EP0370976A2 - Organische Phosphatierlösung und Vorrichtung zu deren Verwendung - Google Patents

Organische Phosphatierlösung und Vorrichtung zu deren Verwendung Download PDF

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Publication number
EP0370976A2
EP0370976A2 EP89830517A EP89830517A EP0370976A2 EP 0370976 A2 EP0370976 A2 EP 0370976A2 EP 89830517 A EP89830517 A EP 89830517A EP 89830517 A EP89830517 A EP 89830517A EP 0370976 A2 EP0370976 A2 EP 0370976A2
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EP
European Patent Office
Prior art keywords
phosphating
solvents
weight
composition according
high boiling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89830517A
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English (en)
French (fr)
Other versions
EP0370976B1 (de
EP0370976A3 (de
Inventor
Gianluigi Guidetti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PAI-KOR Srl
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PAI-KOR Srl
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Publication date
Application filed by PAI-KOR Srl filed Critical PAI-KOR Srl
Publication of EP0370976A2 publication Critical patent/EP0370976A2/de
Publication of EP0370976A3 publication Critical patent/EP0370976A3/de
Application granted granted Critical
Publication of EP0370976B1 publication Critical patent/EP0370976B1/de
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds

Definitions

  • the present invention relates to an orga­nic phosphatizing composition and a system for using it, as well as methods for pre-processing and re­covering solvents.
  • the so-called single stage organic phosphatizing method is a very advantageous method for processing metals, which provides the possibility of degreasing and phosphatizing metals in a single step.
  • This organic phosphatizing method is con­ventionally carried out by using a polyphosphate solution, diluted in suitable solvents, in which metal pieces are immersed for degreasing purposes.
  • the organic single-stage phosphatizing method does not present, unli­ke the conventional phosphatizing method, problems relating to the processing of the sewage polluted materials to be disposed.
  • the mentioned organic single-stage phosphatizing method involves a release into the environment of solvent vapors, however in an amount less than that released from degreasing methods using chlorinated solvent vapours.
  • organic phosphatizing systems have been designed, which provide for the use of different formulation polyphosphates and which provide an improved resistance to corrosion and, moreover, can be also used for particular finishing operations such as, for example, by using polyester powders which could not previously be used in organic phosphatizing methods.
  • the main object of the present invention is to provide such an organic phosphatizing compo­sition which has all of the advantages of known phosphatizing compositions and which, moreover, is not inflammable, free of any chlorinated solvents, free of dangerous products to be specifically in­dicated in the composition formulations, as pro­vided by enforcing rules, and which, moreover, is very satisfactory from a pollution-ecologic stand­point.
  • Another object of the present invention is to provide such a single-stage phosphatizing composition which has a very high metal degreasing capability.
  • Another object of the present invention is to provide such a composition which is adapted to solubilize both polyphosphates and oils and fats.
  • an organic phosphatizing composition comprising two or more mixed solvents in an amount of 85 ⁇ 99%, preferably of about 98% and polyphosphates, including acid phosphates and/­or free phosphoric acid and possible surface active materials in an amount from 1 to 15%, preferably of about 2% by weight.
  • the solvents to be used in the composition of the present invention must have the following properties:
  • the solvent mixtures must be formulated for meeting the above requirements of solubility, hydro­gen binding properties and, moreover, the made mix ture must be a good solvent both for polyphosphates and oils and greases.
  • organic phospha­tizing solutions which do not include any chlori­nated solvents and which can be also spray applied because of the low vapour tension of the contained solvent substances and which compositions, moreover, are not inflammable (they are only combustible) since they have a flash point higher than 65°C, said compositions being prepared starting from the following solvent mixture:
  • the phosphatizing system in turn, com­prises a processing section, a blowing section and a drying section, as well as a solvent recovering section.
  • this system comprises respectively a pro­cessing section 1, a blowing section 2, a drying section 3 and a solvent recovery section 4.
  • the processing section can comprise a static processing basin 5, or a processing in-linebasin 6, which are substantially constructed like basins used for conven­tional organic phosphatizing processes.
  • a manually movable sleeve 8 adapted to facilitate the mechanic­al cleaning operations on the pieces 9 to be pro­cessed which are driven by hoist device 10 provided for sliding along a single rail 11.
  • the orientable jet from the sleeve provides an accurate cleaning of the critical points of the pieces to be cleaned.
  • the nozzles in particular, will be ener­gized as the piece is withdrawn from the processing basin.
  • nozzles can also be arranged at the outlet of said basin, in order to facilitate the cleaning operations of difficult areas.
  • the nozzles will be positioned so as to prevent polyphos­phate aerosols to exit the processing tunnel, the outline of which is indicated at 12.
  • a possible modification of the in-line installation consists of a two-chain system which, with suitable lowering devices, enables to use processing tanks similar to those ones adopted for static installations.
  • the above disclosed basins are pro­vided by a removable double bottom 13 for collecting sludges, as well as an output shut-off valve 14, an inlet shut-off valve 15, a ball valve 16, on the bottom discharge, and a discharge vessel well 17.
  • the above disclosed processing section 1 can also comprise a spray processing tunnel, with related ramps (not specifically shown), the construc­tion of which is similar to that one used in convention­al phosphatizing and/or phosphatizing-degreasing systems.
  • a filtering device which can comprise a bag-filter and can be controlled by the same pump which supplies the spraying nozzles.
  • any suitable nozzles used for conventional phosphatizing methods can be used, possibly made of a stainless steel material (for example AISI 303).
  • nozzles having an opening angle of 60/90 with useful jets of 20-30 cm are preferable using nozzles having an opening angle of 60/90 with useful jets of 20-30 cm.
  • jet shape it will be defined depending on requirements and on the pieces to be phosphatized and considering that: - nozzles with a blade jet provide a greater pressure, with a consequent high mechanical cleaning effect; - spraying heads with a solid conic jet efficiently cover broad surfaces of the piece.
  • the operating pressure ranges usually from 0.5 to 1.5 atm.
  • blowing section 2 Downstream of the processing section there is the blowing section 2 installed to remove quickly the excess processing product remaining on the processed pieces.
  • the blowing step in particular, can be performed by using air circulation generated by centrifugal fans 18, with a high head (100-120 mm or more of water column), the airflow being adjusted so as to provide a flow output rate of at least 5 m/s.
  • suitable spraying nozzles can be provided, as suitably arranged depending on the pieces to be processed and supplied by sources adapted to provide a high output speed of 8 ⁇ 15 m/­sec.
  • the nozzle must operate on the pieces from the top toward the bottom thereof, so as to accelerate the natural gravity draining process and they must operate with a sufficient power to remove any excess of the processing product.
  • blowing step affords the possibility of: - eliminating a long draining time; - eliminating possible held by liquid materials which would be susceptible to cause painting defects; - recovering of the polyphosphates and reduction of the consume due to an entraining of the product.
  • blowing section is advantage­ously located inside a suitable casing (tunneling casing).
  • air blades of suitable strength adapted to operate as pneuma­tic gates.
  • the drying section essentially comprises an air circulating oven, consisting, for example, of a tunnel 19 defined, at the bottom and side por­tions thereof, by a box body 20 having through its inner walls, a plurality of slots 21.
  • This box-like body is supplied with pressu­rized hot air, by means of the air source 22 and centrifugal fans 23 conveying the hot air through ducts 24.
  • the hot air which is "laminated" through the above mentioned slots, arrives into the tunnel 19 with a suitable turbulence, so as to impinge on the metal pieces 19 sliding on the rail 11 through the tunnel itself.
  • an air/air type of exchanger 26 can be advantageously provided for low­ering the temperature of the air.
  • pneumatic doors In order to prevent losses of this hot air saturated in processing solvents, pneumatic doors must bs fitted at the input and output of the tunnel and are controlled by a centrifugal fan 28 which sucks air from the top portion of the section.
  • the tunnel inlet and outlet doors have an extension as small as possible, that is just sufficient to allow for the smallest piece to pass therethrough.
  • This solvent recovery procedure which can also be performed by a simple but expensive cooling (by ther­mal exchange of the hot air sent from the drainage of the drying section, because of the low vapor ten­sion of the selected solvents), is preferably perform­ed by sending the air to be processed to the washing column indicated at 29 in figure 1.
  • an absorbing column can be provided including a spray cyclone 30 and having a tangential air input, whereas the washing liquid is sprayed, as shown in the figure, for a height sufficient to wash air and cool it.
  • the washing column 31 can comprise a plurality of stacked plates 32, in any suitable number, and, in this case, the air to be washed, introduced from the bottom, will move in a counter-current relationship with re­spect to a washing liquid.
  • the washing column 33 is provided with an intermediate portion 34, defined by holding nets 35 and filled with a suitable inert material, the function of which is that of facilitating the contact of the air to be washed and cooled, introduced from the bottom and the washing liquid, introduced from the top with a counter current relationship.
  • the mentioned inert material can consists, for example, of crushed stones, of round shape, ceramic material ring and/or ball members, polypro­pilene hollow balls or rings, of different diameters and the like.
  • the washing column moreover, must be so designed and arranged as to allow the temperature of the air to be lowered to limit values 5 ⁇ 10°C higher than the room temperature, so as to bring the vapor phase in equilibrium with the counter­fed processing liquid.
  • the gray region represents a not mixing zone.
  • a combination of A+B+C having a rate composition of and pertaining to a straight line WA (for example the point P of the diagram) is mixed into the two phases, aqueous W and solvent S.
  • the slopes of the straight lines WS are cha racteristic of each ternary system. It should be apparent that if we start from a point W and add a mixture of the solvents B and C so as to cause the point representative of the composition of the system A+B+C to be displaced substantially along the straight line WS, then we will have the formation of two phases: - a solvent phase substantially holding B+C and a small amount of water - and aqueous phase which is practically nearly equal to the starting phase - the offset is due to the small amount of water which is present in the phase S).
  • At the base of the washing column will have substantially a liquid which is rich in the solvents restrained in the air to be washed or cleaned.
  • washing or cleaning liquid Since the washing or cleaning liquid is always selected with a composition corresponding to the proper point W,it will be mixed into two phases. Thus it will be sufficient to convey it through a duct 37 to a Florentine separator 38 which is substantially formed by a vessel including two possible outlets,that is a bottom outlet 40 and a top outlet 41 provided with corresponding control gates 42.
  • the solvent phase is lighter than water (as shown in the figure)
  • the bottom outlet,or water phase outlet will be coupled,through a pump 43 and an exchanger 44 with the head of a generic washing or cleaning column,whereas the top outlet will convey to the outside the solvent phase.
  • the exchanger 44 is provided for introducing into the column 29 the washing liquid at a sufficiently low temperature to allow for the air to be cleaned to be cooled.
  • the recovered solvent in particular,is alternatively sent to a first 45 and second 46 vessel which form an integrating portion of a subsequent de­hydration section,indicated overally at the reference number 47.
  • the Florentine separator can comprise a labyrinth path,as exemplary shown in figure 12a.
  • the solvents brought to the vessels 45 and/or 46 also hold a water fraction.
  • the developped brown color causes the processed piece to be discarded,even if the results, from the corrosion resistance standpoint would be acceptable.
  • this solvent must be dehydrated,before reusing it.
  • This section comprises,in particular, a dehydrating apparatus 48 including a cylinder provided, at its end portions,with very fine mesh nets and made of a thermal resistant glass or steel,with a large inspection port.
  • a dehydrating material consisting of molecular sieves or highly water absorbing salts or, preferably,silica gel,holding an indicating or labeling substance to color the product in blue if it is anhydrous or in pale pink if it is water saturated.
  • the apparatus 48 must contain a sufficient silica gel amount,with a proper safety tolerance range,to recover or regenerate the product held in the vessels 45 and 46.
  • shut off valve 50 there are moreover provided a passage in the bottom cover, with a related shut off valve for the air at 120°C coming from the drying air source, and an air outlet through the top cover,also provided with a shut off valve 50.
  • a treatment for about two hours will be sufficient :however the silica gel loaded material must be held under control in order to detect a possible water saturation thereof.
  • the solvent,at this time, is ready to be reused. 4) the pump 58 is stopped 5) the gates 53 to 57 are closed again.
  • the dehydrated solvent can be stored in the vessel 45 and,as it must be reused,it can be removed through the gate 59.
  • outlet air of said apparatus will contain at the start the solvents which have wetted the silica gel and then the water stripped therefrom.
  • the recovered solvent amount is small,then the solvent can also be dehydrated in a simplified way by arranging in the vessel 45 a bag containing a sufficient amount of silica gel.
  • This silica gel as water saturated,can be easily brought to the drying oven to be regenerated.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Saccharide Compounds (AREA)
  • Detergent Compositions (AREA)
  • Extraction Or Liquid Replacement (AREA)
EP89830517A 1988-11-23 1989-11-22 Organische Phosphatierlösung und Vorrichtung zu deren Verwendung Expired - Lifetime EP0370976B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT8822705A IT1227716B (it) 1988-11-23 1988-11-23 Fosfatazione organica in solventi non clorurati aventi flash point > 65 c ed impianto per la sua utilizzazione comprendente il recupero deisolventi
IT2270588 1988-11-23

Publications (3)

Publication Number Publication Date
EP0370976A2 true EP0370976A2 (de) 1990-05-30
EP0370976A3 EP0370976A3 (de) 1991-07-17
EP0370976B1 EP0370976B1 (de) 1996-03-27

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ID=11199456

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89830517A Expired - Lifetime EP0370976B1 (de) 1988-11-23 1989-11-22 Organische Phosphatierlösung und Vorrichtung zu deren Verwendung

Country Status (5)

Country Link
EP (1) EP0370976B1 (de)
AT (1) ATE136065T1 (de)
CA (1) CA2003639A1 (de)
DE (1) DE68926101T2 (de)
IT (1) IT1227716B (de)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2270642A (en) * 1935-02-08 1942-01-20 Budd Induction Heating Inc Cleaning and degreasing system
FR1075889A (fr) * 1952-05-27 1954-10-20 American Chem Paint Co Perfectionnements apportés aux procédés et produits pour le traitement préalablede métaux pour leur déformation à froid
GB887159A (en) * 1959-11-09 1962-01-17 Du Pont Degreasing and coating apparatus and process
FR1450079A (fr) * 1964-10-10 1966-05-06 Hoechst Ag Agent de nettoyage et de passivation de surfaces métalliques
US3356540A (en) * 1964-05-28 1967-12-05 Baron Ind Of California Method of phosphatizing articles
US3424177A (en) * 1965-06-18 1969-01-28 Baron Blakeslee Inc Degreasing,phosphatizing and cleaning apparatus
US4038155A (en) * 1976-04-05 1977-07-26 Purex Corporation Ltd. Energy saving vapor degreasing apparatus
FR2362202A1 (fr) * 1976-08-20 1978-03-17 Haertol Werk Agent de traitement chimique de la surface des metaux et des matieres thermodurcissables, ainsi que des metaux portant un revetement de transformation mineral non metallique
DE2754724A1 (de) * 1976-12-10 1978-06-15 Projectus Ind Produkter Ab Verfahren und vorrichtung zum trocknen von maschinenteilen
DE3708909A1 (de) * 1986-04-02 1987-10-15 Werner Dreisoerner Gmbh Entfettungs- und korrosionsschutzmittel

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2270642A (en) * 1935-02-08 1942-01-20 Budd Induction Heating Inc Cleaning and degreasing system
FR1075889A (fr) * 1952-05-27 1954-10-20 American Chem Paint Co Perfectionnements apportés aux procédés et produits pour le traitement préalablede métaux pour leur déformation à froid
GB887159A (en) * 1959-11-09 1962-01-17 Du Pont Degreasing and coating apparatus and process
US3356540A (en) * 1964-05-28 1967-12-05 Baron Ind Of California Method of phosphatizing articles
FR1450079A (fr) * 1964-10-10 1966-05-06 Hoechst Ag Agent de nettoyage et de passivation de surfaces métalliques
US3424177A (en) * 1965-06-18 1969-01-28 Baron Blakeslee Inc Degreasing,phosphatizing and cleaning apparatus
US4038155A (en) * 1976-04-05 1977-07-26 Purex Corporation Ltd. Energy saving vapor degreasing apparatus
FR2362202A1 (fr) * 1976-08-20 1978-03-17 Haertol Werk Agent de traitement chimique de la surface des metaux et des matieres thermodurcissables, ainsi que des metaux portant un revetement de transformation mineral non metallique
DE2754724A1 (de) * 1976-12-10 1978-06-15 Projectus Ind Produkter Ab Verfahren und vorrichtung zum trocknen von maschinenteilen
DE3708909A1 (de) * 1986-04-02 1987-10-15 Werner Dreisoerner Gmbh Entfettungs- und korrosionsschutzmittel

Also Published As

Publication number Publication date
IT8822705A0 (it) 1988-11-23
DE68926101T2 (de) 1996-11-21
CA2003639A1 (en) 1990-05-23
EP0370976B1 (de) 1996-03-27
DE68926101D1 (de) 1996-05-02
EP0370976A3 (de) 1991-07-17
IT1227716B (it) 1991-05-06
ATE136065T1 (de) 1996-04-15

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