EP0373174A1

EP0373174A1 - Process and device for purifying degreasing solutions

Info

Publication number: EP0373174A1
Application number: EP88907046A
Authority: EP
Inventors: Rolf Reuter
Original assignee: Gut Gesellschaft fur Umweltschonende Technik Mbh
Current assignee: Gut Gesellschaft fur Umweltschonende Technik Mbh
Priority date: 1987-08-04
Filing date: 1988-07-20
Publication date: 1990-06-20
Also published as: DK28290A; FI900505A0; JPH02504652A; AU2086088A; ES2009344A6; DK28290D0; BR8807640A; DE3725819A1; WO1989001056A1

Abstract

Un procédé d'épuration de solutions usées de dégraissage d'une installation de dégraissage d'huiles et graisses émulsifiées comprend les étapes suivantes: (a) réchauffement des solutions usées de dégraissage jusqu'à des températures dans une plage comprise entre 80° et 100°, (b) refroidissement des solutions de dégraissage réchauffées, (c) filtrage de la solution de dégraissage refroidi à travers un filtre fin (50) afin de séparer les huiles et les graisses, (d) ajustage de la solution résiduelle ainsi obtenue jusqu'à obtenir une solution de dégraissage ayant la composition voulue, (e) remise en circulation de la solution de dégraisage ainsi épurée et ajustée dans l'installation de dégraissage. L'invention concerne également un dispositif d'application de ce procédé.A process for purifying used degreasing solutions from an installation for degreasing emulsified oils and fats comprises the following steps: (a) heating the used degreasing solutions to temperatures in a range between 80 ° and 100 °, (b) cooling the heated degreasing solutions, (c) filtering the cooled degreasing solution through a fine filter (50) in order to separate the oils and greases, (d) adjusting the residual solution thus obtained until to obtain a degreasing solution having the desired composition, (e) recirculating the degreasing solution thus purified and adjusted in the degreasing installation. The invention also relates to a device for applying this method.

Description

₅ METHOD AND DEVICE FOR CLEANING DEGREASING SOLUTIONS

Technical field

¹⁰ The invention relates to a method for cleaning used degreasing solution from a degreasing system of emulsified oil and fat, in which the used degreasing solution is heated to temperatures in the range from 50 ° to 100 ° and then by heating

15 separated oil and fat layer is separated from a residual solution.

Degreasing solutions are used in many areas of technology _. eg in the automotive industry or in the

2.0 Electroplating technology used for cleaning metal surfaces. Such degreasing solutions usually contain a number of chemicals which have the effect that the desired cleaning effect is achieved and the impurities (oil or fat) in the

25 degreasing solution remain dissolved. Among other things, such a degreasing solution contains an emulsifier, which causes oil and fat to be emulsified in the degreasing solution. The degreasing solution becomes increasingly contaminated over time and less and less

30 effective. The invention is concerned with the cleaning of such degreasing solutions.

35 ¹ The invention also relates to a device for cleaning used degreasing solution for carrying out this method, comprising

⁵ (a) a heater for heating the used degreasing solution and

(b) means for removing oil and fat which is separated from the heated degreasing solution after splitting ¹⁰ the emulsion,

Underlying state of the art

So far the used degreasing solutions ^~ - ^{~~ have been} discarded. This had the disadvantage that considerable disposal problems arose because the used degreasing solutions contained chemicals which were harmful to the environment.

20 It is known to break the emulsions of oil or fat in water in such degreasing solutions and to separate the oil or fat components thus formed. From DE-C2-29 27 275 it is known to thermally cleave the emulsion by heating the degreasing solution to one

25 temperature between 50 ° and 100 ° C. It is also known from this document to add a flocculant to this degreasing solution before heating. The. DE-C2-29 27 275 recommends the addition of Wasserstoff¬ peroxide and heating to 75 ° to 85 C. The ^he

30 separated oil or fat is reused or burned. The degreasing solution freed from the oil is added to the sewage network.

35 ¹ Also in "Ullmann's Encyclopedia of Technical Chemistry" 4th ed. Volume 10 page 453 mentions temperature rise as a means of breaking an emulsion.

⁵ In an essay by Rathgeber "Processes and plants for the treatment of oil-contaminated wastewater" in the journal "Wasser.luft und Betrieb" 17 (1973), 69-71, various processes and plants for the treatment of waste water, including degreasing solutions, are described , ° in which emulsions of oil in water are broken. In some of these processes, the breaking of the emulsions is achieved by adding precipitants. A method and a plant (Fig. 8) are also known in which the emulsion is broken by heating with the addition of 5 acids. This is done in a container filled with packing (column), whereby the oil. I count in the upper one. Settles part of this column.

0 In all the processes described there, the liquid freed from the oil is treated as waste water and added to the waste water system.

DE-A1-35 12 207 describes a method for reprocessing aqueous, oil and fat-containing substances

Degreasing solutions are known in which oil and fat are separated from the degreasing solution by means of an oil separator. The mixture of oil, fat and degreasing solution separated by the oil separator is thickened by evaporation. The steam also serves to heat the oil separator, while the

Condensate water into the degreasing solution

Regeneration is supplied. The oil separator is based on the different density of oil and water. The separated oil rises and is replaced by a Overflow deducted. Such mechanical separation of the oil and fat still leaves a very large proportion of these contaminants in the degreasing solution. A "regeneration" of the degreasing solution after separation of the oil takes place there only by distilled water, namely the condensate of the evaporation. The degreasing solution cleaned in this way shows only a reduced degreasing effect and largely corresponds to the "waste water" of the prior art discussed above. The degreasing solution can only be used for a limited time even when using this oil separator.

Disclosure of the invention

The invention has for its object to provide a method and an apparatus by which the "service life" of a degreasing solution is extended considerably while maintaining the required degreasing effect.

The method of the invention contains the method steps:

(a) heating the used degreasing solution to temperatures in the range from 80 ° to 100 °,

(b) then re-cooling the heated degreasing solution,

(c) Filter the cooled degreasing solution through a fine filter to separate l and

Fat, (d) Setting the residual solution thus obtained in the degreasing system to the respectively desired composition of the degreasing solution and

(e) returning the cleaned and re-adjusted degreasing solution to the degreasing system.

A device of the type mentioned at the outset for cleaning used degreasing solution for carrying out the aforementioned method is characterized in that

(c) the heating device is followed by a cooling device for re-cooling the ^" degreasing solution heated to ^" ,

(d) downstream of the cooling device in the flow path a fine filter for the one to be cleaned. Degreasing solution is arranged

(e) means are arranged downstream of the fine filter for adding used or destroyed components of the degreasing solution and

(f) the flow path is returned to the degreasing system.

According to the invention, the degreasing solution with the oil and fat is thus cooled again after breaking the emulsion. It turns out that: - d ^'hese cooling at the flocculation of the previously emulsified oil and fat does not change. However, this cooling makes it possible to put the degreasing solution contaminated with oil and fat on a fine filter, for example an activated carbon filter. 1 which virtually completely removes the oil and fat from the degreasing solution. It has been shown that a significant part of the other impurities ⁵ contained in the used degreasing solution are separated with the oil and fat. At the elevated temperature of 80 ° to 100 ° C, the filter effect would deteriorate significantly, so that an impermissibly large proportion of the oil and fat would pass through the filter. The degreasing solution which has been largely freed of oil and fat is then adjusted to the desired composition by replacing the used components, in particular the emulsifier. The cleaned and re-adjusted degreasing solution thus obtained is fed back to the degreasing system 5. This saves degreasing solution. The degreasing solution is not drained into the sewage system after the oil and fat have been removed. _ This significantly reduces the disposal problems.

Embodiments of the invention are the subject of the claims.

Two exemplary embodiments of the invention are explained in more detail below with reference to the associated drawings.

Brief description of the drawings

1 shows schematically a degreasing system with a degreasing bath and a device for

Cleaning used degreasing solution and

Recycle this degreasing solution to that

Degreasing bath.

3.5 Fig. 2 shows a modified version. Preferred embodiments of the invention

10 denotes a degreasing bath in which there is a degreasing solution 12. The degreasing solution is usually an aqueous solution that contains an emulsifier in addition to other components. This is a substance which is able to bind oil and fat in an emulsion in the degreasing solution. This degreasing bath is used to free parts of adhering oil and fat, for example to prepare the surfaces of these parts for a subsequent electroplating process. In this way, the degreasing solution 12 takes a considerable amount of time. Share of oil and fat in emulsified form. The degreasing effect of the degreasing solution 12 becomes increasingly worse as a result.

A pump 14 therefore draws degreasing solution out of the degreasing bath via a line 16. The flow path 18 of the extracted degreasing solution contains a heat exchanger 20. The heat exchanger 20 has a first flow channel 22 and a second flow channel 24. The flow channels 22 and 24 are in close heat-exchanging contact with one another. The flow channel 22 connects downstream to the line 16. The outlet of the 26 flow channel 22 is connected to the inlet 28 of a heating device 30.

The heater 30 _. contains a container 32. The container 32 is surrounded by thermal insulation 34. A heater 36 in the form of a heating element sits in the container 32. A sensor 38 detects the temperature of the degreasing solution within the container 32. The signal from the sensor 38 is connected to a controller 40. The controller 40 controls the heater 36 so that ^" a temperature of the degreasing solution in the container between 80 ° C and 100 ° C is maintained. The volume of the container 32 and the delivery rate of the pump 14 are coordinated with one another in such a way that the heated degreasing solution remains in the container 32 for a minimum residence time and thus at the controlled temperature. This minimum residence time is chosen so that thermal breakage of the emulsion is ensured. A residence time of about 10 minutes has proven to be advantageous for this. However, the residence time does not exceed a maximum residence time after which the degreasing solution is changed by chemical reactions. However, this is a multiple of the minimum residence time mentioned.

The degreasing solution emerging from an outlet 42 of the heating device 30 then flows through the second passage 22 of the heat exchanger 20. As a result, the degreasing solution heated in the heating device 30 is cooled again. The ^" heat exchanger 20 acts as a cooling device for this heated degreasing solution. Two advantages are achieved in this way: First, the heated degreasing solution is cooled down again to, for example, 70 °. This is important for the filter process to be described. On the other hand, the degreasing solution is used before Preheated heating device, which saves heating power.

From the outlet 44 of the passage 24, the flow path 18 runs through a coarse filter 46, a conventional oil separator 48 and a fine filter 50. The fine filter 50 consists of a paper filter 52 and an activated carbon filter 54 connected downstream of it. The paper filter 52 is made from a band of highly effective filter paper educated. This band of filter paper is drawn off from a supply roll 54 by a motor 53 and wound onto a roll 56. Degreasing solution appears at the outlet of the fine filter 50 and is practically completely free of oil and fat. The fine filter removes oil and grease to a much greater extent than is possible mechanically with an oil separator. The oil separator 48 separates the oil or fat that has formed larger droplets that float to a layer and can be removed by an overflow. However, it has been shown that oil droplets still remain in the degreasing solution, which are not separated by a conventional oil separator even after the emulsion has broken. On the other hand, it has been shown that these "suspended oil droplets" become filterable after heating and re-cooling the degreasing solution and are retained by the fine filter. However, freed from the oil and fat degreasing solution contains no more emulsifier, as it has been destroyed the previous steps in ^•. This emulsifier is added again from a storage container 60 by a metering device 58. The metering device 58 is arranged in the flow path 18 downstream of the fine filter 50.

In the preferred embodiment shown, the pump 14 is located downstream of the metering device 58 in the flow path 18. The cleaned and re-adjusted degreasing solution is returned to the degreasing bath 10 via a line 62.

The arrangement described causes the degreasing solution to be cleaned as follows. Method: The degreasing solution is sucked into the flow path 18 by the pump 14 continuously or when a certain, predetermined degree of contamination of the degreasing solution 12 in the degreasing bath 10 is reached and, after appropriate treatment, returned to the degreasing bath 10. The aspirated degreasing solution is preheated in the heat exchanger 20 as it passes through the passageway 22. This is done by exchanging heat with the heated degreasing solution in the flow channel 24. The preheated degreasing solution is heated in the heating device 30 to a temperature of 80 ° C. to 100 ° C. It remains in the container 32 for a residence time of about 10 minutes at this temperature. The emulsion of oil and fat in the aqueous degreasing solution is broken. Droplets of oil and fat form. The degreasing solution is then cooled again to a temperature of, for example, 70 ° C. This cooling takes place in the passage 24 of the heat exchanger 20 ^′ by heat exchange with the degreasing solution which flows into the heating device 30. On the one hand, this results in a preheating of the degreasing solution which flows to the heating device and, at the same time, a re-cooling of the degreasing solution heated in the heating device 30. The cooled degreasing solution passes through the coarse filter 46. Coarse dirt, which could be present in the used degreasing solution, is removed by this coarse filter 46.

The degreasing solution then enters an oil separator 48. Such an oil separator 48 is known per se. The oil separator 48 alone is not able to remove the separated oil and fat from the degreasing solution to the required extent. However, it causes a "rough separation" of oil and fat, so that only that oil and fat reaches the fine filter that are not separated by the conventional oil separator can. This prevents the fine filter from clogging up and being consumed too quickly. The oil separator extends the life of the fine filter considerably. Since the costs of the filter materials are by no means negligible, this extended service life is an important factor for the economy of the process.

The degreasing solution thus "coarsely" freed from most of the oil and fat is then passed to the fine filter. Here, too, the upstream, relatively inexpensive paper filter 52 _ initially absorbs a considerable part of the "fine" residue of oil and fat. The gradual or continuous feeding of the paper filter prevents the paper filter from becoming clogged. The activated carbon filter 54 finally absorbs the last remnant of oil and fat. It results on

■ Output of the fine filter is largely oil and grease free

Degreasing solution. In this, however, the emulsifier is missing, while the remaining inorganic constituents of the degreasing solution are essentially still contained in the cleaned degreasing solution. The emulsifier is added by the metering device 58. The degreasing solution thus adjusted to the desired composition is then returned to the degreasing bath 10.

It is important that during cleaning the oil and fat are removed as completely as possible in one pass, so that the degreasing liquid needs to be pumped through the device as little as possible. The emulsifier is destroyed in each such run. This emulsifier must be added again. The quality of the filtering is therefore directly related to the consumption of emulsifier. The design according to Fig. 2 is constructed similarly to the design according to Fig. 1. Corresponding parts are provided with the same reference symbols in both figures.

In the embodiment according to FIG. 2, the cooling device is formed by a first heat exchanger 64, in which a heat exchange takes place between the heated degreasing solution and a second liquid. The second liquid serves as a coolant here. A second heat exchanger 66 is provided upstream of the heating device 30 between the heating device and the degreasing bath 10. In this second heat exchanger 66, heat is exchanged between the degreasing solution to be heated from the etching bath 10 and the sawn-off second liquid. The two heat exchangers 64 and 66 are related to. the second liquid is switched into a circuit. The outlet 68 of the heat exchanger 64 is connected to the inlet 70 of the heat exchanger 66. The outlet 72 of the heat exchanger 66 is connected to the inlet 74 of the heat exchanger 64. A pump 76 circulates the second liquid in this circuit. This removes heat from the ■ heated degreasing solution in the heat exchanger 64 and cools the degreasing solution again. This heat is transferred to the second liquid and is released in the heat exchanger 66 to the degreasing solution to be heated. This degreasing solution to be heated is therefore preheated.

The cleaned and re-adjusted degreasing solution has a temperature of approximately 70 ° C. Since the degreasing solution 12 in the degreasing bath 10 usually has to be kept at an elevated temperature anyway, the cleaning device described serves at the same time to maintain this elevated temperature.

Claims

1. Process for cleaning used Eπtfettungs¬ solution from a degreasing plant of emulsified oil and fat, in which the used degreasing solution is heated to temperatures in the range from 50 ° to 100 ° - and then the oil and fat layer separated by the heating a residual solution is separated off,

characterized by the process steps:

(b) then re-cooling the heated ones

Degreasing solution,

(c) filtering the cooled degreasing solution through a fine filter (50) to separate oil and fat,

(d) Adjustment of the residual solution thus obtained to the respectively desired composition of the degreasing solution and

(e) returning the cleaned and re-adjusted degreasing solution to the degreasing system. l 2. The method according to claim 1, characterized in that the re-cooling of the heated Entfettungs¬ solution is carried out by heat exchange with the not yet heated degreasing solution, whereby these ⁵ degreasing solution is preheated.

3. The method according to claim 1 or 2, characterized gekenn¬ characterized in that the cooled degreasing solution before filtering through the fine filter (50) by a

10 oil separator (48) is passed.

4. The method according to claim 3, characterized in that the cooled degreasing solution before being introduced into the. oil separator (48) through a

15 ^• Coarse filter (46) is passed.

5. The method according to claim 1, characterized in that the heated and again cooled Entfettungs¬ solution for fine filtering through a paper filter (52)

2.0 and then passed through an activated carbon filter (54).

6. Device for cleaning used degreasing solution to carry out the method

25 according to claim 1, containing

(a) a heating device (30) for heating the used degreasing solution and

30 (b) means for removing oil and fat which is separated from the heated degreasing solution after the emulsion is split,

35 characterized in that

(c) the heating device (30) is followed by a cooling device (24) for re-cooling the heated degreasing solution,

(d) a fine filter (50) for the degreasing solution to be cleaned is arranged downstream of the cooling device (24) in the flow path (18),

(e) downstream of the fine filter (50) are means (58, 60) for adding used or destroyed parts of the degreasing solution by the cleaning and

(f) the flow path (18) is returned to the degreasing system.

7. The device according to claim, characterized in that the cooling device is part of a heat exchanger

(20), by means of which there is a heat exchange between the degreasing solution to be heated by the heating device (30) from the degreasing system and the heated degreasing solution leaving the heating device (30).

8. The device according to claim 7, characterized in that

(a) the cooling device (24) is part of a heat exchanger (20) which contains a first flow channel (22) and a second flow channel (24) in heat-exchanging contact with one another, (b) the first flow channel (22) is arranged in a flow path (18) of the degreasing solution to be cleaned between the degreasing system and the heating device (30),

(e) the second pass anal (24) in the flow path (18) of the degreasing solution to be cleaned is arranged downstream of the heating device (30).

10

9. The device according to claim 7, characterized in that

(a) the cooling device has a first heat exchanger

15 contains, by means of which heat is exchanged with a second liquid serving as a cooling medium,

(b) a second upstream of the heater

20 heat exchanger is arranged, from the degreasing solution to be heated from the

Degreasing system flows through and in which a heat exchange with said second liquid takes place, and

25

(c) a pump is provided, by means of which a circulation of the second liquid between the first and the second heat exchanger can be generated. aα

10. The device according to claim 6, characterized in that an oil separator (48) is connected upstream of the fine filter (50).

35 ¹ 11. The device according to claim 10, characterized in that the oil separator (48) is preceded by a coarse filter (46).

⁵ 12. Device according to one of claims 6 to 11, characterized in that the fine filter (50)

Paper filter (52) and downstream of this contains an activated carbon filter (54).

° 13. The device according to claim 12, characterized in that the paper filter (52) is formed by a band of filter paper which can be unwound from a supply roll (55) and advanced over a filter cross section. 5

14. Device according to one of Claims 6 to ^'13, characterized in that

(a) the heating device (30) contains a heated container 0 (32) in which the one to be heated

Degreasing solution is kept at a controlled temperature by a temperature controller (40), and

-5 (b) the degreasing solution is conveyed through the container (32) by a pump (14) at such a conveying rate that the minimum residence time required for breaking the emulsion does not fall below and the maximum residence time 0 is not exceeded.

5