Decolorization of dye-containing textile wastewater with composite polymers exhibiting photocatalytic properties

Abstract

The invention relates to the removal of dyes from wastewater using polymer composite particles with magnetic and photocatalytic properties.

Description

[0001] Decolorization of dye-containing textile wastewater with composite polymers exhibiting photocatalytic properties

[0002] FIELD OF THE INVENTION

[0003] The invention relates to the removal of dyes from wastewater using polymer composite particles with magnetic and photocatalytic properties.

[0004] PRIOR ART

[0005] In the textile industry, traditional methods such as filtration, sedimentation, and adsorption are used for wastewater treatment. The filtration method is effective for removing large particles and solid waste but can be inadequate for fully removing dissolved dyes. In sedimentation, chemical processes can sometimes remove dyes from water. However, the efficiency of these methods varies depending on the type of dye, pH, and other characteristics of the solution. Adsorption methods, using materials like activated carbon, can absorb dyes, but this method tends to be costly and can reach saturation points, which limits its effectiveness..

[0006] Some decolorization methods used for dye decomposition in the prior art involve processes that require high energy, such as UV radiation. This increases the process cost and limits their applicability due to the availability or cost of such energy sources. While these methods can quickly remove dyes from water, they often fall short of complete decomposition or total elimination of pollution, thus potentially creating an additional pollution risk.

[0007] The following documents were encountered during the preliminary patent search..

[0008] In the document with publication number of CN103041866B describes a method for preparing titanium dioxide-mesoporous polymer nano-porous composite visible light photocatalytic material. The polymerization involves the use of azodiisobutyronitrile as the initiator, divinylbenzene as the cross-linking monomer, 4-vinylpyridine or 1 - vinylimidazole as functional monomers, and n-butyl titanate as the titanium source, under solvothermal conditions at 80-140°C for 12-24 hours. The solvent group used to achieve porous polymers with a wide surface area includes ethyl acetate, methyl acetate, tetrahydrofuran, toluene, and ethanol. The resulting nano-porous composite visible light photocatalytic material has the capability to decompose organic pollutants.

[0009] In the document with publication number of EP2138230B1 presents a method for preparing highly porous and high surface area post-crosslinked polymer adsorbents in a single process. Porous crosslinked aromatic copolymers are frequently used adsorbents for separating and purifying organic compounds. The monomer used in the current invention is a mixture of meta- and para-diphenylbenzenes. The pore-forming solution is selected from a group including methylene chloride, ethylene chloride, propylene chloride, chlorobenzene, chlorotoluene; hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene, methyl iso-butanol, and di-iso-butanol.

[0010] In the document with publication number of describes a magnetic and photocatalytic polymeric composite particle containing ethylene glycol dimethacrylate, polyvinyl alcohol, toluene, Fe3O4, TiO2, and benzoyl peroxide for the treatment of wastewater arising from the textile sector. Its distinguishing feature is the inclusion of vinyl pyridine. To increase the surface area per gram of the obtained material, R&D efforts are required to synthesize a polymer with a larger surface area.

[0011] As a result, all abovementioned problems have made it necessary to make an improvement in the relevant technical field.

[0012] AIM OF THE INVENTION

[0013] The present invention aims to eliminate the abovementioned problems and to make a development in the relevant technical field.

[0014] The main objective of the invention is to provide an environmentally friendly and effective method for treating colored dye wastewater in the textile industry.

[0015] Another objective of the invention is to prevent the formation of secondary pollution by combining adsorption and heterogeneous photocatalysis methods.

[0016] Another object of the invention is to use polymer composite particles with non-toxic properties. Another object of the invention is to achieve an efficient treatment process for effectively removing dyes.

[0017] Another object of the invention is to ensure easy separation of the particles from an aqueous solution using an external magnet by employing magnetic-sensitive particles. to ensure the removal of pollutants by adsorption onto surfaces.

[0018] Another object of the invention is heterogeneous photocatalysis, which involves using photocatalysts to facilitate the oxidation of pollutants through the utilization of light energy.

[0019] BRIEF DESCRIPTION OF THE INVENTION

[0020] The invention is related to a polymer composite particles with magnetic and photocatalytic properties for the treatment of wastewater in the textile industry. This composition is used to remove dyes from wastewater and prevent the formation of harmful waste loads to the environment. The composition includes following steps;

[0021] Polyvinyl Alcohol (PVA) at a weight ratio of 1.12-1.22%, which ensures the homogeneous dispersion of the organic phase in droplets and creates the dispersion medium.

[0022] Benzoyl Peroxide (BPO) at a weight ratio of 0.74-0.82%, which provides the initiator properties for the copolymerization between the monomer and cross-linker.

[0023] Titanium Dioxide (TiO2) at a weight ratio of 3.72-4.12%, which imparts photocatalytic properties to facilitate heterogeneous photocatalysis and decolorization.

[0024] Toluene at a weight ratio of 32.01 -35.41%, which evaporates from the reaction environment to ensure the polymers have a porous and large surface area.

[0025] Divinylbenzene at a weight ratio of 16.97-18.77%, which is used as a cross-linker during polymerization to make the polymers rigid, inert, and networked.

[0026] 4-Vinylpyridine (4-VP) at a weight ratio of 36.63-40.63%, which is used as a monomer during polymerization.

[0027] Barium Ferrite at a weight ratio of 3.72-4.12%, which provides magnetic properties to the polymers. A preferred embodiment of the invention involves using a new polymer synthesized through the copolymerization of 4-Vinylpyridine and Divinylbenzene. This polymer, which contains a photocatalyst, combines adsorption and heterogeneous photocatalysis methods to eliminate pollution in wastewater.

[0028] Another preferred embodiment of the invention involves obtaining a polymer composite with magnetic and photocatalytic properties that eliminates pollution in wastewater by combining adsorption and heterogeneous photocatalysis methods. The process consists of the following steps:

[0029] In step A, for the preparation of the dispersion phase, 1.12-1 .22% by weight of Polyvinyl Alcohol (PVA) is added to 5% by weight of distilled water, and the mixture is stirred using a magnetic stirrer in a heating unit until it becomes homogeneous,

[0030] In step B, for the preparation of the organic phase, 0.74-0.82% by weight of Benzoyl Peroxide is added as the initiator and 32.01 -35.41 % by weight of Toluene is added as the pore-forming agent,

[0031] In step C, for the preparation of the polymerization environment, 3.72-4.12% by weight of Barium Ferrite and 3.72-4.12% by weight of Titanium Dioxide are added to a cylindrical polymerization reactor along with the dispersion phase from step A and the organic phase from step B. The mixture is stirred at 70°C and 400 rpm until homogeneous,

[0032] In step D, after the polymerization in step C is complete and the polymers have settled, the dispersion phase from step A is filtered to separate the particles. The obtained particles are then washed in a water-ethanol mixture to remove unreacted monomers and solvent,

[0033] In step E, the drying process is carried out for a minimum of 48 hours.

[0034] BRIEF DESCRIPTION OF DRAWINGS

[0035] The surface morphology of the polymer matrix composite particles as observed through Scanning Electron Microscopy (SEM) images are given in Figure 1.

[0036] The N2 adsorption-desorption graph of the polymer particles are given in Figure 2.

[0037] The density-magnetic field graph for the polymer particles are given in Figure 3. The X-ray Diffraction (XRD) graph of the polymer particles are given in Figure 4.

[0038] The Fourier Transform Infrared (FTIR) spectrum of the polymer matrix composite particles are given in Figure 5.

[0039] The figures are not required to be scaled and the details which are not necessary for understanding the present invention may be neglected. Moreover, the elements that are at least substantially identical or have at least substantially identical functions been shown by the same number.

[0040] DETAILED DESCRIPTION OF THE INVENTION

[0041] Bu detayli agiklamada bulug konusu fotokatalitik bzellik gbsteren kompozit polimerler ile renklilik igeren tekstil atik boyama sulannin renksizlegtirilmesi sadece konunun daha iyi anlagilabilmesi igin higbir smirlayici etki olugturmayacak brneklerle agiklanmaktadir.

[0042] In this detailed description, the invention the decolorization of textile dyeing wastewater containing color using photocatalytic composite polymers described by means of examples only for clarifying the subject matter such that no limiting effect is created.

[0043] The invention relates to the removal of dyes from wastewater using polymer composite particles with magnetic and photocatalytic properties.

[0044] Traditional methods commonly used for treating wastewater in the textile industry include filtration, sedimentation, and adsorption. Filtration separates solid particles from wastewater by passing it through filters with different pore sizes. Sedimentation aims to allow particles to settle out of the water through gravity or chemical processes. Adsorption involves using special adsorbent materials to remove organic or inorganic contaminants from the water

[0045] Traditional treatment methods can quickly remove dyes from water; however, these methods are not always sufficiently efficient. In some cases, complete removal of dyes may not be achieved, which can leave the wastewater with a certain level of pollution. This situation suggests that while the wastewater may appear to be treated, the pollution has not been entirely eliminated. In such cases, contaminants may only become transportable within the water and cause additional environmental pollution. Some decolorization methods may require specific conditions, such as high-energy UV rays, to break down or remove the dyes. This limits the applicability and widespread use of these methods, as well as increases energy requirements and operational costs.

[0046] The process of removing dyes from wastewater using polymer composite particles with magnetic and photocatalytic properties is addressed as follows:

[0047] Step A Preparation of the Dispersion Phase:

[0048] 0.3 grams of polyvinyl alcohol (PVA) is first added to 100 mL of distilled water. The mixture is stirred with a magnetic stirrer in a heater until it becomes homogeneous.

[0049] Step B Preparation of the Organic Phase:

[0050] 0.2 grams of benzoyl peroxide is used as an initiator and added to 10 mL of toluene, which acts as the pore-forming agent. This mixture is stirred until it becomes homogeneous, and then 10 mL of 4-vinylpyridine (4-VP) and 5 mL of divinylbenzene (DVB) are added.

[0051] Step C Preparation of the Reaction Environment

[0052] In a specialized cylindrical polymerization reactor, 1 gram of barium ferrite, 1 gram of titanium dioxide (TiO2), the dispersion phase, and the organic phase are sequentially added. The mixture is stirred at 70°C and 400 rpm until it becomes homogeneous.

[0053] Step D Sedimentation Process and Particle Separation:

[0054] The polymers formed as a result of the reaction are subjected to the sedimentation process. After sedimentation is complete, the dispersion phase is filtered to separate the particles. The obtained particles are then washed by soaking in a water-ethanol mixture to remove unreacted monomers and solvents.

[0055] Step E Drying Process:

[0056] After step D, the polymer matrix composite particles are dried in an oven for 48 hours. Figure 1 shows the surface morphology of the polymer matrix composite particles obtained through Scanning Electron Microscopy (SEM). Upon examining the provided SEM images, it is determined that the structure consists of interwoven porous particles.

[0057] The amounts of elements present in the structure have been determined using Energy Dispersive X-ray Spectroscopy (EDS) analysis. The EDS spectrum and the percentages of the elements in the structure are as follows:

[0058] Figure 2 shows the N2 adsorption-desorption graph of the polymer particles, and this isotherm is classified as type IV. The pore size distribution of the polymer particles is also shown in the figure; the pore size distribution ranges from 2.8 to 8.05 nm. These values indicate that the polymer particles exhibit a mesoporous distribution.

[0059] A high surface area and pore volume are effective in enabling the polymer to be used as an adsorbent. The specific surface areas of the polymer particles have been determined to be 41 .8 m2 / g, the total pore volumes are 0.2033 cm3 / g, and the BJH pore diameters are 2.87 nm..

[0060] Figure 3 shows the density-magnetic field graph for the polymer particles. Barium ferrite is the structural component responsible for the sensitivity of the polymer particles to the magnetic field. The G factor measures the contribution of spin movements to magnetization. The experimentally determined G factor value of 2.1 1 is consistent with the G factor value in the literature. This consistency confirms the presence of barium ferrite in this structural composition..

[0061] Figure 4 shows the X-ray diffraction (XRD) graph of the polymer particles. A prominent peak observed at 20 = 25° is attributed to the presence of the anatase phase of TiO2, which is known for its high photocatalytic activity. This observation indicates that the anatase phase of TiO2 is dominant within the structure. Additional characteristic peaks of the anatase phase are observed at 20 = 49° and 61 °. Furthermore, the XRD analysis reveals the presence of barium ferrite as another component within the structure. Barium ferrite is identified by distinct peaks at 20 = 30°, 32°, 35°, 37°, 38°, and 64°. Figure 5 shows the Fourier Transform Infrared (FTIR) spectrum of the polymer matrix composite particles. The prominent peaks observed at 1579.6 cm-1and 1415 cm-1correspond to the presence of C=N and C-N bonds in the vinyl pyridine compound, respectively. Additionally, the peaks observed around a wavenumber of 3000 cm-1represent the characteristic vibrations of C-H bonds present in the molecular structure.

[0062] The new monomer-crosslinking structure obtained with the composition mentioned in the invention significantly enhances the beneficial properties of the polymer as an adsorbent, resulting in a polymer with superior characteristics.

[0063] The scope of protection of the invention is stated in the attached claims and cannot be limited to what is explained in this detailed description for exemplary purposes. Because it is obvious that a person skilled in the art can produce similar structures in the light of those described above, without deviating from the main theme of the invention.

Claims

CLAIMS1. A composition used in the textile industry for treating wastewater by using polymer composite particles with magnetic and photocatalytic properties to remove dyes from wastewater and prevent the formation of environmentally harmful waste loads, the composition is characterized by;• 1.12-1 .22% by weight of Polyvinyl Alcohol (PVA) to create a dispersion medium by ensuring the homogeneous distribution of the organic phase in the form of droplets,• 0.74-0.82% by weight of Benzoyl Peroxide (BPO) to provide initiator properties for the copolymerization reaction between the monomer and the cross-linking agent,• 3.72-4.12% by weight of Titanium Dioxide (TiO2) to provide photocatalyst properties for the heterogeneous photocatalysis process and decolorization,• 32.01 -35.41 % by weight of Toluene to ensure that the polymers have a porous and large surface area by evaporating from the reaction medium,• 16.97-18.77% by weight of Divinyl Benzene to make the polymers hard, inert, and network-structured by being used as a cross-linking agent during polymerization,• 36.63-40.63% by weight of 4-Vinylpyridine (4-VP) to be used as a monomer during polymerization,• 3.72-4.12% by weight of Barium Ferrite to provide magnetic properties to the polymers.

2. A composition for treating wastewater by using polymer composite particles with magnetic and photocatalytic properties to remove dyes from wastewater and prevent the formation of environmentally harmful waste loads according to Claim 1 , wherein the composition includes polymer composite particles with magnetic and photocatalytic properties characterized by containing a photocatalyst polymer synthesized through the copolymerization of 4-vinylpyridine and divinylbenzene, and employing both adsorption and heterogeneous photocatalysis methods to remove pollutants from the wastewater.

3. A method for producing a wastewater treatment composite material, characterized by the following steps;A. Preparation of the dispersion phase,B. Preparation of the organic phase,C. Preparation of the polymerization medium,D. Subjecting the polymers formed as a result of polymerization to processes of precipitation, filtration, and separation,E. Drying the polymer matrix composites formed in step D in an ovenIn order to obtain a polymer composite with magnetic and photocatalytic properties that eliminates pollution in wastewater by using both adsorption and heterogeneous photocatalysis methods, the method for producing wastewater cleaning composite materials is characterized by the following steps:• in step A the dispersion phase is being prepared by adding 1.12-1 .22% by weight of polyvinyl alcohol (PVA) to 5% by weight of pure water and mixing the mixture in a heater using a magnetic stirrer until it becomes homogeneous,• in step B the organic phase is being prepared by adding 0.74-0.82% by weight of Benzoyl Peroxide as a reaction initiator and 32.01 -35.41% by weight of toluene to provide pore-forming properties,• in step C the polymerization medium is being prepared by adding 3.72-4.12% by weight of barium ferrite and 3.72-4.12% by weight of titanium dioxide to a cylindrical polymerization reactor, along with the dispersion phase prepared in step A and the organic phase prepared in step B, and mixing at 70°C and 400 rpm until homogeneous,• In step D, after the precipitation process of the polymers formed as a result of polymerization in step C is complete, the dispersion phase prepared in step A is filtered to separate the particles. The obtained particles are then washed in a water-ethyl alcohol mixture to remove unreacted monomers and solvents.• in step E the drying process is being performed for at least 48 hours.

Images