Superhydrophobic and superoleophilic composite sponge material and the production method thereof

Abstract

The invention relates to a superhydrophobic and superoleophilic composite sponge material and the production method thereof. The material of the invention selectively removes petroleum-derived products, oily substances, and organic solvents in water. Additionally, said material has a high sorption capacity.

Description

[0001] SUPERHYDROPHOBIC AND SUPEROLEOPHILIC COMPOSITE SPONGE MATERIAL AND THE PRODUCTION METHOD THEREOF

[0002] Technical Field

[0003] The invention relates to a superhydrophobic and superoleophilic composite sponge material and the production method thereof. The material of the invention selectively removes petroleum-derived products, oily substances, and organic solvents in water. Additionally, said material has a high sorption capacity.

[0004] State of the Art

[0005] Today, petroleum-based products, various oils and toxic organic solvents are used in large quantities in various application areas, such as transportation fuels, fuels for heating and electricity generation, asphalt and road oil, as well as as raw materials for the production of chemicals, plastics and synthetic materials. However, various accidents, malfunctions, leaks or explosions that occur during the production, storage, distribution, refining or transportation of such substances have both economic and ecological effects. Cleaning petroleum derivatives, oily substances, and toxic organic solvents from aquatic environments such as seas, oceans or lakes requires high costs. These substances used in industry or at home not only harm potable water resources, but also cause the death of fish and plants living in the water. For this reason, rapid and effective cleaning of petroleum derivatives, oily substances and toxic organic solvents accumulated on the water surface is extremely important for a sustainable environment. In the state of the art, various oily substance-water mixture separation techniques, including in-situ combustion

[0001] , centrifugation [2], coagulation [2], filtration [3], sedimentation [4], flotation [5], sorption with biological materials [6] and sorption with chemical materials [7] are used to clean said substances. Although the in-situ combustion technique can be carried out at low cost, in order to use this technique, the thickness of the oily substance or organic solvent pollutant layer on the water must be at least 2-3 mm, and harmful gases are produced as a result of its use [8]. Traditional techniques such as centrifugation, coagulation and flotation are generally not preferred due to reasons such as not being effective enough in separating oily substance-water mixtures, having low oil-water separation performance, requiring high energy costs, and requiring complex separation devices. Apart from these, sorption technique is the general name given to the removal of a compound from the solution environment by a solid sorbent [9], the sorbent materials traditionally used in this technique include inorganic minerals such as vermiculite, zeolite and bentonite, natural fibrous materials such as corn cob, nonwoven wool and cotton fibers

[0010] and wood dust

[0011] . However, the oily substance or organic solvent sorption capacity of these sorbent materials is not very high (< 25 g / g), and for this reason, porous materials such as sponges, wire mesh, foam, fabric and airgel have been widely used in recent years as sorbent materials for the removal of petroleum-derived products, oily substances or organic solvent pollutants in water by sorption

[0012] , However, classical sorbent materials can sorb a small amount of petroleum-derived products, oily substances, and toxic organic pollutants, but since many of these sorbent materials are not sufficiently suitable for the regeneration process, they must be discarded after being saturated with pollutants up to their sorption capacity values. In addition, the degree of wettability of the sorbent materials used in the sorption technique against water or oil is one of the most important factors affecting the performance of these materials in the selective sorption of oily substances / organic solvents and the separation of oily substances / organic solvent-water mixtures. For this reason, it is desirable for the sorbent material to be used in the selective removal of petroleum-derived products, oily substances, and organic solvents from water to have superhydrophobic and superoleophilic properties.

[0006] In the state of the art, one of the chemicals used to prepare materials with superhydrophobic surfaces is alkyl chloro silanes. Since alkyl chloro silanes are very sensitive to humidity in the air, they can only be opened and used in special cabins under inert atmospheric conditions in studies on obtaining superhydrophobic surfaces. In normal air atmosphere, opening and using alkyl chloro silane compounds is extremely dangerous due to their toxicity. The most commonly used inorganic particles to obtain superhydrophobic surfaces are SiO2 nanoparticles with hydrophilic or hydrophobic forms, and the most commonly used silane compounds are alkyl silanes. Halloysite nanotube (HNT), which is abundant in nature and has a hollow cylindrical structure, is a good alternative in the preparation of superhydrophobic sorbent materials. Guo et al.

[0013] first modified HNT with hexadecyltrimethoxysilane (HDTMS) and y-(2,3-epoxypropoxy)propyltrimethoxysilane and they prepared a surface with a water contact angle of 154° by spraying it on a stainless steel wire mesh soaked with epoxy resin E-44 and ethanolamine to prepare a superhydrophobic stainless steel wire mesh material capable of selective oil-water separation. In another study, Feng and his team

[0014] modified the clay mineral by using fixed concentrations of HDTMS and tetraethoxysilane and different concentrations of HNT, coated them on various surfaces with a simple spray gun, and determined the oil-water separation performance of the prepared superhydrophobic material to be 83%. In a study conducted by Song et al.

[0015] , after adding the octadecyltrimethoxysilane compound drop by drop into the aqueous ethyl alcohol solution, a coating formulation was prepared by adding HNT and using this formulation, the cotton fabric was coated with the dip coating technique and a superhydrophobic cotton fabric was obtained. A coating material with superhydrophobic and UV-protective properties was prepared by Chen and his team

[0016] using polydimethylsiloxane (PDMS) / HNT / CeO2 mixture. By applying the dip coating technique, the HNT composite material modified with HDTMS was coated on the surface of the polyurethane foam, thus creating a foam surface with superhydrophobic properties

[0017] , However, in the state of the art [13-17], no activation process is applied to HNT with siloxane (Si-O-Si) groups on its outer cylindrical surface in order to obtain a superhydrophobic surface with HNT and therefore, the modification of the HNT surface with alkoxy silane compounds having functional alkyl groups is carried out only at the ends and inner surface of the cylindrical structure of the clay. In other words, in the preparation of superhydrophobic coating formulations, modification of HNT with silanes cannot be carried out on the outer surface of the cylindrical tubeshaped clay structure. This causes the coating process to not be fully carried out on the entire substrate surface.

[0007] In the state of the art, many techniques such as chemical etching, spray coating, drip coating, spin coating, chemical vapour deposition coating, dip coating and electrospinning coating can be applied in the preparation of superhydrophobic sorbent materials used to selectively remove petroleum-derived products, oily substances, and toxic organic pollutants in water. In these techniques, although it is a simple and inexpensive technique, the chemical etching technique does not guarantee the formation of a homogeneous roughness on the substrate surface

[0018] and in addition, corrosive chemicals such as strong acids used in this technique are extremely harmful to the environment and human health

[0019] . In the spray coating technique used to ensure uniform coating of the substrate surface with the coating formulation, the roughness of the film formed on the surface can be well adjusted by optimising the pressure, solution concentration and coating time

[0018] . On the other hand, in the spray coating technique, due to the inorganic particles in the coating formulation not being distributed homogeneously (precipitating to the bottom), sometimes a homogeneous coating process cannot be fully achieved, and blockages may occur in the nozzles of the spray gun. In the drip coating technique, which is a low-cost and easy-to-use technique, a superhydrophobic coating mixture is dropped onto the substrate and the coated substrate is allowed to dry in a controlled temperature and pressure environment. An important disadvantage of this technique is that a uniform surface topography and coating thickness cannot be obtained

[0018] . Spin coating is a technique used to achieve uniform superhydrophobic coating on many substrates. In this technique, coatings having the desired thickness can be obtained by changing the viscosity of the coating solution, the rotation speed and duration of the coating device. The main disadvantages of the spin coating technique are that a large part of the coating material scatters from the substrate surface and therefore it is not possible to use it, not very good results can be obtained in the corner parts of the substrates, and this technique does not give good results for large surface substrates

[0020] . Although high quality coatings can be obtained in the chemical vapour deposition technique, the fact that this technique is expensive and requires high temperatures, which are the negative aspects encountered in the chemical vapour deposition technique

[0021] , In the dip coating technique, it is possible to coat large-sized substrate materials, but this technique requires the use of large amounts of solvent

[0019] , and furthermore, due to the effect of gravity force towards the end of the coating, the particles in the coating formulation become more concentrated compared to the initial state, and therefore, irregular roughnesses occur on the substrate material. In the electrospinning technique, which is another surface coating technique, the adhesion of the superhydrophobic coating on the substrate is limited and accordingly, difficulties are experienced when the large surfaces are coated with this technique

[0018] . Considering all these differences and disadvantages, the choice of coating technique is important in the preparation of superhydrophobic sorbent materials.

[0008] The patent application numbered US20170036190A1 in the state of the art is related to a sorbent material to be used to clean oil spills and oil slicks from water surfaces and along the coastline, and it is mentioned that, to prepare the hydrophobic and superhydrophobic melamine sponge material of said material, melamine sponges were immersed in a container containing an alkyl chloro silane compound dissolved in toluene and kept for different periods of time (5, 10, 20 and 30 min), a squeezing process was applied to remove excess toluene in the sponge materials, and then the materials were dried at 120 °C for 1 hour. In said study, the water contact angle values of composite sponge materials modified with alkyl chloro silane compound were measured as 147°, 149°, 150° and 151 ° for melamine sponges kept in alkyl chloro silane solution for 5, 10, 20 and 30 minutes, respectively. In this technique where dip coating is carried out; release of toxic hydrochloric acid into the environment after the hydrolysis process due to the use of alkyltrichlorosilane compounds in the coating formulation, the opening and use of alkylchlorosilane compounds in normal air atmosphere being dangerous, the coated sponge material requiring high temperature curing, and also, it being not stated that the inner and outer parts of the obtained sorbent materials were coated homogeneously although it is extremely important to achieve a homogeneous coating on the inner and outer parts of the sponge material in the preparation of superhydrophobic sorbent materials to be used to remove oily substances and organic solvents in water, and water contact angle values of sponge materials coated with alkyltrichlorosilane compounds being realized only on the outer parts are among the significant disadvantages.

[0009] For reasons such as limitations and inadequacies of existing technical solutions, and the facts that the methods used to separate petroleum-derived components in water require high costs, they cause the emission of harmful gases as process output, they are not effective enough in separating oily substance-water mixtures, they have low oil-water separation performance, they require the use of complex devices, gases harmful to the environment and humanity during the coating of superhydrophobic sorbent materials are produced, current coating methods cannot achieve a homogeneous coating, they generally require a high temperature curing process after coating processes, and that a large part of the coating material scatters from the substrate surface and therefore it is not possible to use it, it has become necessary to make an improvement in the production of superhydrophobic and superoleophilic composite sponge materials. Brief Description and Aims of the Invention

[0010] In the invention, a superhydrophobic and superoleophilic composite sponge material and the production method thereof is described. The material obtained by coating the melamine sponge of the invention with alkyl silane containing hydrolyzable alkoxy groups and / or HNT modified with alkyl silanes selectively removes petroleum-derived products, oily substances, and organic solvents in water. The composite sponge of the invention comprises clay or clay mineral containing hydroxyl groups in its outer cylindrical surface structure modified with alkyl silane.

[0011] The aim of the invention is to provide a superhydrophobic and superoleophilic composite sponge material that selectively removes petroleum-derived products, oily substances, and organic solvents in water with high efficiency. By means of to its high sorption capacity, ability to float (not submerge in water), durability in aqueous environment, reusability and ability to recover oily contaminant from the sorbent, the material of the invention can selectively and efficiently remove petroleum-derived products, oily substances, and organic solvents from water.

[0012] Another aim of the invention is to provide a superhydrophobic and superoleophilic composite sponge material that can be produced easily and in a short time at low cost. In the invention, a cheap, non-toxic, naturally abundant clay and / or clay mineral is used in the coating of melamine sponge after being modified with alkyl silane and / or alkyl silanes containing hydrolyzable alkoxy groups. In addition, after the coating process, there is no need to perform any extra operations on the sponge such as purification, drying, or solvent removal, thus the coated superhydrophobic sponge material becomes ready for use directly. In addition, carrying out the sponge coating process in a supercritical CO2 environment with the coating formulation prepared to transform the superhydrophilic sponge into a sponge material with superhydrophobic and superolephilic properties enables the coating process to be completed in a shorter time.

[0013] Another aim of the invention is to provide a superhydrophobic and superoleophilic composite sponge material with homogeneous coating on both the inner and outer surfaces. The coating applied in the invention is transferred into the sponge in the coating reactor at high pressure in a supercritical CO2 environment, ensuring that every part of the hollow structure in the sponge (inner and outer parts) is coated homogeneously.

[0014] Description of Drawings

[0015] Figure 1. XPS survey spectra of cleaned (A) and uncleaned (B) melamine sponge materials.

[0016] Figure 2. XPS survey spectra of uncoated melamine sponge and melamine sponge coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes.

[0017] Figure 3. Static water contact angle values measured for melamine sponges coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, which were kept in HCI and NaOH solutions having different concentrations and in 5% NaCI solution for 16 hours.

[0018] Figure 4. Variation of water contact angle value with the number of abrasion cycles for melamine sponge material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes.

[0019] Figure 5. Water contact angle values of melamine sponge material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, stored at different temperatures for 24 hours.

[0020] Figure 6. Compressive stress-compressive strain curves of coated sponge material subjected to 10 cycles of compression testing at a constant % strain (E) of 50%.

[0021] Figure 7. Sorption capacity values of melamine sponge material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes for various petroleum derivatives, oily substances, and organic solvents.

[0022] Figure 8. Change of the amount of sorbed substance and the amount of residual substance in the melamine sponge sorbent material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, which has been applied sorption and hand squeezing process for diesel fuel, as a result of 15 times of use. Figure 9. Change of the amount of sorbed substance and the amount of residual substance in the melamine sponge sorbent material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, which has been applied sorption and hand squeezing process for machine oil, as a result of 15 times of use.

[0023] Figure 10. Change of the amount of sorbed substance and the amount of residual substance in the melamine sponge sorbent material coated with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, which has been applied sorption and hand squeezing process for chloroform, as a result of 15 times of use.

[0024] Figure 11. Supercritical CO2 coating system

[0025] Definition of Elements / Parts Composing the Invention

[0026] 1. One-way valve

[0027] 2. Three-way valve

[0028] 3. Needle valve

[0029] 4. Filter

[0030] 5. Temperature control

[0031] 6. Pressure control

[0032] 7. Back pressure control

[0033] 8. Bottom valve

[0034] 9. Pressure gauge

[0035] 10. Reaction reactor

[0036] 11. Coating reactor

[0037] 12. Pressing pump

[0038] 13. CO2 tube

[0039] 14. Air compressor Detailed Description of the Invention

[0040] In the invention, a superhydrophobic and superoleophilic composite sponge material and the production method thereof is described. The material to the invention obtained by coating the melamine sponge with alkyl silane containing hydrolyzable alkoxy groups and / or clay or clay mineral modified with alkyl silanes, selectively removes petroleum-derived products, oily substances, and organic solvents in water by means of its high sorption capacity, ability to float (not submerged in water), durability in aqueous environment, reusability, and ability to recover oily contaminants from the sorbent.

[0041] In the invention, at least one or a combination of methyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane undecyltriethoxysilane, dodecytrimethoxysilane, dodecyltriethoxysilane tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane tetradecyltriethoxysilane, pentadecyltrimethoxysilane, penradecyltriethoxysilane hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane nonadecyltrimethoxysilane, nonadecyltriethoxysilane, tetramethoxysilane tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1 H, 1 H, 2H, 2H- perfluorooctyltrimethoxysilane, 1 H, 1 H, 2H, 2H-perfluorooctyltriethoxysilane, 1 H, 1 H,

[0042] 2H, 2H-perfluorononyltrimethoxysilane, 1 H, 1 H, 2H, 2H-perfluorononyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorodecyltriethoxysilane, 1 H, 1 H, 2H, 2H- perfluorodecyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, tris(trimethylsiloxy)silane, isobutyl(trimethoxy)silane, trimethoxy(3,3,3- trifluoropropyl)silane, trimethoxy(2-phenylethyl)silane, trimethoxy(3-

[0043] (methylamino)propyl)silane, trimethoxy(7-octen-1 -yl)silane, methyltris(2- methoxyethoxy)silane, ethoxytris(2-methoxyphenyl)silane compounds containing hydrolyzable groups can be used as silane material. The superhydrophobic sorbent material of the invention comprises a substrate and, in addition, at least one clay or clay mineral or inorganic SiO2 material and at least one silane compound.

[0044] In the invention, water and organic solvent (methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, straight chain and / or branched forms of heptyl alcohol, dioxane, acetonitrile or acetone) can be used as reaction media and hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide or ammonia can be used as pH adjuster. The products in the reaction medium are removed after coating the sponge surface in a supercritical CO2 environment.

[0045] In the invention, sponges with a porous structure (melamine sponge, polyurethane sponge), fabrics (woven or non-woven cotton cellulosic fabrics containing hydroxyl groups) and materials in the form of airgels, foams and membranes prepared from substances containing hydroxyl or amine groups can be used as substrates.

[0046] In the invention, at least one of bentonite, kaolin, metakaolin, sepiolite, kaolinite, halloysite nanotube, montmorillonite, illite, vermiculite, smectite, beidellite, mica, saponite, rectorite, chlorite, attapulgite as well as SiO2 and / or their derivatives or modified products, or any combination thereof, can be used as clay or clay mineral.

[0047] In the invention, the coating of melamine sponge with halloysite nanotube (HNT) modified with methyltriethoxysilane (METES) takes place in the presence of the system shown in Figure 1 1. Said system comprises one-way valve (1 ), three-way valve (2), needle valve (3), two filters that prevent any impurities from CO2 from coming to the system line (4), temperature control (5), pressure control (6), back pressure control (7), bottom valve (8), pressure gauge (9), reaction reactor (10), coating reactor (1 1 ), pressing pump (12) and CO2 tube (13), and air compressor (14) to condition the pump Here, the one-way valve (1 ) ensures that the CO2 gas moves in one direction and does not rotate in the reverse direction. Three-way valve (2) provides controlled distribution of gas to more than one line. The needle valve (3) controls the flow rate of the fluid and distributes it in a certain direction. The filter (4) holds foreign solids and prevents them from entering the system. Temperature control (5) enables the reactor temperature to be adjusted and measured digitally. Pressure control (6) enables digital measurement of reactor pressure. Back pressure control (7) enables the reactor pressure to be reduced in a controlled manner. The bottom valve (8) ensures controlled removal of the liquid at the bottom of the reactor. The pressure gauge (9) enables analogue measurement of the reactor pressure. The reaction reactor (10) is the upper reactor where the sol-gel reactions take place. The coating reactor (11 ) is the lower reactor where the coating is made. The pressing pump (12) ensures that the liquid is transferred to the system at high pressure. The CO2 tube (13) is the siphon tube in which the CO2 fluid is stored. The air compressor (14) provides air between 3 and 9 bars, which is used to condition the pump.

[0048] Production method of the superhydrophobic and superoleophilic composite sponge material that is the subject of the invention comprises the process steps of; i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding H2O2 solution into a container containing clay or clay mineral in order to remove organic impurities in the clay or clay mineral, and then mixing the resulting mixture in a magnetic stirrer, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution, vi. subjecting the mixture to centrifugation to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral first in an oven and / or vacuum oven and storing it in glass jars with lids to be used in the process step viii, viii. first preparing a suspension mixture consisting of purified clay or clay mineral with pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature, xi. separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device, xii. washing the washing water of the separated clay or clay mineral several times with pure water, xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface first in an oven and / or vacuum oven and storing in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor (10), adding the clay or clay mineral obtained in the process step xiii and adding HCI, H2SO4, CH3COOH, NaOH or NH3solution, xv. mixing the mixture in the supercritical phase and meanwhile filling the coating reactor (11 ) with liquid CO2 (carbon dioxide) and waiting, xvi. opening the valve between the reaction reactor (10) and the coating reactor (11 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (11 ) containing the modified suspension depending on the pressure difference and keeping it there, xvii. performing the degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor (11 ), xviii. washing by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (11 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature.

[0049] In an embodiment of the invention, production method of the superhydrophobic and superoleophilic composite sponge material that is the subject of the invention comprises the process steps of; i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions at 20-120°C, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding H2O2 solution between 3% and 30% by mass in a volume between 20-200 mL into a container containing 1 -120 g of clay or clay mineral to remove organic impurities in clay or clay mineral and then mixing the resulting mixture in a magnetic stirrer at a temperature between room temperature and 80°C for 1 -10 hours, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution for 1 -60 minutes, vi. subjecting the mixture to centrifugation at 9000 rpm for 15 minutes to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral for 1 -36 hours at 70-150°C in an oven and / or vacuum oven and storing it in glass jars with lids to be used in the process step viii, viii. first preparing a suspension mixture consisting of 0.1 -30 g purified clay or clay mineral with 100 mL pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding 0.001 -10 g NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature for 0.5-24 hours, xi. at the end of the 0.5-24-hour period, separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device at 9000 rpm for 15 minutes, xii. washing the washing water of the separated clay or clay mineral several times with pure water until its pH value is 7, xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface first at a temperature between 70-150°C for a period of 1 -36 hours in an oven and / or vacuum oven and storing in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor (10) so that alkyl silane / (sponge) ratio by mass is 0.5-30, the (water + organic solvent) / alkyl silane ratio by mass is 1 -30, and the water / organic solvent ratio by mass is 0.05-5, additionally, adding the clay or clay mineral obtained in the process step xiii in an amount between 0.01 -10 times the melamine sponge mass obtained in the process step iii, and adding 0.01 -5 M HCI, H2SO4, CH3COOH, NaOH or NH3 solution to make the initial pH value of the environment 2-14, xv. mixing the mixture in the supercritical phase for 0.5-8 hours at a pressure of 75-125 bar, a temperature in the range of 25-50°C and a stirring speed of 50-400 rpm and meanwhile, filling the coating reactor (1 1 ) with liquid CO2 (carbon dioxide) at a pressure of 65 bar and a temperature of 25 °C and waiting for 0.5-5 hours, xvi. opening the valve between the reaction reactor (10) and the coating reactor (1 1 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (1 1 ) containing the modified suspension depending on the pressure difference and keeping it there for 0.5-20 minutes, xvii. performing the 100-1500 seconds degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor (1 1 ), xviii. washing for 1 -10 minutes by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (1 1 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature in a period of 0.5-5 days.

[0050] In an embodiment of the invention, production method of the superhydrophobic and superoleophilic composite sponge material that is the subject of the invention comprises the process steps of; i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions at 80°C, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding 30% H2O2 solution by mass in 200 mL into a container containing 30 g clay or clay mineral in order to remove organic impurities in the clay or clay mineral, and then mixing the resulting mixture in a magnetic stirrer for 1 hour at room temperature, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution for 10 minutes, vi. subjecting the mixture to centrifugation at 9000 rpm for 15 minutes to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral for 12 hours at 110°C in an oven and / or for 12 hours at 60°C in vacuum oven and storing it in glass jars with lids to be used in the process step viii, viii. first preparing a suspension mixture consisting of 2.0 g purified clay or clay mineral with 100 mL pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding 0.058 g NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature for 24 hours, xi. at the end of the 24-hour period, separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device at 9000 rpm for 15 minutes, xii. washing the washing water of the separated clay or clay mineral several times with pure water until its pH value is 7, xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface, in an oven and / or vacuum oven at a temperature between 70-150°C for a period of 1 -36 hours, in an oven at 110°C for 12 hours and / or in a vacuum oven at 60°C for 12 hours, and storing it in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor (10) so that alkyl silane / sponge ratio by mass is 10, the (water + organic solvent) / alkyl silane ratio by mass is 7.5, and the water / organic solvent ratio by mass is 1 .0, additionally, adding the clay or clay mineral obtained in the process step xiii in an amount between 0.25 times the melamine sponge mass obtained in the process step iii, and adding 0.01 -5 M HCI, HSC , CH3COOH, NaOH or NH3 solution to make the initial pH value of the environment 12, xv. mixing the mixture in the supercritical phase for 2 hours at a pressure of bar, a temperature in the range of 25-50°C and a stirring speed of 200 rpm and meanwhile, filling the coating reactor (1 1 ) with liquid CO2 (carbon dioxide) at a pressure of 65 bar and a temperature of 25°C and waiting for 1 hour, xvi. opening the valve between the reaction reactor (10) and the coating reactor (1 1 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (1 1 ) containing the modified suspension depending on the pressure difference and keeping it there for 5 minutes, xvii. performing the 500 seconds degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor (1 1 ), xviii. washing for 3 minutes by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (1 1 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature for 1 day.

[0051] In the method that is the subject of the invention, the optimum values applied in the 25-50°C temperature range mentioned in the process step xv are 35°C for methyltriethoxysilane (METES) used as alkyl silane, 40°C for octyltriethoxysilane (OTES) and hexadecyltrimethoxysilane (HDMTS), and 45°C for 1 H, 1 H, 2H, 2H- perfluorooctyltriethoxysilane (PFOTES) and phenyltriethoxysilane (PTES).

[0052] In the method that is the subject of the invention, the alcohol mentioned in the process step ii is methyl alcohol or ethyl alcohol. In the invention, X-ray photoelectron spectroscopy (XPS) technique was used to determine the chemical composition on the surfaces of purified clay or clay mineral and surface-activated clay or clay mineral with NaOH or NH3 solution. The presence of 70.9% O, 2.6% C, 15.4% Si and 1 1 .1 % Al was detected on the surface of the clay or clay mineral purified by the XPS technique and after the surface activation process, the amount of O in the surface activated clay or clay mineral was found to be 70.0%, the amount of C was 3.2%, the amount of Si was 15.1 % and the amount of Al was 11 .7%. After activation with NaOH or NH3 solution, the Al / Si concentration ratio in the purified clay or clay mineral increased from 72.1 % to 77.5%. This increase occurred because a very small portion of the silica on the clay or clay mineral surface was separated from the structure in the form of SiOa2’ after treatment with NaOH or NH3 solution. In addition, due to the fact that the silica structure on the outer cylindrical surface of the clay or clay mineral has a much higher affinity for NaOH or NH3 than the alumina structure in the interior of the clay or clay mineral, some of the Si-O-Si groups on the clay or clay mineral surface transforms into the 2Si-OH structure, and thus, the formation of hydroxyl groups on the clay or clay mineral surface occurs. High-resolution Si2p spectra of purified clay or clay mineral and NaOH or NH3 solution-activated clay or clay mineral samples were recorded to prove the formation of hydroxyl groups on the clay or clay mineral surface after treatment with NaOH or NH3 solution. In the high-resolution Si2p spectrum of the purified clay or clay mineral sample, the presence of a single peak with a peak maximum at 102.4 eV and corresponding to Si-O-Si or Si-O-AI siloxane groups was detected. In other words, the amount of Si-O-Si or Si-O-AI siloxane groups on the surface of purified clay or clay mineral was determined as 100%. On the other hand, in the high resolution Si2p spectrum of clay or clay mineral activated with NaOH or NH3 solution, it was observed that the peak maximum value corresponding to Si-O-Si or Si-O-AI siloxane groups shifted slightly from 102.4 eV to 102.2 eV and also that a new peak corresponding to the Si-O-H group occurred at 101 .5 eV. After the activation process with NaOH or NH3 solution, the amount of Si-O-Si or Si-O-AI siloxane groups on the clay or clay mineral surface was determined as 87.3%, while the amount of Si-O-H group formed was determined as 12.7%. This result proved that hydroxyl (Si-OH) groups were successfully formed on the outer surface of clay or clay mineral after treatment with NaOH or NH3 solution. In addition, in the invention, separate XPS analyses of uncleaned and cleaned melamine sponge materials were carried out to see the effect of the cleaning process applied to the melamine sponge, and the results are shown in Figure 1. Using the data in Figure 1 , the presence of 65.41 % and 66.60% C 17.36% and 13.81 % O, 10.88% and 18.67% N, 2.56% and 0.44% Na, and 3.80% and 0.48% S were determined in the uncleaned and cleaned melamine sponge, respectively. This result shows that some of the sodium bisulfite used during the production of the melamine sponge remains in the sponge material in a free form without reacting and is removed from the melamine sponge during the cleaning process. XPS analysis was carried out in the invention to see the change of chemical composition on the surface of the melamine sponge material as a result of coating it with alkyl silane modified clay or clay mineral under optimum process conditions in a supercritical CO2 environment, and XPS survey spectra of uncoated melamine sponge and melamine sponge coated with alkyl silane modified clay or clay mineral under optimum process conditions in supercritical CO2 environment are shown in Figure 2. It is clearly seen in Figure 2 that there is no Si element on the cleaned melamine sponge surface. When the XPS spectrum of the cleaned and uncoated melamine sponge is compared with the XPS spectrum of the melamine sponge coated with alkyl silane modified clay or clay mineral, it is seen that a new peak belonging to the Si element appears in the melamine sponge coated with alkyl silane modified clay or clay mineral. In addition, the intensity of the peak of the N element in the cleaned melamine sponge structure decreases with the coating applied. While uncoated melamine sponge contains 66.60% C, 13.81 % O, 18.67% N, 0.44% Na and 0.48% S, melamine sponge coated with alkyl silane modified clay or clay mineral contains 30.07% C, 35.94% O, 3.16% N, 0.27% Na, 28.59% Si and 1 .98% Al. It was observed that there was a large decrease in the amount of the N element in the structure of the melamine sponge after the coating process with alkyl silane modified clay or clay mineral. When compared with uncoated melamine sponge, it was determined that there was a decrease in the amount of C element from 66.60% to 30.07% and an increase in the amount of O element from 13.81 % to 35.94% in the melamine sponge coated with alkyl silane modified clay or clay mineral, and at the same time, the amount of Si element not present on the uncoated melamine sponge surface was 28.59% in the melamine sponge material coated with alkyl silane modified clay or clay mineral. However, the source of the Al element, which is found in very small amounts in melamine sponge coated with alkyl silane modified clay or clay mineral, is clay or clay mineral. These results obtained by XPS analysis proved that the melamine sponge was successfully coated with alkyl silane modified clay or clay mineral.

[0053] In the invention, uncoated and coated melamine sponge materials were placed in a container with water to see the behaviour of cleaned melamine sponge and melamine sponge coated with alkyl silane modified clay or clay mineral under optimum process conditions in a supercritical CO2 environment. When the uncoated melamine sponge material is dropped into the water, it absorbs the water and sinks to the bottom of the water, whereas when the melamine sponge material coated with alkyl silane modified clay or clay mineral is thrown into the water under optimum process conditions in the supercritical CO2 environment, it has been observed that the composite sponge material repels the water and remains on the surface of the water. This proves that the prepared sponge sorbent material coated with alkyl silane modified clay or clay mineral has a water-repellent property. When the sorbent material is immersed in water as a result of applying an external force to the sponge material coated with alkyl silane modified clay or clay mineral held with the help of a clip, due to the large number of air bubbles trapped in micro / nano hierarchical structures in the sponge material, a shiny and mirror-like surface appearance was formed, and the formation of this appearance is another proof that the sponge material coated with alkyl silane modified clay or clay mineral has a water-repellent surface feature.

[0054] In order to see the behaviour of melamine sponge material coated with alkyl silane modified clay or clay mineral against different types of liquid drops under optimum process conditions in a supercritical CO2 environment, a drop of 0.01 M HCI solution, a drop of 0.01 M NaOH solution, a drop of olive oil, a drop of 5% NaCI solution and a drop of water were added to the prepared sponge material, respectively. Accordingly, the surface of the sponge coated with alkyl silane modified clay or clay mineral does not like and repels 0.01 M HCI and NaOH solution drops, 5% NaCI solution drops and water drops. On the other hand, the same sorbent material completely absorbs olive oil. This result shows that the sponge structure coated with alkyl silane modified clay or clay mineral has a superoleophilic character and has a water-repellent surface structure.

[0055] Water contact angle measurements were carried out on the outer surface of the cubeshaped sponge coated with alkyl silane modified clay or clay mineral and on the inner surface of the sponge divided into two with the help of a scalpel, and the water contact angle values on the outer and inner surfaces of the sponge were found to be 153.0° and 152.8°, respectively. This result proves that both the outer and inner surfaces of the sponge material are coated homogeneously with METES modified HNT in a supercritical CO2 atmosphere. To test the chemical stability of the sponge coated with alkyl silane modified clay or clay mineral, the prepared sponge material was placed in HCI and NaOH solutions with different concentrations and 5% NaCI solution for 16 hours, and then the static water contact angle of the sponge material was measured. The measured static water contact angle values of the sponge coated with alkyl silane modified clay or clay mineral that was kept in 0.01 M HCI, 0.1 M HCI, 1 M HCI, 5% NaCI, 0.01 M NaOH, 0.1 M NaOH and 1 M NaOH solutions for 16 hours are shown in Figure 3. It is understood that the static water contact angle value of the coated sponge kept in 0.01 M HCI, 0.01 M NaOH and 5% NaCI solutions for 16 hours is still above 150° and the sorbent material maintains its superhydrophobic surface feature. Additionally, as the acid (HCI) concentration of the solution in which the coated sponge material was kept was increased (increased to 0.1 M and 1 M), there was a slight decrease in the water contact angle of the sorbent material. The water contact angle value of the composite sponge material, which maintained its superhydrophobic surface feature in 0.01 M NaOH solution, decreased significantly (to 121.2°) in 0.1 M NaOH solution and the surface of the sponge material changed from a superhydrophobic surface to a hydrophobic surface. It has been observed that if the NaOH solution concentration value with which the superhydrophobic sponge material is contacted is further increased to 1 M and left there for 16 hours, a sponge material with a superhydrophilic surface feature is obtained as a result of the complete deformation of the coating in the sorbent structure. In order to determine the change of the static water contact angle and sliding angle values of the coated sponge material with the amount of wear, an abrasion process of 5, 10, 15, 20 and 25 cycles was applied respectively to the sorbent material with a mass of 50 g on it on sandpaper, and at the end of each cycle, the static water contact angle and sliding angle values of the composite sponge material were measured and the obtained values are presented in Figure 4. There was a slight decrease in the water contact angle of the coated sponge material with the increase in the number of wear cycles applied. In addition, the coated sponge material maintains its superhydrophobic surface feature even in 10 cycles of abrasion application. After 25 cycles of abrasion, the water contact angle value of the sorbent material was measured as 146.8°, and this result indicates that even after 25 cycles of abrasion, the coated sponge material has a water contact angle value close to the superhydrophobic surface feature.

[0056] In order to determine the thermal stability of the coated sponge material, the water contact angle values of the sorbent material kept for 24 hours at different temperatures (25°C, 40°C, 60°C and 80°C) were measured. The change in the water contact angle value of the coated sponge material stored for 24 hours at different temperatures is presented in Figure 5 as a function of temperature. As seen in Figure 5, the water contact angle value of the coated sponge material does not show any change until the storage temperature of 80°C. In other words, the thermal stability of the composite sponge material prepared in the invention is extremely high up to 80°C. Additionally, in order to determine the mechanical stability of the coated sponge material, the cubeshaped sponge sample was subjected to compression for 10 consecutive cycles in the compression test measuring device at a constant % strain (E) value of 50% and a certain compression speed. The compressive stress-compressive strain curves of the 1st, 2nd, 3rd, 4th, 5th, 6th, 8thand 10thcycles of the mechanical compression test repeated 10 times in a row are shown in Figure 6. The mechanical strength of the coated sponge material at 50% compressive strain was found to be 10.70 kPa in the 1stcycle and 10.00 kPa in the 10thcycle. Therefore, after 10 cycles of compression, no serious loss in the mechanical strength of the coated sponge material was observed, and the amount of deformation in the height of the sponge was calculated as only 0.14% after 10 cycles of compression at 50% compression strain. These results prove that the mechanical stability of the composite sponge material prepared in the invention is quite good.

[0057] In the invention, to determine the petroleum derived product, oily substance and organic solvent sorption capacity values of the sponge material coated with alkyl silane modified clay or clay mineral, gasoline, diesel oil, kerosene, machine oil, olive oil, toluene, n-hexane, N,N-dimethylformamide, dimethylsulfoxide, chloroform, petroleum ether, ethyl alcohol and crude oil were used. The initial mass value (Wi) of each melamine sponge sorbent whose sorption capacity value was to be determined was weighed on a precision balance, and then, the composite sponge sample, whose sorption capacity value was to be determined, was placed separately in beakers containing 25 mL of pollutant (petroleum-derived product, oily substance or organic solvent) whose temperature was adjusted to 25±2°C, and the sorption process was carried out. In preliminary studies, it was observed that all pollutants reached sorption equilibrium within 1 -2 minutes, and an equilibration period of 10 minutes was used to determine the sorption capacity values. After 10 minutes, the sorbent material whose sorption capacity value was to be determined was removed from the beaker containing the contaminant and the mass of the sponge material (W2) was weighed again. With the equation sorption capacity = [(W1 - Wo)] I Wo, the sorption capacity value of the sponge material was calculated as g pollutant / g sorbent. The sorption capacity values of the composite sponge for various petroleum derivatives, oily substances and organic solvents are shown in Figure 7. As seen in Figure 7, it can be seen that the lowest sorption capacity value for the coated sponge material was obtained for petroleum ether (49.6 g / g) and the highest sorption capacity value for chloroform (122.4 g / g). In addition, the sorption capacity values of dimethyl sulfoxide (1 10.2 g / g) and chloroform (122.4 g / g) for the coated sponge material reached values more than 100 times the gram amount of sorbent. The N,N-dimethylformamide sorption capacity value for the coated sponge sorbent material was calculated as 97.7 g / g. While the sorption capacity value of the sorbent for gasoline and diesel was determined as 65.2 g / g and 60.6 g / g, respectively, this value increased to 88.4 g / g for crude oil. Additionally, by selecting diesel oil as a petroleum-derived pollutant, machine oil as an oily substance pollutant, and chloroform as an organic solvent pollutant, 15 sorption-squeezing (desorption) cycles were applied to the sponge material to see the regeneration performance and sorption performance of the pollutant-loaded sponge material. Before each sorptionsqueezing process, the mass of the sponge material was weighed, and after the weighing, the amount of pollutants sorbed by the sponge and the amount of residual pollutants remaining in the sponge were calculated for each sorption-squeezing cycle, respectively. The change in the amount of sorbed substance and the amount of residual substance in the composite sponge material to which sorption and hand squeezing processes were applied, as a result of 15 uses, is shown in Figure 8 for diesel fuel, Figure 9 for machine oil and Figure 10 for chloroform. For diesel fuel, the sorption capacity value of the sponge material after the first use and the amount of residue in the sorbent after hand squeezing were found to be 60.6 g / g and 4.59 g / g, respectively; after the 10thuse the sorption capacity value of the sorbent material and the amount of residue in the sorbent after hand squeezing were found to be 53.0 g / g and 4.14 g / g, respectively; and after the 15thuse, the sorption capacity value of the sorbent material and the amount of residue in the sorbent after hand squeezing were found to be 50.3 g / g and 3.55 g / g, respectively (Figure 8). While there is only a 12.5% decrease in the sorption capacity value of the sponge material for diesel fuel after the 10thuse, this decrease increases to 17.0% after the 15thuse. After the 1st, 10thand 15thuse of machine oil, while the sorption capacity value of the sorbent material showed a change as 87.7 g / g, 83.5 g / g and 80.6 g / g, respectively, the amount of pollutants remaining in the sponge material is 10.8 g / g in the 1stcycle, 1 1.3 g / g in the 10thcycle and 1 1.9 g / g in the 15thcycle (Figure 9). The machine oil sorption capacity of the sponge material coated with alkyl silane modified clay or clay mineral decreased by only 4.8% and 8.1 %, respectively, as a result of hand squeezing in the 10thand 15thuses. After the 1st, 10thand 15thuse of chloroform, while the sorption capacity value of the sponge material was 122.4 g / g, 105.5 g / g and 91.8 g / g, respectively, the amount of residual chloroform remaining in the sorbent material after hand squeezing for the same cycles was 6.22 g / g, 5.71 g / g and 5.44 g / g, respectively (Figure 10). These results show that the sorption capacity value of the sponge material for various pollutants is quite high even after 15 uses.

[0058] In order to determine the performance of coated melamine sponge in spontaneously and selectively separating the organic solvent-water mixture, two pieces of 2 cm x 2 cm x 2 cm sized sorbent material were placed at the bottom of a vertical cylindrical glass tube with open ends and stained with 10 mL Methylene Blue from the other (top) end of the apparatus, and filtration was carried out by pouring an equal volume of chloroform-water mixture containing simulated ocean water and 10 mL of Oil Red O dyed chloroform. To prepare simulated ocean water, First, a 1 L volumetric flask was taken and 24.53 g NaCI, 5.2 g MgCh, 4.09 g Na2SO4, 1.16 g CaCh, 0.695 g KCI, 0.201 g NaHCOa, 0.101 g H3BO3 and 0.025 g SrCh were added into the volumetric flask, and then after ensuring that the solids are dissolved by adding ultrapure water the total volume of the solution was made up to 1 L with ultrapure water, afterwards, the percentage separation efficiency value for an equal volume of chloroform -water mixture was calculated with the help of the equation: Separation efficiency (%) = [mi / mo] x 100 (mo; the amount of water in the mixture before the separation process, mi; the amount of water passing into the filtrate after the separation process). Additionally, the flow amount (J) value for the filtration of the chloroform-water mixture through the sponge material was calculated with the equation J = V / (A.t) (V denotes the filtrate volume (L), A denotes the effective separation area of the material (m2) and t denotes the filtration time (h)). Chloroform in an equal volume of chloroform-water mixture is selectively separated by spontaneous separation technique by sponge material coated with alkyl silane modified clay or clay mineral and the separation efficiency value of this process was calculated as 99.93% and the flux (J) value was 2780 L / (m2.h).

[0059] In order to determine the performance of the coated melamine sponge in selectively separating an equal volume of diesel oil-water mixture by using the continuous separation technique, a sorbent material of 2 cm x 1 cm x 1 cm size was placed at one end of the hose, which was open at both ends and the other end of the hose is placed in a collection container connected to the vacuum pump. Continuous separation technique application was initiated by dipping the hose end with sorbent material into an equal volume of diesel-water mixture containing 50 mL of simulated ocean water dyed with Methylene Blue and diesel fuel dyed with 50 mL of Oil Red O, and simultaneously turning on the vacuum pump. The sorbent material placed at the end of the hose was contacted with both the pollutant and water in the separated dieselwater mixture throughout the process. The separation efficiency value was calculated as 99.06% in the separation of diesel oil-water mixture with the continuous separation technique using the composite sponge material that is the subject of the invention, and this result shows that sponge material coated with alkyl silane modified clay or clay mineral can be used successfully as a sorbent in separating the diesel-water mixture with the continuous separation technique. Additionally, to determine the crude oil removal performance of the melamine sponge coated with alkyl silane modified clay or clay mineral on simulated ocean water, 1 mL volume of crude oil with an API gravity value of 21 .90 was added to a beaker containing a magnetic fish and 100 mL volume of simulated ocean water. While the temperature of the mixture was kept at 25±2°C, simulated ocean water and crude oil were mixed in the magnetic stirrer, the composite sponge material was dropped into the beaker. After approximately 1 minute, the sorbent material was removed from the simulated ocean water-crude oil mixture, and after manually squeezing the crude oil sorbent onto the sponge onto a watch glass, the sponge material was placed back into the simulated ocean water-crude oil mixture mixed in the magnetic stirrer in the beaker. After selectively sorbing the crude oil onto the sorbent material from the simulated ocean water-crude oil mixture for approximately 2 more minutes, the sorbent material was removed from the beaker. The separation efficiency value of the sponge coated with alkyl silane modified clay or clay mineral for the crude oil-simulated ocean water mixture was calculated as 99.99%. REFERENCES

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Claims

CLAIMS1. A superhydrophobic and superoleophilic composite sponge material, comprising one substrate and at least one clay or clay mineral or inorganic SiO2 material, and at least one silane compound.

2. Composite sponge material according to Claim 1 , wherein the substrate:silane ratio is 0.033-2 by mass.

3. Composite sponge material according to Claim 2, wherein the substrate:silane ratio is 0.1 by mass.

4. Composite sponge material according to Claim 1 , wherein said clay or clay mineral is 0.01 -10 times the mass of the substrate.

5. Composite sponge material according to Claim 4, wherein said clay or clay mineral is 0.25 times the mass of the substrate.

6. Composite sponge material according to Claim 1 , wherein said substrate is a material in the form of melamine sponge, polyurethane sponge, woven or nonwoven cotton cellulosic fabric containing hydroxyl groups, air-gel, foam or membrane prepared from substances containing hydroxyl or amine groups.

7. Composite sponge material according to Claim 1 , wherein said clay or clay mineral is at least one of bentonite, kaolin, metakaolin, sepiolite, kaolinite, halloysite nanotube, montmorillonite, illite, vermiculite, smectite, beidellite, mica, saponite, rectorite, chlorite, attapulgite as well as SiO2 and / or their derivatives or modified products, or any combination thereof.

8. Composite sponge material according to Claim 1 , wherein said alkyl silanes are at least one or a combination of methyltrimethoxysilane (METES), ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane octyltriethoxysilane (OTES), nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecytrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, penradecyltriethoxysilane, hexadecyltrimethoxysilane (HDMTS),hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane (PTES), 1 H, 1 H, 2H, 2H-perfluorooctyltrimethoxysilane (PFOTES), 1 H, 1 H, 2H, 2H- perfluorooctyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorononyltrimethoxysilane, 1 H, 1 H, 2H, 2H-perfluorononyltriethoxysilane, 1 H, 1 H, 2H, 2H- perfluorodecyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorodecyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, tris(trimethylsiloxy)silane, isobutyl(trimethoxy)silane, trimethoxy(3,3,3-trifluoropropyl)silane, trimethoxy(2- phenylethyl)silane, trimethoxy(3-(methylamino)propyl)silane, trimethoxy(7- octen-1 -yl)silane, methyltris(2-methoxyethoxy)silane, ethoxytris(2- methoxyphenyl)silane compounds.

9. Production method of a superhydrophobic and superoleophilic composite sponge material, comprising the process steps of: i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding H2O2 solution into a container containing clay or clay mineral in order to remove organic impurities in the clay or clay mineral, and then mixing the resulting mixture in a magnetic stirrer, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution, vi. subjecting the mixture to centrifugation to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral first in an oven and / or vacuum oven and storing it in glass jars with lids to be used in the process step viii,viii. first preparing a suspension mixture consisting of purified clay or clay mineral with pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature, xi. separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device, xii. washing the washing water of the separated clay or clay mineral several times with pure water, xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface first in an oven and / or vacuum oven and storing in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor(10), adding the clay or clay mineral obtained in the process step xiii and adding HCI, H2SO4, CH3COOH, NaOH or NH3solution, xv. mixing the mixture in the supercritical phase and meanwhile filling the coating reactor (1 1 ) with liquid CO2 (carbon dioxide) and waiting, xvi. opening the valve between the reaction reactor (10) and the coating reactor (11 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (11 ) containing the modified suspension depending on the pressure difference and keeping it there, xvii. performing the degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor(1 1 ), xviii. washing by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (1 1 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature.A method according to claim 9, comprising the steps of: i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions at 20-120°C, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding H2O2 solution between 3% and 30% by mass in a volume between 20-200 mL into a container containing 1 -120 g of clay or clay mineral to remove organic impurities in clay or clay mineral and then mixing the resulting mixture in a magnetic stirrer at a temperature between room temperature and 80°C for 1 -10 hours, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution for 1 -60 minutes, vi. subjecting the mixture to centrifugation at 9000 rpm for 15 minutes to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral for 1 -36 hours at 70-150°C in an oven and / or vacuum oven and storing it in glass jars with lids to be used in the process step viii, viii. first preparing a suspension mixture consisting of 0.1 -30 g purified clay or clay mineral with 100 mL pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding 0.001 -10 g NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature for 0.5-24 hours, xi. at the end of the 0.5-24-hour period, separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device at 9000 rpm for 15 minutes, xii. washing the washing water of the separated clay or clay mineral several times with pure water until its pH value is 7,xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface first at a temperature between 70-150°C for a period of 1 -36 hours in an oven and / or vacuum oven and storing in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor (10) so that alkyl silane / (sponge) ratio by mass is 0.5-30, the (water + organic solvent) / alkyl silane ratio by mass is 1 -30, and the water / organic solvent ratio by mass is 0.05-5, additionally, adding the clay or clay mineral obtained in the process step xiii in an amount between 0.01 -10 times the melamine sponge mass obtained in the process step iii, and adding 0.01 -5 M HCI, H2SO4, CH3COOH, NaOH or NH3 solution to make the initial pH value of the environment 2-14, xv. mixing the mixture in the supercritical phase for 0.5-8 hours at a pressure of 75-125 bar, a temperature in the range of 25-50°C and a stirring speed of 50-400 rpm and meanwhile, filling the coating reactor (11 ) with liquid CO2 (carbon dioxide) at a pressure of 65 bar and a temperature of 25 °C and waiting for 0.5-5 hours, xvi. opening the valve between the reaction reactor (10) and the coating reactor (11 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (11 ) containing the modified suspension depending on the pressure difference and keeping it there for 0.5-20 minutes, xvii. performing the 100 -1500 seconds degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor (1 1 ), xviii. washing for 1 -10 minutes by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (1 1 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature in a period of 0.5-5 days.

11. A method according to claim 10, comprising the steps of: i. cutting the plate-shaped melamine sponge into small pieces with a scalpel, ii. washing the sponges first with alcohol and then with pure water to remove impurities from the cut sponge, iii. drying the washed sponges at room conditions at 80°C, in an oven or in a vacuum oven, and storing them in glass jars with lids to be used in the process step xiv, iv. adding 30% H2O2 solution by mass in 200 mL into a container containing 30 g clay or clay mineral in order to remove organic impurities in the clay or clay mineral, and then mixing the resulting mixture in a magnetic stirrer for 1 hour at room temperature, v. applying ultrasonication treatment to the suspension mixture consisting of clay or clay mineral and H2O2 (hydrogen peroxide) solution for 10 minutes, vi. subjecting the mixture to centrifugation at 9000 rpm for 15 minutes to separate the clay or clay mineral in suspension from the liquid phase, vii. drying the separated clay or clay mineral for 12 hours at 110°C in an oven and / or for 12 hours at 60°C in vacuum oven and storing it in glass jars with lids to be used in the process step viii, viii. first preparing a suspension mixture consisting of 2.0 g purified clay or clay mineral with 100 mL pure water to activate the surface of the clay or clay mineral with dilute or concentrated NaOH (sodium hydroxide) or NH3 (ammonia) solution by creating reactive hydroxyl groups on the surface of the clay or clay mineral, ix. adding 0.058 g NaOH or NH3 to the prepared mixture, x. mixing the mixture in a magnetic stirrer at room temperature for 24 hours, xi. at the end of the 24-hour period, separating the clay or clay mineral containing hydroxyl groups formed on its surface from the environment by centrifuging it in a centrifuge device at 9000 rpm for 15 minutes, xii. washing the washing water of the separated clay or clay mineral several times with pure water until its pH value is 7, xiii. drying the clay or clay mineral, which has hydroxyl groups formed on the outside of its cylindrical surface, in an oven and / or vacuum oven at atemperature between 70-150°C for a period of 1 -36 hours, in an oven at 110°C for 12 hours and / or in a vacuum oven at 60°C for 12 hours, and storing it in a container with a lid to be used in the process step xiv, xiv. adding alkyl silane, water and organic solvent into the reaction reactor (10) so that alkyl silane / sponge ratio by mass is 10, the (water + organic solvent) / alkyl silane ratio by mass is 7.5, and the water / organic solvent ratio by mass is 1 .0, additionally, adding the clay or clay mineral obtained in the process step xiii in an amount between 0.25 times the melamine sponge mass obtained in the process step iii, and adding 0.01 -5 M HCI, HSO4, CH3COOH, NaOH or NH3 solution to make the initial pH value of the environment 12, xv. mixing the mixture in the supercritical phase for 2 hours at a pressure of bar, a temperature in the range of 25-50°C and a stirring speed of 200 rpm and meanwhile, filling the coating reactor (1 1 ) with liquid CO2 (carbon dioxide) at a pressure of 65 bar and a temperature of 25 °C and waiting for 1 hour, xvi. opening the valve between the reaction reactor (10) and the coating reactor (11 ) and thus transferring the alkyl silane in the reaction reactor to the coating reactor (11 ) containing the modified suspension depending on the pressure difference and keeping it there for 5 minutes, xvii. performing the 500 seconds degas process by first removing the modified clay or clay mineral and then CO2 gas from the bottom valve (8) in the coating reactor (1 1 ), xviii. washing for 3 minutes by pumping liquid CO2 into the coating reactor and keeping the degas tap open during this time ensures that the CO2 coming out of the pump is washed out by washing the coated sponge in the coating reactor (1 1 ), and xix. removing the sponge coated with alkyl silane modified clay or clay mineral from the reactor and keeping it in a desiccator at room temperature for 1 day.

12. A method according to Claims 10 or 11 , wherein the optimum values applied in the 25-50°C temperature range mentioned in the process step xv are 35°C for methyltriethoxysilane (METES) used as alkyl silane, 40°C for octyltriethoxysilane (OTES) and hexadecyltrimethoxysilane (HDMTS), and 45°C for 1 H, 1 H, 2H, 2H-perfluorooctyltriethoxysilane (PFOTES) and phenyltriethoxysilane (PTES).

13. A method according to any of the Claims 9 to 1 1 , wherein said alkyl silanes are at least one or a combination of methyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane dodecytrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, penradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorooctyltrimethoxysilane, 1 H, 1 H, 2H, 2H- perfluorooctyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorononyltrimethoxysilane, 1 H, 1 H, 2H, 2H-perfluorononyltriethoxysilane, 1 H, 1 H, 2H, 2H- perfluorodecyltriethoxysilane, 1 H, 1 H, 2H, 2H-perfluorodecyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, tris(trimethylsiloxy)silane, isobutyl(trimethoxy)silane, trimethoxy(3,3,3-trifluoropropyl)silane, trimethoxy(2- phenylethyl)silane, trimethoxy(3-(methylamino)propyl)silane, trimethoxy(7- octen-1 -yl)silane, methyltris(2-methoxyethoxy)silane, ethoxytris(2- methoxyphenyl)silane compounds.14.A superhydrophobic and superoleophilic composite sponge material produced by a method according to any one of claims 9-1 1 .

15. Use of a superhydrophobic and superoleophilic composite sponge material according to claim 1 or 14 for the selective removal of petroleum-derived products, oily substances and organic solvents present in water.

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