preferably with 6 to 14 C atoms,
(b) aromatischen Mono- und Dicarbonsäuren, vorzugsweise substituierten und unsubstituierten Benzolmono- und Benzoldicarbonsäuren und substituierten und unsubstituierten Arylsulfonylaminocarbonsäuren,(b) aromatic mono- and dicarboxylic acids, preferably substituted and unsubstituted benzene mono- and benzenedicarboxylic acids and substituted and unsubstituted arylsulfonylaminocarboxylic acids,
(c) den wasserlöslichen Alkalimetall-, Ammonium-, Amin- und Alkanolaminsalzen der unter (a) und (b) genannten Säuren,(c) the water-soluble alkali metal, ammonium, amine and alkanolamine salts of the acids mentioned under (a) and (b),
(d) Gemischen der unter (a) bis (c) genannten Säuren und Salzen.(d) Mixtures of the acids and salts mentioned under (a) to (c).
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Carbonsäuren ausgewählt sind aus aliphatischen, gesättig¬ ten, geradkettigen oder verzweigten Monocarbonsäuren mit 6 bis 9 C-Atomen, insbesondere aus Heptansäure, Octansäure und Iso- nonansäure.3. Use according to claim 1 or 2, characterized in that the carboxylic acids are selected from aliphatic, saturated, straight, or branched monocarboxylic acids having 6 to 9 carbon atoms, in particular from heptanoic acid, octanoic acid and isononanoic acid.
4. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Carbonsäuren ausgewählt sind aus aliphatischen, gesättigten, geradkettigen α, C -Dicarbonsäuren mit 6 bis 10 C-Atomen, insbesondere aus Adipinsäure und Sebacinsäure.4. Use according to claim 1 or 2, characterized in that the carboxylic acids are selected from aliphatic, saturated, straight-chain α, C -dicarboxylic acids with 6 to 10 C atoms, in particular from adipic acid and sebacic acid.
5. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Carbonsäuren ausgewählt sind aus Benzolmono- und Benzol- dicarbonsäuren, die gegebenenfalls einen oder mehrere Substi- tuenten, ausgewählt aus Alkylresten mit 1 bis 3 C-Atomen, Ni- tro-, Amino-, Methoxy- und Sulfonsäuregrupppen, aufweisen, ins¬ besondere aus Benzoesäure, Nitrobenzoesäure und den stellungs¬ isomeren Phthalsäuren.5. Use according to claim 1 or 2, characterized in that the carboxylic acids are selected from benzene mono- and benzene-dicarboxylic acids, which optionally have one or more substituents selected from alkyl radicals having 1 to 3 carbon atoms, nitro, Amino, methoxy and sulfonic acid groups, in particular from benzoic acid, nitrobenzoic acid and the positionally isomeric phthalic acids.
6. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Carbonsäuren ausgewählt sind aus Benzolsulfonylaminocar- bonsäuren, die gegebenenfalls am N-Atom durch einen Alkylrest mit 1 bis 3 C-Atomen substituiert sind, insbesondere Benzolsul¬ fonyl-N-methyl-£-aminocapronsäure.6. Use according to claim 1 or 2, characterized in that the carboxylic acids are selected from benzenesulfonylaminocarboxylic acids which are optionally substituted on the N atom by an alkyl radical having 1 to 3 C atoms, in particular benzenesulfonyl-N-methyl £ aminocaproic acid.
7. Verwendung nach einem oder mehreren der Ansprüche 1 bis 6, da¬ durch gekennzeichnet, daß die Salze der Carbonsäuren ausgewählt sind aus Natrium- und Kaliumsalzen der genannten Säuren.7. Use according to one or more of claims 1 to 6, characterized in that the salts of the carboxylic acids are selected from sodium and potassium salts of the acids mentioned.
8. Verwendung nach einem oder mehreren der Ansprüche 1 bis 7, da¬ durch gekennzeichnet, daß die Mittel zum Behandeln von Metall¬ oberflächen ausgewählt sind aus Kühlschmiermitteln, Reinigungs¬ mitteln und Korrosionsschutzmitteln.8. Use according to one or more of claims 1 to 7, characterized in that the agents for treating Metall¬ surfaces are selected from cooling lubricants, cleaning agents and anti-corrosion agents.
9. Verwendung nach einem oder mehreren der Ansprüche 1 bis 8, da¬ durch gekennzeichnet, daß die Aufbereitung der Mittel aus einem wäßrigen Milieu und die Wiedergewinnung der Carbonsäuren in einem mehrstufigen Trennverfahren erfolgt, welches die folgen¬ den Schritte umfaßt:9. Use according to one or more of claims 1 to 8, characterized in that the preparation of the agents from an aqueous environment and the recovery of the carboxylic acids takes place in a multi-stage separation process which comprises the following steps:
(i) Anwendung mindestens eines Me brantrennverfahrens, ausgewählt aus Mikrofiltration, Ultrafiltration, Nanofiltration und Umkehrosmose, insbesondere Ultrafiltration, zur Abtrennung einer wäßrigen Lösung, welche die Carbonsäuren oder deren Salze enthält,(i) application of at least one chemical separation process, selected from microfiltration, ultrafiltration, nanofiltration and reverse osmosis, in particular ultrafiltration, for the separation of an aqueous solution which contains the carboxylic acids or their salts,
(ii) Einstellen des pH-Wertes der im Schritt (i) gewonnenen wäßrigen Lösung auf Werte im Bereich von 0 bis 6, vorzugsweise im Bereich von 2 bis 4,(ii) adjusting the pH of the aqueous solution obtained in step (i) to values in the range from 0 to 6, preferably in the range from 2 to 4,
(iii) Anwendung mindestens eines der im Schritt (i) genannten Membrantrennverfahren, insbesondere Ultrafiltration, und/oder mindestens eines Separatortrennverfahrens auf die gemäß Schritt (ii) angesäuerte wäßrige Lösung zur Abtrennung der nicht-dissoziierten Carbonsäuren,(iii) application of at least one of the membrane separation processes mentioned in step (i), in particular ultrafiltration, and / or at least one separator separation process to the aqueous solution acidified according to step (ii) to separate off the non-dissociated carboxylic acids,
(iiii)gegebenenfalls Raffination der im Schritt (iii) abgetrennten Carbonsäuren.(iiii) optionally refining the carboxylic acids separated off in step (iii).
10. Verwendung nach Anspruch 9, dadurch gekennzeichnet, daß man die in Stufe (iii) und/oder Stufe (iiii) gewonnenen Carbonsäuren, gegebenenfalls nach Neutralisation derselben, erneut als Korro¬ sionsschutzkomponente in Mitteln zum Behandeln von Metallober¬ flächen einsetzt.10. Use according to claim 9, characterized in that the carboxylic acids obtained in stage (iii) and / or stage (iiii), optionally after neutralization thereof, are used again as a corrosion protection component in agents for treating metal surfaces.
11. Verfahren zur Aufbereitung von Mitteln zum Behandeln von Me- talloberflachen, die als essentielle Korrosionsschutzkomponente Carbonsäuren oder deren Salze enthalten, und Wiedergewinnung der Carbonsäuren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man ein mehrstufiges Trennver¬ fahren nach Anspruch 9 und gegebenenfalls Anspruch 10 anwendet. 11. A process for the preparation of agents for treating metal surfaces which contain carboxylic acids or their salts as an essential corrosion protection component, and recovery of the carboxylic acids according to one or more of claims 1 to 8, characterized in that a multi-stage separation process according to claim 9 and optionally claim 10 applies.
PCT/EP1994/002227 1993-07-16 1994-07-07 Use of carboxylic acids in agents for the treatment of metal surfaces WO1995002712A2 (en)

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DE4323907A DE4323907A1 (en) 1993-07-16 1993-07-16 Use of carboxylic acids in agents for treating metal surfaces

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EP1277853A1 (en) * 2000-04-27 2003-01-22 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy
WO2014031305A1 (en) 2012-08-22 2014-02-27 Invista North America S.A R.L. Aliphatic dicarboxylic acid mixture formulation
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Publication number Priority date Publication date Assignee Title
EP1277853A1 (en) * 2000-04-27 2003-01-22 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy
EP1277853A4 (en) * 2000-04-27 2004-04-07 Otsuka Kagaku Kk Process for producing part made of magnesium and/or magnesium alloy
US6787192B2 (en) 2000-04-27 2004-09-07 Otsuka Kagaku Kabushiki Kaisha Process for producing part made of magnesium and/or magnesium alloy
US11272740B2 (en) 2012-07-16 2022-03-15 Nicoventures Holdings Limited Electronic vapor provision device
WO2014031305A1 (en) 2012-08-22 2014-02-27 Invista North America S.A R.L. Aliphatic dicarboxylic acid mixture formulation
US12082604B2 (en) 2015-03-31 2024-09-10 Nicoventures Trading Limited Article for use with apparatus for heating smokable material

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WO1995002712A3 (en) 1995-06-22

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