DE2051439A1 - - Google Patents

Description

Minnesota Mining and Manufacturing Company, Saint Paul,

Minnesota 55101 (V.St.v.A.)

Method and device for removing oil from aqueous liquids

The invention relates to a method for removing and Separation of oil from water and a device to be used in this process.

The invention relates in particular to the use of a vessel which is at least in part made of a fibrous material and consists of a means, which is the materia} in which Carrying out the deposition. The material is oleophilic and preferably absorbs oil but not water. After complete saturation of the fibrous material causes the hydrostatic pressure in the saturated material that the oil appears on the inside of the material. The material can be used together with a frame not only to remove oil from

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an oil-water mixture but also for collecting of the oil, for which purpose the vessel formed by the fibrous material is simply emptied.

The invention provides a particularly useful device for removal of oil from aqueous solutions of .Nahrungsmitteln or their byproducts before "> With the device according to the invention may eg grease or greasy layers of soups, gravies, etc. · easily removed _e The device can also used for industrial purposes are e.g. for removing oil stains on bodies of water.

The term used in the present description. "Oil" is said to be the one in the Hackh 'Chemical Dictionary . Third edition . "Blackiston Company, Inc., JNew York, Toronto, 1953. The term" oil ", however, is not limited to the group of compositions that are liquid at room temperature. The term" oil "is intended to include those at tree temperature solid oleophilic materials, which correspond to the definition in the above dictionary. At extremely high temperatures the polymeric material can be decomposed or substantially weakened, oils which are feet at such temperatures, therefore, cannot be separated with the device according to the invention.

Numerous well-known methods and devices for separating oil were indeed effective of water, but particularly W inefficient and relatively expensive and cumbersome out by. As is well known, soups, broths or gravies can be cooled in order to curdle the fat on the surface, which is then skimmed off, and attempts have been made to separate the oil by the blotting paper process, with the oleophilic surface in contact with a sheet of the material is brought, which then absorbs certain amounts of the oil. As far as the applicant is aware, no method has been described so far with which a separation and recovery of oils from an oil-water mixture can be carried out as easily and effectively as with the method according to the invention. It is just

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required, the mixture with the vessel according to the invention or Bringing the container into contact so that the vessel can fill, after which the vessel is emptied either by hand or mechanically and the physically and chemically unchanged oil can be collected.

The preferred embodiment of the invention consists of a pliable fibrous material and a frame supporting the material to which are attached plague holding means attached to attack at least part of the material, while the remaining part of the material forms a container for the oil. In the embodiment shown in the accompanying drawing the Feathalthaltermittel consists of a hinged to the frame Link that is folded down onto the frame.

In the accompanying drawing are the

Figure _e 1 and 3 diagrammatic representations of the frame 7 and the second member 6 and arranged between these components fibrous material, while the

Figo 2 and 4 vertical sections through the inventive Show device and the position of the device in an oil-water mixture after the material has a much of the oil hate absorbed

Fig. 3 shows a diagram of the opened Device according to the invention prior to the insertion of the material 10.

In preparation for the use of the device, the material 10 is attached around the base 12 and that on the frame 6 Bridging link 8 put around. Thereafter, the plague holding member 7 is pivoted around to hold the material at the point 14. Thereafter, the releasable locking means 4 is passed through the opening 16 on the frame 6, the lip 5 on the strip 15 of the opening 16 rests · The material is now on Device attached and ready for use as shown in FIGS. The device is then operated using the handle 2 immersed in an oil-water mixture, as shown in Pig «4, and the material is then prewetted with oil or not, depending on the paser used, with the deposition

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is initiated "

In the preferred embodiment of the device there is a locking means is provided by means of which the material is pinched between the hinge and an articulated member can, which serves as a pest control agentο It can also be desired be to support the container on the inside or outside by other members that the opposite sides of the container bridge. In the illustrated embodiment, a base is provided from which the bridging members attached to the frame come off so that the bottom of the container made of a fibrous material is supported. Y / ird the If the container is larger, the inner and possibly the outer support must of course be increased.

Although, according to the representation in the figures, the Eesthalteglied is movable, this is not absolutely necessary. The link can, for example, be made of paper or a similar material exist and have open areas into which the fibrous material has been inserted. The paper can also be the fastening means represent, or this can consist of the same material that is used to reinforce the container material is used ο

For the implementation of the method according to the invention Suitable fiber-forming materials are preferably composed of materials derived from the oil of an oil-water mixture t be wetted to the extent that the water from the cavities of the material is repelled, but the oil is retained. Although not all fiber-forming materials are used for this purpose however, it has been found that a wide variety of fiber-forming materials are suitable is effective within the scope of the invention »These, normally polymeric materials, when immersed in a Oil-water mixture that the oil the water from the smooth The outside is displaced and forms a contact angle with the outside that is smaller than 90 °. The effectiveness of the fiber-forming Materials is inversely related to size

r
of the mentioned contact angle. All materials to be preferred

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Polypropylene and polyethylene are listed, since with these materials the oil has a contact angle of essentially 0 ° can form. The surface energy parameters for the components of the particular system (which is made up of the combination of Water, oil and the fiber) are known or can be determined by methods known per se »

To determine the functionality of a particular fibrous material within the scope of the invention, the following can be used Procedure to be applied »

First, the adhesive force (W ₀ ) becomes an oil / solid

(Fiber) interface calculated. Then the cohesive force (W) of the oil / v / water interface is calculated. To determine The following mathematical considerations may indicate the utility of the particular fiber-forming material for the purposes of the invention Relationships evaluated / grounded:

1) If W, - W »0, then in the presence of water

Etc

ser an essentially unlimited usage of the fiber-forming material with oil in the form of a smooth film, and is

2) '.Va - _o = 0, the oil has an essentially

lent uniform capillarity of the fiber-forming material an interruption of the water / solid (d »h» fiber) Intermediate area, being the capillary area wetted and the water is repelled *

M «a, W., W is greater than 1/2 of the Y / up to the value of W _rt

in the system under consideration, the fibrous material are considered suitable for the purposes of the invention. However, it must be taken into account that3 when choosing of the fibrous material, care must be taken that the material must not melt at the highest temperatures, that of the oil-water mixture during the removal of the oil may occur. The materials suitable for the purposes of the invention include polyolefin fibers, such as polypropylene, Polyethylene and their copolymers, poly-4-methylpentene, parylene and styrene polymers, as well as polyesters, polyamides and

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Polycarbonates.

The adhesive force (W _Q ) can be called the interfacial tension

el

between the water and the oil plus the interfacial tension between the water and the solid fiber-forming material minus the interfacial tension between the oil and the solid fiber-forming material. The cohesive force can be characterized as twice the interfacial tension between the oil and the water. These interfacial tension values can be calculated from the essential factors known from physical chemistry, for example from the dispersion forces of polar interactions with the surface energies of the components of the system. See: Contact An ^ Ie Wettability and Adhesion , Advances in Chemistry Series, Chapter 6, pp. 9y ff, American Chemical Society, Washington, DC, 1964. The fiber-forming materials suitable for the invention can be regarded as those materials which cooperate with one another in an oil-water system in such a way that the above conditions are met Process violently repel the water as cavities and retain the oil. Examples of fibrous materials exhibiting this relationship are polypropylene, polyethylene, polytrifluoroethylene and polytetrafluoroethylene. The other formal, ie »

W - _c = 0 includes both the above-mentioned preferred ones Materials as well as the less preferred materials, i.e. those that are less hydrophobic. These, the requirements less sufficient materials can be pre-wetted with oil, so that in the process according to the invention be effective. Pre-wetting can be carried out by immersing it in oil • before assembling the device. Forms The oil has a separate layer on top of the water, so that the device is initially only in the oil layer for pre-wetting be immersed. With the less preferable materials

there is the possibility that the cavities contain some Waeser,

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if these materials are not pre-wetted with oil.

The sheets of material can be produced by various methods known per se, in particular by the method described in American patent specification No. ₀ 3 231 639 of Jan. 25, 1966. Hach this particular method, a thermoplastic material (for example, 400-450 ⁰ C for polyethylene) Not long heated for 1.5 minutes over the decomposition temperature of addition, as and for example, "pulled by means of a spinneret into filaments, said air streams to thin drawing the filaments and and rapid cooling can be used. Within the scope of the invention, the diameter of the threads and the density of the sheets of material can of course be varied slightly depending on the particular oil to be separated. For most uses, threads with a diameter of 0.1 microns to ^ bO microns have been found suitable, while the density of the material, expressed as a percentage of the fiber density, should be 2 to and preferably 4 to 35 o For a given fiber diameter Of course, the density of the material affects the rate at which the oil is absorbed from a given mixture. For a special purpose, the most favorable density for the oil absorption must of course be matched to the required strength of the material sheet. Should ZoB. If the device according to the invention is used for separating oil in a deep vessel, a material with a high fiber density and / or a device must be used that does not allow the material to float in great depths of the mixture.

For degreasing liquid foods iJaterialblätter are commonly used whose fibers have a diameter of from 0.1 micron to about 100 microns, while the Llaterialdichte expressed as a percentage of the fiber density, "can be s. To 35 $ In said use is in 90 $ of the fibers are 1 to about 11 microns in diameter, while the preferred density, expressed as a percentage of the fiber density, is 4 bxs about 10. Although the specifications of the material used must of course correspond to the particular purpose, it has nevertheless been shown that

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that the values given above are suitable for most foods »

A container with a a fibrous sheet of material produced during the deposition system comprising the fibrous material and a water-insoluble oil in an aqueous medium. With the absehe mentioned i dation system is the adhesive force for the system as a whole greater than half to the full value of the cohesive force for the oil-water part of the system. In the system mentioned, there is also the oil with the smooth surface of the fiber-forming material formed contact angle less than 90 ° e Mach the formation of the system, the material is by Ab- " sorption with oil is essentially saturated. Then the oil is under the action of the hydrostatic pressure in the Container pressed in.

For aesthetic reasons, the device according to the invention will preferably float on the surface of the oil-water mixture Left As the oil is absorbed by the material, the device becomes heavier and slowly sinks in. laugh finished The part of the device located above the material sheet should only partially absorb above the surface of the liquid lie. The deeper the device swims in the mixture, the stronger the hydrostatic effect on the material as a whole Pressure, so that the oil in the loading) container flows in faster. The oil can be removed from the container without any special Difficulties are removed. Depending on the size of the container, it can either be picked up and emptied by hand or the container is emptied by a conventional pump.

For removing oil deposits on fairly large bodies of water or for other purposes where large areas are to be de-oiled, larger sheets of material can be used will. For this purpose, of course, the container must be better supported. A support for both the inside and the The outer part of the sheet of material can be attached when the device according to the invention is used in open waters, e.g. a lake or a feich is used. The skimming of the

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Oil can be continuously carried out using a vacuum pump that is attached to one or a group of containers »The pump can transfer the oil to a central container convey and increase the speed of the oil flow into the container as a result of the negative pressure generated. Even though the vacuum pump is also effective when the oil inlet into the Oil is immersed, it may be desirable to provide a sealed lid for the container that has only one opening for the inlet part of the pump a very large increase in the speed of the oil flow due to the negative pressure that initially sucks the oil into the container. The pump helps to increase the flow rate, before there is oil in the container. When using a vacuum pump, the container begins to fill up, without the material being completely saturated.

example 1

250 g of mineral oil were mixed with approximately 1500 milliliters of water at room temperature in a cylindrical glass vessel with a depth of 10 cm and a diameter of 19 cm. The viscosity of the oil was 15.6? / 18.14 centistokes at 37.7 ⁰ C. It is a sheet-like material made of polypropylene microfibers was used with a expressed as a percentage of Paserdichte density of 9 $ where $ 90 of the fibers having a diameter from 1 to 11 microns "The dimensions of the Laterialblattes were 10.16 χ 10.16 cm while the weight was 1.35 g. The sheet of material was anchored in a device as shown in the figures. In the machine, the sheet of material formed a container 7.62 cm in diameter and 3.81 cm deep. The container was then lowered into the oil and water mixture and floated on the surface of the mixture. The oil penetrated the fibers to the inside of the container while the water was retained. After about 15 minutes awake, most of the oil appeared to be removed from the mixture. The amount of oil collected and removed was 238 g, while the microfiber material contained 10 g of oil. The total amount of η oil removed from the mixture was therefore 248 g or 99.2 $ of the oil originally present.

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Example 2

200 g of exuberant Hinder suet 3000 milliliters of water at a temperature of 37.7 ⁰ G in a metal pot with a diameter of 15.2 cm and a 'k fiefe of 0.3 cm mixed with about!. The mixture was kept at a temperature between 87.7 and 3.3 ° C. A sheet of material made of polypropylene microfibers with the dimensions 10.16 cm × 10.16 cm and a weight of 1.3 s was attached to the device described in Example 1. The density of the microfibers, expressed as a percentage of the fiber density, was 6.8 microns while the diameter of the fibers was 1 to 5 microns. The device was then immersed in the fat / water mixture, the beef fat penetrating through the fibers to the inside of the container while the water was retained. The device was then periodically drained when the O level was 1.27 to 1.5 cm from the top of the jar, after 45 minutes most of the oil appeared to have been removed from the mixture. The amount of fat collected was 186 grams while the material contained 12 grams of fat. So 198 g, or 99%, of the fat was removed from the mixture.

Example 3

In the device according to the invention, the material was after Example 1 used together with the fat-water mixture according to Example 2. The same procedure was followed, and the The amount of fat collected was measured after 10 minutes. 195 g of fat were deposited, which is $ 97.5 of the original existing Fettea.

Example 4

200 g of white mineral oil (viscosity from 15.67 to 18.14 centistokes and having a temperature of 83.3 ⁰ O) was mixed with 100 g of water in a high intensity mixer, until a homogeneous suspension was produced. This suspension was poured apparatus used in the two preceding Beispulen which had a depth of 6.35 cm and a diameter of 87.62 cm. The material consisted of polypropylene microfibers measuring 20.3 x 15.2 cm and weighing 5.2 g.

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In the pot L'L, 91 g of the suspension charged, d "h" 97 β "wetter and 195 grams of mineral oil Lur the oil penetrated the parsers are;.. IS Cl was collected in a metal cup" The lüeiige the collected after 10 Linuten oil "was 169, bg or 97» ü $ of the oil originally available.

Examples 5-10

In the examples below, the features of the various other fibers are described, which are used for performing the process of the invention ₀ belongs on the materials used toylon to those materials which have to be soaked with oil before use. In the present case, the oil was immersed in the oil layer, and the oil layer itself caused the pre-soaking. For certain uses where, for example, _e flexibility, heat resistance, shear strength, etc ₀ of particular Hutr: his are en, some fibers that require pre-wetting with oil before use, preferable, and as can be seen from the table below are still very large amounts of oil removed from these fibers, especially when compared to other separators currently available. In all of the examples below, 1500 milliliters of water and 3/4 g of oil were poured into a cylindrical glass vessel with a depth of 10 cm and a diameter of 19 cm. The device according to the invention was then immersed in the mixture, as described in the preceding examples, the fibers listed in Examples 5-10 being used for the material. The results of these tests are summarized in the table below.

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, ·.
Beep . Paser Material- T 8 ⁰ O determined FIG E. remove » 75 to the Art in the examples 5-10 temperature 1 density in diameter weight total t oil > 96 Dist. of of ro $ the pa at least $ 90 of the Ma lot in $ 81 Trains Oil Mixture 1 density the Pasern material of 98 permit in leaf removed. exceptionally 67 at least micron 10.6 χ Oil in el, pr.öls 90 10.6 cm of the 151.7 84 in the pa 192.4 98 * Gram 161.9 80 ^{1 r}
co
CXJ 5 Polyethylene 9.15 # iy6.4 90 17th Pett 54.4 ⁰ C 2.0-20.0 2.2 134.9 91 35 is. ·> "Ns 6th Polyethylene 9.1596 179.8 97 15th mineral 21, O ⁰ C O ISJ
(- \ 2.0-20.0 2.15 167.6 23 oil cn OD 7th polyester 4,429έ 195.5 22nd Pett 51.6 ⁰ C .0 K> 1.5-15.0 1.3 160.5 35 OO 8th polyester 4.42 # 180.3 22nd mineral 21.0 ⁰ C CD 1.5-15.0 1.25 182.6 27 oil 9 JSyI on 5.51 # 193.6 15th Pett 51.6 ⁰ C 1.5-15.0 0.61 27 10 nylon 5.51 # 23 Mineral- 21, O ⁰ C 1.5-15.0 0.65 25th the viscosity in the examples previously described at of mineral oil became like: and pointed a temperature of 37 » 15 »67 / 18.4 centistoles. a value of

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Example 11

In this example, the use of the device according to the invention for solving a problem is described with the preparation and serving of many foods that contain solid oleophilic materials. vBerden such Cooked food, some substances contained in the food melt and enter the surrounding medium, e.g. in Soups, sauces or broths, which affect the taste and appearance of the medium.

To remove oil from such a product, the apparatus of the present invention for removing liquefied oleophilic substances was used in the preparation of fried meatballs. A sheet of polypropylene microfiber material measuring 10.16 10.16 cm and weighing 1.2 g was used in the device. The fibers were 1 to 10 microns in diameter while the density was 8.1 of the fiber density.

The sample was as follows zubereitetι Part of scraping or Haokfleischmenge was set aside for subsequent fat extraction, while the remaining portion Were you provided with the following additions for the preparation of a typical American "Hamburgers ¹ ·

Scraper or shark iron 810 g Vegetable juice V-8 610.4 g

finely chopped onions 35 ml

Spices 15 ml

(V-8 is a trademark of Campbell Soup Co. and the vegetable juice contains vegetable juices, salt, monosodium glutamate, vitamin 0 and flavorings, so essentially all of the oleophilic material in the mixture is derived from the meat).

The ingredients were poured into a 1/2 liter sauce pan and quickly brought to the boil. After heating for 15 minutes, the device according to the invention was placed in the Mixture used, with the boiling continued. | Yes

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After the container formed by the material had been filled with the oleophilic material, the container was emptied and the material collected. At certain times the olepphili-, see material was weighed and the relationship between d _; it determines the action, time and the amount of oleophilic material removed. In the table below are the results of this. Trials put together.

Total amount of fat removed in the relevant time period

Effective time in Minutes -. 5 _u ., J \ O - 9 Ul - 15 9 - 25th 15th - 40 25th - 55 40 - 60 55

21.4 22.6 20.9 18.4 12.5
4.6

From the table it can be seen that the removal of the fat is faster than initially in the course of the process later. In fact, the process with the inclusion of the oleophilic material contained in the material sheet becomes more than 60 # of the material removed after 15 minutes and more than 70 $ after 25 minutes. Removal of the fat from broths, soups and other completely liquid foods is done with the same Speed up at the beginning of the procedure and slow down until about $ 100 of the fat has been removed. After 60 minutes had elapsed, the device was removed and the sheet of material removed from the device and weighed in order determine the amount of oleophilic material contained in the material sheet. The material sheet contained 17 g> so that a total of 141.2 g of the oleophilic material had been removed.

D _a a scraping or minced unused was weighed and placed in a Soxhlet extraction apparatus. The oleophilic material was extracted with petroleum ether for 15 hours. Then the meat was removed from the device, again

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chopped and extracted for another hour, after which The meat was found to be $ 22.2 oleophilic material contained. The meat in the recipe therefore contained 178 g of oleophilic material, 79 of which was used in the process removed.

Although the percentage of fat extracted appears to be relatively small compared to the previous examples, it must be taken into account that some of the oleophilic material contained in the cockroach or minced meat is either physically or chemically bound to the meat and is not leached out by the sauce. In the sustained extraction process, however, essentially all of the oleophilic material contained in the sample is extracted. This means that the entire liquid phase of the oleophilic material, d _e h. a fraction of the sauce has been removed, and a close inspection shows that in fact all of the oleophilic material contained in the sauce has been removed

The examples described above do not represent any restriction on the possible uses of the invention The invention itself is therefore only delimited by the accompanying patent claims.

Claims

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Claims (1)

20SHlV Claims Device for separating oils insoluble in water from a mixture of the oils with an aqueous medium, characterized by a barrel for the oil, by a that Vessel-bearing frame, and through a Peethalteglied, to Attaching the vessel to the frame, and characterized in that at least part of the vessel consists of a fibrous The material sheet consists of putting the oil into the vessel ■., W ^- - ■ · ■■■■■■ · - ^; ~ '■■ ·; ■': "' ι *' can penetrate while water is returned. 2. Device according to claim 1, characterized in that the foot-holding element is hinged to the frame at one edge and can be releasably locked to the opposite edge of the frame * 3 · Device according to claim 1, characterized by bridging links, which promote the support of the vessel 4 · Device according to claim 5, characterized in that the Bridging links move away from a common base. 5. Device according to claim 1 ,. characterized in that the β the) frame should float on the water. 6. Apparatus according to claim 1, characterized in that the Pipes of the sheet of material have a diameter of 0.1 to 250 microns and a density of 2 to 65 $ .I as you can. 7. Apparatus according to claim 6, characterized in that the The diameter of the filaments does not exceed 100 microns. 8 · Product according to claim 6, characterized in that the density of the sheet of material is $ 2 to $ 25. 1 0981 7/2082 _ ₁₇ _ Product according to claim 6, characterized in that 90 $ of the lasers have a durometer of 1 to 11 microns, and that the laser density is 4 to 10 # 10o process for separating oils insoluble in water - from a G-emisoh of oils and an aqueous medium, characterized in that an oleophilisohes fibrous Vessel containing material in contact with the mixture is brought that the fibrous material forms together with the oil-water Gemisoh in system, in which the adhesive force for the system as a whole is greater than half to the full cohesive force for the oil-water part of the System, and that the contact angle formed by the oil and the fiber-forming material in an oil-water mixture is smaller than 90 ° is that the sheet of material is substantially saturated with the Ul, and that the vessel with the oil as a result of the hydrostatic druoke is filled, the rom ul after. an essentially complete saturation of the material sheet is produced 11 · The method of claim 1O ₉ characterized in that said contact angle is substantially 0 °. 12. Method according to claim 10, characterized in that the adhesive force is essentially equal to the cohesive force but is not smaller than this 10981 7/2082 Blank page