The present invention relates to meshes for oil-water separation comprising a surface comprising hydrated aluminium oxides, in particular γ-ΑΙΟΟΗ thereby providing hydrophilic properties to the surface of the mesh. The invention furthermore relates to a process for manufacturing such mesh by coating an uncoated mesh with aluminum or aluminum oxide and converting such coating to hydrated aluminum oxide. Furthermore, the invention relates to the use of such mesh for oil-water separation.

Oil-water separation is a worldwide challenge. Typical separation problems comprise the separation emulsions of crude oil and (formation) water, the separation of industrial oily waste water or separation in connection with the removal of oil spills. It is known in the art to separate oil-water emulsions or other oil-water mixtures by the addition of chemical additives such as demulsifiers and/or deoilers. Examples of such demulsifiers are disclosed for instance in EP-A 0 264 841 , EP-A 0 499 068 or

EP-A 0 267 517. It is furthermore known to use materials which are capable of selectively absorbing organic solvents, including but not limited to oils. Examples comprise open-cell foams based on a melamine-formaldehyde modified with a hydrophobic coating such as disclosed in

WO 2007/1 10361 A1 or WO 2008/107439 A1. J. K. Yuan, X. G. Liu, O. Akbulut, J. Q. Hu, S. L. Suib, J. Kong, F. Stellacci, Nat. Nanotechnol. 2008, 3, 332 disclose superwetting nanowire membranes for selective absorption. Such membranes are obtained by coating nanowire membranes with silicones.

It has also been suggested to use meshes for separation of oil and water. L. Feng, Z. Y. Zhang, Z. H. Mai , Y. M. Ma, B. Q. Liu, L. Jiang, D. B. Zhu, Angew. Chem. 2004, 116, 2046; Angew. Chem. Int. Ed. 2004, 43, 2012 disclose a super-hydrophobic and super-oleophilic coating mesh film for the separation of oil and water. The coating is peformed by using a homogeneous emulsion comprising 50 % by wt. of water, 30 % by wt. of polytetrafluoroethylene (teflon), 10 % by wt. of polyvinylacetate as adhesive , 8 % by wt. of polyvinylalcohol as dispersant 2% dodecylbenzenesulfonate as surfactant. As shown in the cited document drops of water remain on the mesh and do not pass it while drops of diesel oil flow through the mesh.

However, the described hydrophobic/oleophilic oil-removing materials are easily fouled or clogged by oils. Thus the separation efficiency is drastically reduced after a limited number of uses. Additionally, adhered oils are hard to remove which results in secondary pollution during this cleaning process as well as in a waste of both oil and oleophilic material. Z. Xue, S. Wang, L. Lin, L. Chen. M. Liu, L. Feng and L. Jiang, Adv. Mater. 2011, 23, 4270 - 4273 report about the manufacture of a superhydrophilic and underwater superoleophobic hydrogel-coated steel mesh for oil-water separation. The steel mesh was coated with a radiation curable, aqueous composition of acryl amide, Ν,Ν'- methylene bis acrylamide as crosslinker, a photoinitiator and high molecular polyacrylamide (M _n = 3,000,000 g/mol) as adhesive agent and the coated mesh was cured with UV-light. The netting described has the opposite separation characteristics than the netting described by L. Feng et al. A drop of water can pass through the netting while oil remains on the netting. Such materials have the advantage that they are easy to clean, the equipment is reusable, the oil-phase can be processed after separation and the equipment is protected from oil-fouling. However, the polyacrylamide coating described by Xue et al. suffers from a lack of efficiency and stability with respect to the separation of crude oil - water emulsions. Our tests showed that a mesh coated in the manner described separated hexane-water mixtures but did not separate sufficiently crude oil - water emulsions.

W. Zhang, Z. Shi, F. Zhang, X. Liu, J. Jin, and L. Jiang, Adv. Mater. 25, 2071 - 2076 disclose superhydrophobic and superoleophilic PVDF membranes for effective separation of water-in- oil emulsions with high flux. For the water-in-oil emulsions tested petroleum ether, toluene, isooctane and dichloromethane were used as oil phase. Emulsions of crude oil and water were not tested.

P. Kim, M. J. Kreder, J. Alvarenga and J. Aizenberg, Nano Lett., 2013, 13 (4), pp 1793-1799, disclose the use of γ-ΑΙΟΟΗ (Boehmite) with infiltrated perfluorated solvents to achieve an omniphobic surface. The publication does not disclose coating meshs and their use for oil- water separation.

It was the objective of the present invention to provide improved coated meshes being hydrophilic and oleophobic which also show good results in the separation of crude oil - water emulsions.

Correspondingly, in a first aspect the present invention relates to a mesh for oil-water separation comprising a surface comprising hydrated aluminumoxide, preferably γ-ΑΙΟΟΗ. In a second aspect the invention relates to a method of manufacturing such mesh wherein the method at least comprises the following steps:

(1 ) Coating a mesh with aluminum or aluminum oxide, and

(2) converting the aluminum or aluminum oxide coating into hydrated aluminum

oxides by treating the coating with water or water vapor at a temperature above room temperature.

In a third aspect the invention relates to a mesh available by such a process. In a fourth aspect, the invention relates to a process for manufacturing such mesh, wherein a mesh made of aluminum is used as starting material followed by converting the surface of the mesh into hydrated aluminum oxides by treating the mesh with water and increasing the temperature to more than room temperature.

In a fifth aspect, the invention relates to a mesh available by such a process.

In a sixth aspect, the use of such mesh for oil-water separation has been found.

List of figures:

With regard to the invention, the following should be stated specifically:

The mesh to be used for oil-water separation according to this invention comprises a surface comprising hydrated aluminumoxide. "Hydrated aluminium oxides" include

aluminiumoxyhydroxides, such as a-AIOOH or y-AIOOH having a defined crystalline structure but also aluminumoxyhydroxides having a less defined structure, i.e. products being amorphous or having at least amorphous portions. "Hydrated aluminum oxides" may comprise besides aluminium ions also other metal ions such as for instance ferric ions being understood that usually at least 90 mol % of the metal ions present are aluminum ions.

Preferably, the surface of the mesh comprises γ-ΑΙΟΟΗ which is also known as Boehmite.

The thickness of layer of hydrated aluminum oxides on the surface of the mesh typically may be 50 nm to 500 nm, preferably 100 nm to 200 nm. The mesh according to the invention may be made by converting the surface of an aluminum mesh to a surface comprising hydrated aluminum oxides or by coating a mesh of another material, for instance a mesh of stainless steel with aluminum or aluminum compounds such as aluminum oxides and converting the coating to hydrated aluminum oxides. Mesh used for coating:

For manufacturing the coated mesh an uncoated mesh is used as starting material. Any suitable material for the mesh may be selected. Examples include meshes made of metals such as steel, stainless steel, bronze, brass, or aluminum or meshes made of polymeric materials such as polyethylene, polypropylene, polyacrylamide, or polyethersulfone. In one embodiment of the invention metals, preferably stainless steel is selected as material for the mesh. The mesh may comprise wires or fibers which are arranged as a net but of course also other types of mesh may be used such as sheets with openings, e.g. openings stamped into the sheet. The latter method has the advantage that also openings having irregular shape may be used which may be difficult when using wires. If the mesh comprises fibers and/or wires, such the fibers/wires of the net may have a thickness of 0.02 to 0.2 mm, for instance 0.03 mm to 0.1 mm.

The mesh and the geometry of the openings in the mesh used may be chosen by the skilled artisan according to his/her needs, for example in a tetragonal, hexagonal or octagonal manner or a combination of two or more than two geometries. Examples of tetragonal openings include squares, rectangles or parallelograms. Other shapes include circles, ovals, star-like openings or openings of irregular shape.

The mesh size may be chosen by the skilled artisan according to his/her needs. In particular, the mesh size may be from 10 μηη to 100 μηη, for example 50 μηη to 70 μηη. Said number relates to the longest straight distance from one point along the border of the opening to another point along the border of the same opening. Bye the way of example it may be the diagonal in a square, the long diagonal in a rectangle or the diameter of a circle. Should the mesh comprise different openings, the number relates to the arithmetic average.

Surface modification

By modifying the surface of an unmodified mesh a surface-modified mesh comprising a surface comprising hydrated aluminumoxide, preferably γ-ΑΙΟΟΗ is obtained. The modified surface provides hydrophilic, preferably superhydrophilic properties to the mesh thereby rendering it suitable for oil-water separation. The term "superhydrophilic" means that the contact angle for an oil is > 150° while the contact angle for water is < 5°.

In a first embodiment of the invention a mesh as described above is coated with aluminum or aluminum oxide. Any technology for coating may be used. Examples of suitable coating technologies include physical vapor deposition methods such as thermal evaporation, sputtering, electron beam evaporation techniques, or CVD technologies. Such techniques are known to the skilled artisan and are for example disclosed in Mahan, John E. "Physical Vapor Deposition of Thin Films" New York: John Wiley & Sons, 2000; Dobkin and Zuraw (2003) "Principles of Chemical Vapor Deposition"; or or Kluwer, Smith, Donald (1995) "Thin- Film Deposition: Principles and Practice" McGraw-Hill. The thickness of the layer of aluminum or aluminum oxide is selected by the skilled artisan according to his/her needs and usually is from 50 nm to 500 nm, preferably 100 nm to 200 nm.

Layers of aluminum /aluminum oxide may also coated onto the mesh by sol-gel methods followed by thermal treatment. Also such techniques are known to the skilled artisan and are for example disclosed in C. Jeffrey Brinker, George W. Scherer (Hrsg.) "Sol Gel Science.

The Physics and Chemistry of Sol-Gel Processing. The Physics and Chemistry of Sol-gel

Processing", Academic Press, Boston (1990) or Kim, Philseok; Kreder, Michael J.;

Alvarenga, Jack; et al. NANO LETTERS Volume: 13 Issue: 4 Pages: 1793-1799 Published: APR 2013.

Optionally, the uncoated mesh may be precoated with an adhesion layer. Such an adhesion layer may be a layer of Cr or Ti which also may be applied by using by physical vapor deposition methods but also layers of other oxides may be possible. The thickness of such an additional coating may be from 1 to 20 nm, for example 3 to 10 nm.

The material of the uncoated mesh to be modified according to this technology may be any material. Preferably, the material of the uncoated mesh is selected from steel, stainless, steel, bronze or brass, in particular stainless steel. The mesh size may be chosen by the skilled artisan according to his/her needs. In particular, the mesh size may be from 10 μηη to 100 μηη, for example 40 μηη to 60 μηη. Further details of the unmodified meshs to be used have been described above and we explicitly refer to the description.

In an additional step following the coating with aluminum or aluminum oxides the coating is converted into hydrated aluminum oxides, preferably γ-ΑΙΟΟΗ, by treating the coating with water, preferably deionized water, or water vapor at a temperature above room temperature, preferably more than 50°C and more preferably more than 95°C. In one embodiment the coated mesh may be put into boiling water. The duration of the treatment with water is selected by the skilled artisan according to his/her needs and may be from 10 to 40 min, preferably 15 to 30 min.

The thickness of the layer of hydrated aluminum oxides on the surface of the mesh usually is from 50 nm to Ι μηη, preferably 100nm to 500 nm.

The present invention also relates to a mesh comprising a surface comprising hydrated aluminum oxides, in particular a surface comprising γ-ΑΙΟΟΗ which is available by the method of the first embodiment described above. In a second embodiment of the invention an aluminum mesh is used as starting material. The mesh size may be chosen by the skilled artisan according to his/her needs. In particular, the mesh size may be from 10 μηη to 100 μηη, for example 40 μηη to 60 μηη. Further details of unmodified meshes to be used have been described above and we explicitly refer to the description. The surface of the mesh is converted into hydrated aluminum oxides, preferably γ-ΑΙΟΟΗ by treating the mesh with water at a temperature above room temperature, preferably more than 50°C. In one embodiment the aluminum mesh may be put into boiling water for about 10 to 40 min, preferably 15 to 30 min. The present invention also relates to a mesh comprising a surface comprising hydrated aluminum oxides, in particular a surface comprising γ-ΑΙΟΟΗ which is available by the method of the second embodiment described above.

Use of the surface modified meshes for separating oil-water separation

The meshes according to the invention may be used for oil-water separation.

The term "oil" as used herein encompasses any kind of organic liquids which form emulsions with water. Examples of oils include hydrocarbons, such as aliphatic and/or aromatic hydrocarbons, in particular hydrocarbons having a boiling point of more than 150°C, crude oil, mineral oils such as diesel oil, gasoline, heavy fuel oil, engine oil, vegetable oils such as coconut oil, tall oil or rape oil, or synthetic oils such as silicone oils. In one preferred embodiment? the oil is crude oil. The term water-oil mixtures shall include any kind of mixtures of oil and water comprising an oil phase and a water phase, including but not limited to oil-water emulsions or water-oil emulsions, in particular emulsions of crude oil and water such as formation water.

Examples of specific water-oil separation processes include separation processes in course of oil production and oil refining, such as the separation of emulsions of crude oil and water produced from an oil bearing formations, the separation of heavy oil emulsions from oil sands tailings or heavy oil emulsions obtained from SAGD techniques, de-oiling of water, oil sludge dewatering or the removal of hydrocarbons from drilling fluids. Further examples comprise the separation of oil-water mixtures from tank bottoms at refineries or other storage facilities, collections points for disposable waste oils, waste from chemical factories, ballast water or the removal of oil spills.

In one preferred embodiment of the invention, the oil-water mixture to be separated is a mixture of crude oil and water, in particular an emulsion of crude oil and water. In order to separate oil-water mixtures according to this invention the oil-water mixture may be pressed against a mesh. The force applied may simply be gravity forces but of course also pressure may be applied. Due to the (super)hydrophilic surface properties of the coated mesh, water may pass through the mesh while the passage of oil through the mesh is impeded so that at least part of the oil is retained on the mesh and may be removed from the mesh.

In one embodiment of the invention for the separation of oil-water mixtures a separating device is used which a least comprises: a first chamber at least comprising an inlet for fluids and an outlet for fluids, wherein the first chamber is connected with a second chamber at least comprising an outlet for fluids and wherein furthermore a coated mesh according to this invention separates the first chamber from the second chamber. In a preferred embodiment the device is a device for cross-flow filtration.

For separating oil-water mixtures using the device described, the oil-water mixture to be separated is allowed to flow into the first chamber. A suitable pressure selected by the skilled artisan may be applied. Water or at least part of the water of the oil-water mixture passes through the mesh into the second chamber and may be recovered from the second chamber from the outlet of the second chamber. Oil or an oil-water mixture with decreased water content may be recovered from the outlet of the first chamber. The process may be continuous or discontinuous. In a preferred embodiment the process is a continuous cross- flow filtration.

If one separating step is not sufficient to separate oil and water completely the separation step may be repeated using the same or another device. For example for separating a cascade of two or more of the devices described successively assembled may be used.

In one further embodiment a separator for the separation of crude oil and water may be used which is equipped with meshes according to the present invention. A schematic

representation of such a separator is shown in figure 2. The separator is a cylinder shaped hollow body which at least comprises an inlet for an oil-water emulsion, an oil bucket for separated oil, outlets for separated water and separated oil and furthermore a mist extractor and an outlet for separated gas. Meshes may be incorporated vertically (1 a) or almost vertically (1 b) into the separator at a location close to the inlet for the oil-water emulsion. A mesh may also be incorporated horizontally. In such embodiment, the inlet for the oil-water emulsion is located above the mesh so that the emulsion may be separated into oil and water under the influence of gravity. In order to hold back oil spills a mesh may furthermore be used as water weir (3) and/or in the mist extractor (2). Of course the skilled artisan may use meshes in an oil-water separator in another manner.

Advantages of the present invention

Using the surface modified mesh according to the present invention has the advantage that it is not necessary to use demulsifiers for oil-water separation or it is at least possible to reduce the amount of demulsifiers and/or deoilers used. Without wishing to be bound by theory, it seems to be so that hydrated aluminum oxides, in particular Boehmite incorporates water and forms a hydrophilic water slip film on the surface in a wet state. The inorganic surface coating furthermore has the advantage that they are mechanically more stable than organic coatings of a mesh.

The invention is illustrated in detail by the examples which follow.

Manufacture of coated meshs

Example 1 :

A stainless steel metal grid 1 .4401 with square cells having a mesh size of 50 μηη and a diameter of the wire of 0,036 mm was used. Pieces with a size 5 cm x 5 cm were cut. The metal grid pieces were cleaned with acetone, deionized water and again acetone and dried with air.

The cleaned metal grid pieces were coated with 5 nm Cr (as adhesion layer) and 100 nm Al by thermal evaporation according to processes well known to the skilled artisan. Details are disclosed in K.S. Sree Harsha, "Principles of Vapor Deposition of Thin Films", Elsevier, 2006; R.GIang "Vacuum Evaporation", Handbook of Thin Film Technology, McGraw-Hill, NY, p 1 -130, 1970, I. A. Blech "Step Coverage by Vapor Deposited Thin Aluminum Films", Solid StateTechnology, p123, 1983 In a following step the Al layer was converted into aluminum oxyhydroxide by putting the coated grids into boiling deionized water for 30 min.

Comparative example 1 :

A stainless steel metal grid 1.4401 with square cells having a mesh size of 50 μηη and a diameter of the wire of 0,036 mm was used. Pieces with a size of 5 cm x 5 cm were cut. The metal grid pieces were cleaned with acetone, deionized water and again acetone and dried with air. In the next step, the cleaned metal grid piece was clamped on top of a 100 ml_ Schott glass bottle (GL 45 thread). The glass bottle with the metal grid on top were put upside down into the the coating solution disclosed below, thereafter removed and cured under UV-light (365 nm).

For coating, the hydrogel precursor solution described in Adv. Mater. 201 1 , 23, 4270 was used: 50 g acrylamide, 1 .5 g Ν,Ν ^' -methyl-bis acrylamid (crosslinking agent), 1.0 g 2,2 - diethoxyacetophenon (photoinitiator) and 0.5 g polyacrylamide, having an M _w of 2,000,000 g/mole (adhesive agent) were dissolved in 47 g deionized water and stirred for 45 min. To achieve best solubilities, PAM is dissolved as the first ingredient. Oil-water separation test

The coated grids were used for oil-water separation. The test apparatus is schematically shown in Figure 1 . A sample of the mesh (2) is fixed at the bottom opening of a vertical glass pipe (3) (length: 60 cm, diameter: 1 ,5 cm. Then 150 ml of the oil water mixture to be tested is poured into the glass pipe using a funnel and any solvent passing the mesh is collected using a beaker. The volume of organic phase that is not held back by the grid, i.e. collected in the beaker is measured. For each test mixture a fresh grid is used. Each test with a specific oil/water mixture and a specific grid was repeated three times with a freshly prepared grid. All tests were performed at room temperature.

The following oil-water test mixtures were used:

Hexane/Water 30 / 70 vol%

Toluene/Water 30 / 70 vol%

Hexane/Toluene/Water 24 / 6/ 70 vol%

Cooking (Thistle) oil / Water, 30 / 70 vol%

Heavy gasoline / Water, 30 / 70 vol%

Crude oil (oilfield in Northern Germany) / Water, 30 / 70 vol%

The water phase is colored blue for better visibility with methylene blue. Also emulsions of the mixtures were tested. They were prepared by vigorously shaking the corresponding 2- phase mixtures.

The percentage of oil phase (vol % relating to the total amount of oil used for the test) that is not held back by the grid and passes through the grid is listed in table 1. Since at least three reproduction experiments were performed per grid and per oil / water mixture a range is -if necessary- provided.

Table 1 : Percentage (vol%) of the oil phase of the tested oil/water mixtures that passes the corresponding grid. Blank boxes: no measurements were performed

Discussion

The separation efficiencies of the differently coated grids (see experimental part) for several oil-water mixtures and corresponding emulsions (see experimental part) were determined. Within this series of different oil-water mixtures, the mixture hexane-water is regarded as the one to be separated easiest while for the gasoline-water and especially crude oil - water mixtures separation is known to be much more challenging.

Comparative example C1 with a coating according to the state-of-the art performs best with a hexane-water mixture and there also is some separation efficiency with a hexane-toluene- water mixture. However, for crude oil - water mixtures, gasoline - water mixtures, thistle oil - water mixtures, and toluene - water mixtures no separation was possible.

The mesh coated according to the present invention with an AIOOH coating shows a significantly improved separation of oil and water for mixtures of gasoline and water and of crude oil and water.