(19)
(11) EP 0 370 976 A2

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication:
30.05.1990 Bulletin 1990/22

(21) Application number: 89830517.2

(22) Date of filing: 22.11.1989
(51) International Patent Classification (IPC)5C23C 22/03
(84) Designated Contracting States:
AT BE CH DE ES FR GB GR IT LI NL SE

(30) Priority: 23.11.1988 IT 2270588

(71) Applicant: PAI-KOR S.R.L.
I-20144 Milano (IT)

(72) Inventor:
  • Guidetti, Gianluigi
    I-20144 Milano (IT)

(74) Representative: Cicogna, Franco 
Ufficio Internazionale Brevetti Dott.Prof. Franco Cicogna Via Visconti di Modrone, 14/A
20122 Milano
20122 Milano (IT)


(56) References cited: : 
   
       


    (54) Organic phosphatizing composition and system for using it


    (57) The composition comprises two or are mixed solvents having a flash point higher than 65°C and a vapor tension, at 20°C, lower than 2 mm Hg, which comprises 85 ÷ 99% of the composition. The composition also comprises polyphosphates, including acid phosphates and/or free phosphoric acid and possible surface active agents, in an amount of 1 - 15%.
    The phosphatizing system comprises a processing section (1), a blowing section (2) and drying section (3), as well as a solvent recovery section (4).




    Description


    [0001] 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.

    [0002] As is known, 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.

    [0003] 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.

    [0004] After the degreasing step, because of the acidity of the polyphosphate, an acid attack occurs followed, after the withdrawing of the piece and its drying for evaporating solvents, a deposition of a polymeric film which prepares the metallic surfaces for a subsequent painting step.

    [0005] The above mentioned process, in parti­cular, is of a "permanent" type and, accordingly, for properly carrying out it, it is necessary to provide stable polyphosphates, which are stable in the presence of oils and fats and, moreover, are adapted to provide a film in the presence of these polluting substances.

    [0006] Inflammable and not inflammable chlorina­ted solvent based compositions and chlorinated solvent free inflammable compositions are usual­ly commercially available.

    [0007] These products, however, are preferably used by an immersion process, since, if they would be used in spraying processes, then the evaporation loss of the solvent would be comparatively high with a consequent increase of the processing cost and environment pollution because of the varying con­ditions of the dry residue of the polyphosphate solutions.

    [0008] In this connection, it should be pointed out that, from an ecologic standpoint, 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. On the contrary, 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.

    [0009] Recentely, moreover, 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.

    SUMMARY OF THE INVENTION



    [0010] 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.

    [0011] Another object of the present invention is to provide such a single-stage phosphatizing composition which has a very high metal degreasing capability.

    [0012] Another object of the present invention is to provide such a composition which is adapted to solubilize both polyphosphates and oils and fats.

    [0013] According to one aspect oi the present in­vention, the above mentioned objects, as well as yet other objects, which will become more apparent hereinafter, are achieved by 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.

    [0014] In particular, the solvents to be used in the composition of the present invention must have the following properties:

    1) they must be high boiling solvents (having a boiling temperature higher than 125°C and prefera­bly higher than 200°C),

    2) they must have a very low vapor tension, less than 2 mm Hg at 20°C, and preferably much lower than this value,

    3) they must have a high flash point, usually higher than 65°C and preferably much higher,

    4) they must not comprise chlorinated solvents and, generally, alogenated solvents,

    5) they must not comprise any substances classified as dangerous and, are specifically they must not be labeled as risk substances, according to the en­forcing rules.



    [0015] Thus, by way of an example, the following solvents can be advantageously used:

    1) Glycol ethers from propylene oxide, and prefer­ably dimers or trimers such as, for example:
    - Dipropylenglycolemonomethylether(DPM)
    - Dipropylenglycolemonoethylether (EDP)
    - Dipropylenglycolemono-n-butylether (DPnB)
    - Dipropylenglycolemonoisobutylether (DPiB)
    - Tripropylengiycolemonomethylether(TPM)
    - Tripropylenglycolemono-n-butylether (TPnB)
    - Propylenglycolphenylether (PPh)

    2) Glycolethers from ethylene oxide, and preferably dimers or trimers, such as, for example:
    - Methylether of diethyleneglycole (DM)
    - Ethylether of diethyleneglycole (DE)
    - Butylether of ethyleneglycole (DB)

    3) High boiling acetates such as, for example:
    - EDA= ethyldiglycolacetate
    - BDA= Butyldiglycolacetate
    - DPMA= dipropylenglycolmonomethyletheracetate

    4) High boiling aromatic solvents such as, for ex­ample:
    - Solvesso 150(R), ShellsolAB(R) or the like (S150)
    - Solvesso 200(R) or the like (S200)

    5) Di-acetates, esters, di-basic esters and other solvents such as, for example:
    - Propylenglycolediacetate (PGDA)
    - Dibasic esthers (dimethyladipate, dimethylglutarrate, dimethylsuccinate) (DBE/RPDE)
    - Ehtyl-3-ethoxypropionate (EEP)
    - Propylencarbonate (PC)
    - High boiling alkylacetates (hereinafter indicated as AA) having the formula:
    CH₃COOR
    where R is an alkylic chain having from 7 to 13 carbon atoms.



    [0016] In the following description, the above indicated solvents will be identified with reference to the letters written within parenthesis.

    [0017] In this connection it should be apparent that 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.

    [0018] The above listed solvent mixtures have been experimentally tested with a great success even if they involve small differences in the corro­sion resistance.

    [0019] In the following table have been identified at A the compositions in which prevails the first of the mixture solvents and at B the com­positions in which prevails, as far as possible, the second solvent of the mixture.







    [0020] In actual practice, according to the in­vention, it is possible to prepare 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:

    1) Glycolethers from propyleneoxide (DPM, EDP, DPnB, DBiB, TPM, TPnB, PPh, and so on) 25 - 100%;
    high boiling aromatic solvents (such as S150, S200 or the like), 75-0%;

    2) Diethylenglycole ethers (DM, DE, DB, and so on) 30-70%,
    high boiling aromatic solvents (S150, S200, and so on) 70-30%;

    3) High boiling acetates (EDA, BDA, DPMA, and so on) 80-50%;
    high boiling aromatic solvents (S150, S200, and so on) 20-50%;

    4) Di-ester esters and other high boiling solvents (EEP, PC, DBE, RPDE, PGDA, and so-on) 30-85%;
    high boiling aromatic solvents (S150, S200, and so on) 70-15%;

    5) Propyleneoxide glycolethers
    (DPM, EDP, DPnB, DBiB, TPM, TPnB, PPh, and so on) 15-100%
    high boiling alkylacetates < C7 - C13 > 85 - 0%

    6) Diethylenglycole ethers
    (DM, DE, DB, and so on) 30 - 75%
    high boiling alkylacetates < C7 - C13 > 70 - 25%

    7) High boiling acetates (EDA, BDA, DPMA, and so on) 80 - 50% high boiling alkylacetate < C7 - C13 > 20 - 50%



    [0021] It should be apparent that it will be possi­ble to prepare mixtures including three or more solvents, by mixing at will the above mentioned solvents. This procedure does not involve any form­ulation problems even if it does not provide further advantages and involves a less efficient control of the solvents which can be recovered and/or reused, as it will become are apparent hereinafter.

    [0022] The above mentioned products, in particular, do not require, according to the CEE's standard, any risk labels and have TLV's which can not be practical­ly achieved and, accordingly, can be used safely.

    [0023] The phosphatizing system, in turn, com­prises a processing section, a blowing section and a drying section, as well as a solvent recovering section.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0024] Further characteristics and advantages of the phosphatizing composition and system, according to the present invention, will become more apparent from the following detailed disclosure of some pre­ferred embodiment thereof, which are illustrated, by means of an indicative but not limitative example, in the figures of the accompanying drawings, where:

    Figure 1 shows an operating sketch of the phosphatizing system according to the invention;

    Figures 2 and 3 are respectively an eleva­tion and top plan view of a static type of processing basin;

    Figures 4, 5 and 6 are respectively an elevation, top plan and side view illustrating an in­line processing basin;

    Figures 7 and 8 are respectively a front and cross-sectional view illustrating the drying section included in the system according to the invention;

    Figures 9, 10 and 11 illustrate three possible types of washing columns;

    Figure 12 is a schematic view illustra­ting the solvent recovering apparatus of the subject system;

    Figure 12a is a cross-sectional view illustrating a so-called Florentine separator.


    DESCRIPTION OF THE PREFERRED EMBODIMENTS



    [0025] With respect to the atmospheric pollution, it should be pointed out that the processing and blowing stages of the subject system, which will be disclosed in a more detailed way hereinafter, provide very reduced amounts of solvents emissions.

    [0026] In the drying step, on the contrary, are necessari­ly generated solvent vapours in an amount correspond­ing to about 20-25 g/processed m². These emissions are anyhow recovered.

    [0027] With respect to the phosphatizing system, and with reference to figure 1, it should be appa­rent that this system comprises respectively a pro­cessing section 1, a blowing section 2, a drying section 3 and a solvent recovery section 4.

    [0028] More specifically, 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.

    [0029] In particular, on the delivery side of the filtering circuit, indicated overally at the reference number 7, of the above mentioned static basin, there is advantageously arranged 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.

    [0030] In particular, the orientable jet from the sleeve provides an accurate cleaning of the critical points of the pieces to be cleaned.

    [0031] That same result, moreover, can also be achieved by using a plurality of nozzles (of the type which will be disclosed in a more detailed way hereinafter), so as to provide a mixed immersing/­spraying system.

    [0032] The nozzles, in particular, will be ener­gized as the piece is withdrawn from the processing basin.

    [0033] Even when an in-line basin 6 is used, nozzles can also be arranged at the outlet of said basin, in order to facilitate the cleaning operations of difficult areas.

    [0034] In case a spraying nozzle ramp is used, the nozzles will be positioned so as to prevent polyphos­phate aerosols to exit the processing tunnel, the outline of which is indicated at 12.

    [0035] Also in this case, it is indispensable to provide air blades at the inlet and outlet of the tunnel with a limited drainage which, after filtering-out of the aerosols, will be sent to a subsequent solvent recovering column.

    [0036] 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.

    [0037] The above disclosed basins, in particular, 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.

    [0038] 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.

    [0039] Also in this case it is recommendable to prepare an organic phosphatizing material plenum chamber in order to avoid oil poliphosphate saturation due to the treatment of too oily and fatty articles.

    [0040] Like in the immersion processing, more-­over, a filtering device will be provided, which can comprise a bag-filter and can be controlled by the same pump which supplies the spraying nozzles.

    [0041] With respect to the latter, any suitable nozzles used for conventional phosphatizing methods can be used, possibly made of a stainless steel material (for example AISI 303).

    [0042] In particular, it is preferable using nozzles having an opening angle of 60/90 with useful jets of 20-30 cm.

    [0043] With respect to the 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.

    [0044] The operating pressure ranges usually from 0.5 to 1.5 atm.

    [0045] Downstream of the processing section there is the blowing section 2 installed to remove quickly the excess processing product remaining on the processed pieces.

    [0046] 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.

    [0047] Alternatively, 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.

    [0048] In this connection, it should be apparent that 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.

    [0049] It should be apparent that the 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.

    [0050] On a suitably blown product, from 20 to 25 g/m² of diluted material should be held, with the exception of possible greater amounts on pieces having specific shapes.

    [0051] In this connection it should be pointed out that the mentioned blowing section is advantage­ously located inside a suitable casing (tunneling casing).

    [0052] At the inlet and outlet of the blowing section, moreover, are provided air blades of suitable strength, adapted to operate as pneuma­tic gates.

    [0053] 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.

    [0054] 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.

    [0055] 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.

    [0056] In this connection it should be apparent that this hot air can be re-cycled with the exception of an air cage corresponding to 10 ÷ 15% which will be sent to the column for washing and recover­ing solvents.

    [0057] In particular, since it is preferably that the air sent to the subsequent washing column through the duct 25 arrives at this column with a temperature as low as possible, an air/air type of exchanger 26 can be advantageously provided for low­ering the temperature of the air.

    [0058] 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.

    [0059] In order to further limit the thermal losses, additional automatic mechanical doors can be pro­vided and adapted to be opened only when the metal pieces to be draied pass therethrough.

    [0060] Moreover, it is recommendable that 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.

    [0061] Downstream of the mentioned drying section will be arranged the above mentioned solvent re­covery section 4.

    [0062] 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.

    [0063] More specifically, 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.

    [0064] According to an alternative embodiment, 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.

    [0065] According to a preferred embodiment, 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.

    [0066] 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.

    [0067] In this connection, it should be pointed out that to the washing column are conveyed the following air drainages:
    - a drainage coming from the optional air blades of the processing section, at room temperature;
    - a drainage coming from the air blades of the blow­ing section, at room temperature;
    - hot drainages coming from the drying section and perimetrical air blades of that same section,

    [0068] 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.

    [0069] From the top of the column washed air 36 will exit. Since, as is known, based on the Raoult law which is valid for vapors following the ideal gas laws, the partial pressure of each component in the vapor is equal to the product of its molar frac­tion (X) in the liquid x the vapor tension (P) of the product under examination at the system tempera­ture:
    pi = Pi x Xi
    where
    pi = partial pressure of the component (i) in the vapor
    Pi = vapor tension of the component (i) at the tempe­rature T of the system
    Xi = molar fraction of the component (i) in the liquid,
    it follows that,since solvents here sele­cted have a very low vapor tension, the concentra­tion of these solvents will be very low, whilst the air will be moisture saturated.

    [0070] In actual practice, however, the solvent vapours are not ideal solvent vapors.

    [0071] Because of this it is necessary to amend the above mentioned law by including therein a multi­plication factor which has a thermodynamic meaning of "activity coefficient" and the value of which, anyhow, is never such as to modify the above qualita­tive disclosure.

    [0072] From the above discussion, it will be appa­rent that the air exiting the washing column is sub­stantially purified and only moisture saturated.

    [0073] In order to understand what occurs at the bottom of the washing column, it should be remember­ed that a ternary mixture, consisting of two organic solvents one of which is a hydrophylic solvent, plus water, usually this mixture naturally separates into two dis­ tinct phases.
    - The first defined for simplicity "aqueous phase" which mainly holds water.
    - The second defined for simplicity "solvent phase" which holds solvents and a small amount of water.

    [0074] All of the disclosed solvents, with the exception of PC, PGDA and PPH are, in the liquid status, lighter than water; accordingly the solvent layering will usually occur with the aqueous phase at the bottom and the solvent phase at the top. By way of an example, in the diagram of figure 13 has been illustrated the case comprising water, in­dicated at A in the diagram, and a completely mix­able solvent both in water and in the other solvent (DPM, EDP, TPM, DM, DE, DB), indicated at B in the diagram, and, finally, a completely water not mix­able solvent (S150, S200 AA C7÷C13), indicated at C in the diagram. More specifically, this diagram shows the ternary mixture of water, TPM, S150.

    [0075] In the diagram 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.

    [0076] 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).

    [0077] From the above it should be apparent that by selecting suitable ratios of B and C which can be determined on the basis of the cross point of the straight line WS and line segment BC, and with small amounts of added water, the system can be controlled in an equilibrium condition.

    [0078] Different solvent systems bring to condi­tions that can also differ from the shown condition but which can always conceptually brought back to the shown condition.

    [0079] 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.

    [0080] 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.

    [0081] If the solvent phase is lighter than water (as shown in the figure),then 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.

    [0082] 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.

    [0083] During the operation it would be advantageous to hold the top outlet in a closed condition.At the end of the working day,a rest condition will provide a perfect separation or "layering" of the two phases. The separation interface will lower because of the evaporated water removed together with the cleaned air. Thus,it will be necessary:

    1) to add water from the water supply system so as to bring the separation interface to the theoretical level. This operation will be facilitated by the provision of an ispection door or port 51.

    2) to open the top outlet so as to cause the solvent recovered from the column to exit the Florentine separator.



    [0084] 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.

    [0085] In order to facilitate a better phase sepa­ration,the Florentine separator can comprise a labyrinth path,as exemplary shown in figure 12a.

    [0086] It should be apparent that if the solvent has a weight greater than that of the water, then one has to work on the top outlet as indicated for the bottom outlet and on the bottom outlet as indicat­ed for the top outlet.

    [0087] The solvents brought to the vessels 45 and/or 46 also hold a water fraction.

    [0088] If,as for example propylene oxide glycolethers are used, the presence of water is significative,then the use of such a solvent will bring to the so-called "flash-rust" effect which occurs at the drying step of the organig phosphatizing method.

    [0089] The developped brown color causes the processed piece to be discarded,even if the results, from the corrosion resistance standpoint would be acceptable.

    [0090] In these cases,accordingly,this solvent must be dehydrated,before reusing it.

    [0091] Because of this requirement,a dehydrating section has been provided which,as stated,must be actually provided only if the water amount held in the solvent phase is such as to originate the mention­ed "Flash-rust" effect.

    [0092] 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. Within this cylinder there is arranged 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.

    [0093] Owing to this provision,it will be practical­ly possible,by a simple visual inspection,to evaluate the efficiency of the dehydrating product.

    [0094] In this connection,it should be further pointed out that 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.

    [0095] For closing the cylinder there are provided two flanged covers supporting tubes for conveying the liquid to be dehydrated.

    [0096] 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.

    [0097] The outlet air will be sent,as shown in the diagram of figure 1,to the air washing or clean­ing column,

    [0098] From an operating standpoint,if the solvent held in the vessel 45 must be dehydrated,then the following method should be used:
    1) the gate 52 is closed so as to prevent any solvent from entering;
    2) the gates 53,54,55,56 and 57 are opened
    3) the pump 58 is actuated and the solvent is circulat­ed.

    [0099] 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.

    [0100] The dehydrated solvent can be stored in the vessel 45 and,as it must be reused,it can be removed through the gate 59.

    [0101] At this time,it will be necessary to rege­ nerate the silica gel for the subsequent dehydration cycle and,to that end,the gates 49 and 50 will be opened and air will be blown into the apparatus 48, at a temperature of about 120°C,supplied by the hot air source of the drying section.

    [0102] In particular the outlet air of said apparatus will contain at the start the solvents which have wetted the silica gel and then the water stripped therefrom.

    [0103] In this connection it should be apparent that if 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.

    [0104] While the invention has been disclosed and illustrated with reference to preferred embodiments thereof,it should be apparent that the disclosed embodiments are susceptible to several modifications and variations,all of which will come within the spirit and scope of the appended claims.


    Claims

    1- An organic phosphatizing composition for de­greasing and phosphatizing metal surfaces in a single stage,characterized in that said composition comprises two or more mixed solvents having a flash point higher than 65°C,of a not toxic, harmful or irritating type, and with a vapor tension at 20°C lower than 2 mm Hg,in an amount of 85-99% by weight,and poly­phosphates,including acid phosphates and/or free phosphoric acid as well as surface active substances in an amount of 15%-1% by weight.
     
    2- A phosphating composition according to claim 1,wherein said composition comprises high boiling not halogenated solvents having a flash point higher than 65°C,said composition being of the combustible but not inflammable type.
     
    3- A phospating composition according to claim 1,wherein said composition comprises solvents having,at 20°C, a vapor tension lower than 2 mm Hg and preferably much lower.
     
    4- A phosphating composition according to claim 1, which contains solvents based on propylene oxide glycol ethers in an amount of 25 to 75% by weight and high boiling aromatic solvents in an amount of 75 to 25% by weight.
     
    5- A phosphating composition according to claim 1, wherein said solvents comprise a single solvent.
     
    6- A phosphating composition according to claim 5,wherein said single solvent consists of dipropyleneglycolemono-n-­butylether.
     
    7- A phosphating composition according to claim 5,wherein said single solvent consists of dipropyleneglycolemonoiso­butylether.
     
    8- A phosphating composition according to claim 5,wherein said single solvent comprises tripropyleneglycolemono-n-­butylether.
     
    9- A phosphating composition according to claim 1,wherein said solvents comprise 30-70% by weight of diethyleneglycole­ ethers and 70-30% by weight of high boiling aromatic solvents.
     
    10- A phosphating composition according to claim 1,wherein said solvents comprise 50-80% of high boiling acetates and 50-20% of high boiling aromatic solvents.
     
    11- A phosphating composition according to claim 1,wherein said solvents comprise 30-85% by weight of high boiling esters or diesters and 70-15% by weight of high boiling aromatic solvents.
     
    12- A phosphating composition according to claim 1,wherein said composition comprises from 15 to 50% by weight of either ethyl-3-ethoxypropionate or propylenecarbonate and from 85 to 50% by weight of high boiling aromatic solvents.
     
    13- A phosphating composition according to claim 1,wherein said solvents comprise from 15 to 100% by weight of propylene oxide glycolethers and from 85 to 0% by weight of high boiling C7 - C13 alkylacetates.
     
    14- A phosphating composition according to claim 1,wherein said solvents comprise 30-75% by weight of diethylene­glycole ethers and from 70 to 25% by weight of high boiling C7 -C13 alkylacetates.
     
    15- A composition according to claim 1,wherein said solvents comprise from 50 to 80% by weight of high boiling acetates and 50-20% by weight of high boiling C7-C13 alkylacetates.
     
    16- A composition according to claim 1,wherein said composition comprise a mixture of more than two of said solvents, according to the various possible combinations.
     
    17- A phosphating composition according to claim 1,wherein said composition is adapted both for spray application operations and for immersion operation.
     
    18- A phosphatizing system for phosphatizing metal pieces by using a composition according to claim 1,characteriz­ed in that said installation comprises both static tanks and in-line tanks including a filtering circuit on a delivery side of which there is provided a manually movable sleeve for mechanically cleaning metal pieces to be cleaned,said metal pieces being driven by hoisting means slidingly supported on single rail means.
     
    19- A phosphating system according to claim 18,wherein said system is a combined immersion/spraying system includ­ing a plurality of spraying nozzles actuated as a said metal piece is withdrawn from a said basin means.
     
    20- A phosphating system according to claim 18, wherein said basin means comprise a line basin, and said system further comprises a plurality of said spraying nozzles arranged at an outlet side of said line basin.
     
    21- A phosphating system according to claim 18, wherein said system a blowing system section for removing from said metal pieces liquid processing material of set amounts,said blowing system section including air generating centrifugal high head fans providing an adjustable air flow having a flow rate of at least 5m/sec.
     
    22- A phosphating system according to claim 18, wherein said system comprises a drying section including a hot air circulat­ ing oven.
     
    23- A phosphating system according to claim 18, wherein said hot air circulating oven is a tunnel oven including a bottom and side box-like body having a plurality of slots,and a pressurized hot air generating-fan assembly adapted to generate pressurized hot air and convey said pressurized hot air through duct means of said oven.
     
    24- A phosphating system according to claim 18, wherein said system comprises a solvent recovering section including an air washing column holding said solvents and operating by an aqueous washing liquid.
     
    25 . A phosphating system according to claim 18, wherein said column comprises spraying cyclone means having a tangential air inlet.
     
    26 A phosphating system according to claim 24, wherein said column comprises a plurality of stacked plates,air to be washed being supplied from a bottom portion of said column to move in counterflow against said washing liquid.
     
    27 - A phosphating system according to claim 24, wherein said washing column comprises an intermediate portion def­ined by holding nets and filled with an inert material, adapted to facilitate the contact of air to be washed and cooled,introduced from the bottom of said column, and the washing liquid, said inert material comprising round crushed stone particles,ceramic material ring and/or ball members,polypropylene hollow ball and ring members of different diameters and the like.
     
    28- A phosphating system according to claim 24, wherein the liquid from the outlet of said washing column is conveyed to a Florentine separator substantially comprising a vessel including two outlets provided with respective gates,one of said outlet,that is the water phase outlet, being coupled through a pump and exchanger to a head portion of said washing column,and the other outlet conveying to the outside the solvent phase,the latter being alternately sent to a first and second vessel included in a subsequent dehydration section.
     
    29- A phosphating system according to claim 28, wherein said de­hydration section comprises an apparatus including a cylinder made of a thermal resistant glass or steel with a large inspection port provided with very fine mesh nets therein a dehydrating material is arranged preferably consisting of silica gel and holding an indicating means adapted to color in blue an anhydrous product and in pale pink a water saturated product, through said apparatus passing both the solcent to be dehydratated and hot air for recovering the silica gel bed.
     




    Drawing