WO2023219581A1 - Utilisation de particules composites de matrice de polymère m-[poly(éthylèneglycol iméthacrylate-2-vinylpyridine)]-tio2 magnétique et photocatalytique dans le traitement d'eaux usées provenant des textiles - Google Patents

Utilisation de particules composites de matrice de polymère m-[poly(éthylèneglycol iméthacrylate-2-vinylpyridine)]-tio2 magnétique et photocatalytique dans le traitement d'eaux usées provenant des textiles Download PDF

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Publication number
WO2023219581A1
WO2023219581A1 PCT/TR2022/050493 TR2022050493W WO2023219581A1 WO 2023219581 A1 WO2023219581 A1 WO 2023219581A1 TR 2022050493 W TR2022050493 W TR 2022050493W WO 2023219581 A1 WO2023219581 A1 WO 2023219581A1
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WIPO (PCT)
Prior art keywords
polymer matrix
matrix composite
range
composite particles
magnetic
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Application number
PCT/TR2022/050493
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English (en)
Inventor
Ali Kara
Şeyma YALÇIN
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Bursa Uludağ Üni̇versi̇tesi̇
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Publication of WO2023219581A1 publication Critical patent/WO2023219581A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the invention relates to magnetic and photocatalytic polymer matrix composite particles developed for use in the treatment of wastewater generated in the textile industry.
  • the polymer composite contains ethylene-glycol-dimethacrylate, magnetite, benzoyl peroxide, or 2,2-bis azo butyronitrile, polyvinyl alcohol, toluene and titanium dioxide-based photocatalyst and vinyl phosphonic acid.
  • VP vinyl pyridine
  • the Chinese patent application with publication numbered CN109206554A relates to the ion imprinted polymer material, and the preparation method and application of the said material.
  • m- [poly(ethyleneglycoldimethacrylate-2-vinylpyridine]-Ti02 polymer matrix composite specifically and the treatment of textile wastewater in this way.
  • the present invention relates to polymer magnetic and photocatalytic polymer matrix composite particles that meet the requirements mentioned above, eliminate all disadvantages and provide some additional advantages.
  • the main objective of the invention is to obtain magnetic and photocatalytic polymer matrix composite particles to be used for fast, easy, non-toxic, high efficiency treatment of dyestuffs from aqueous solution without causing secondary pollution in the textile industry, by using the methods of adsorption and decolorization together. Since the particles in question are sensitive to the magnetic field, they can be easily removed from the aqueous solution with the help of an external magnet.
  • Figure 2 the density graph of polymer matrix composite particles versus magnetic field is given.
  • the invention relates to magnetic and photocatalytic polymer matrix composite particles developed for use in the treatment of wastewater generated in the textile industry.
  • Particles of the invention include Ethyleneglycoldimethacrylate (EGDMA), Vinyl pyridine (VP), Polyvinyl Alcohol (PVA), Toluene, Magnetite (FesC i), TiOs and Benzoyl Peroxide.
  • the polymer matrix composite particle content which is the subject of the invention, further comprises Ethyleneglycoldimethacrylate (EGDMA) in the range of 35 - 40 % Vinyl pyridine (VP) in the range of 15 - 20 %, Polyvinyl Alcohol (PVA ) in the range of 0.5 - 1 %, Toluene in the range of 40 - 45 %, Magnetite (FesO ⁇ in the range of 2 - 3 %, TiOs in the range of 2 - 3 % and Benzoyl Peroxide in the range of 0.4 - 1 % by weight.
  • EGDMA Ethyleneglycoldimethacrylate
  • VP Vinyl pyridine
  • PVA Polyvinyl Alcohol
  • Toluene in the range of 40 - 45 %
  • Magnetite FesO ⁇ in the range of 2 - 3 %
  • TiOs in the range of 2 - 3 %
  • Benzoyl Peroxide in the range
  • polymer matrix composite particle comprises preferably 35.21 % Ethyleneglycoldimethacrylate (EGDMA), 18.72 % Vinyl pyridine (VP), 0.92 % Polyvinyl Alcohol (PVA), 40.05 % Toluene, 2.32 % Magnetite (FesO ⁇ , 2.32 % TiOs and 0.46 % Benzoyl Peroxide.
  • EGDMA Ethyleneglycoldimethacrylate
  • VP Vinyl pyridine
  • PVA Polyvinyl Alcohol
  • Toluene 2.32 % Magnetite (FesO ⁇ , 2.32 % TiOs and 0.46 % Benzoyl Peroxide.
  • m-poly(EGDMA-VP)]-Ti02 synthesis is carried out by suspension polymerization method.
  • PVA Polyvinyl Alcohol
  • a magnetic stirrer heater until it dissolves in 50 mL of pure water and the dispersion phase is prepared.
  • 0.1 grams of benzoyl peroxide (initiator) is added preferably into 10 mL of toluene (pore maker) and mixed.
  • preferably magnetic stirrer with heater is used.
  • the polymer matrix composite particle precipitation is left to settle (preferably by washing in a water-ethyl alcohol mixture) and the dispersion phase is filtered.
  • a vacuum oven is used, and drying is carried out preferably at 40 - 90 G (preferably 70 G) for 48 hours.
  • Ethyleneglycoldimethacrylate (EGDMA) as a crosslinker
  • VP Vinyl pyridine
  • the polymer particles have a reticulated, porous and large surface area.
  • TiOs is used as the photocatalyst, and after the adsorption process, the dyestuffs are left to remain in the solution. This way, nearly 100 % removal is achieved and secondary pollution is prevented at the same time.
  • FesC binds to the polymer, making the polymer matrix composite particles sensitive to magnetic field. Since the polymers are sensitive to particle magnetic field, they are easily removed from the aqueous solution with the help of an external magnet after adsorption and decolorization.
  • AIBN 2,2-bisazobutyronitrile
  • benzoyl peroxide Cumene hydroperoxide
  • Di-tert-butyl Peroxide Di-tert-butyl Peroxide
  • butyl perbenzoate can be used instead of benzoyl peroxide as initiator.
  • Pure water can be used instead of ethyl alcohol to purify the synthesized particles from unreacted monomers and solvents.
  • Divinyl benzene instead of Ethyleneglycoldimethacrylate (EGDMA), and Benzene instead of Toluene in the invention.
  • EGDMA Ethyleneglycoldimethacrylate
  • FTIR spectroscopy is used to give information about the state of bonds in polymer matrix composite particles and to illuminate the structure.
  • the basis of IR spectroscopy is based on the absorption of rays in the infrared region by the vibrational motions of the molecule.
  • FTIR spectroscopy of the polymer matrix composite particles, which is the subject of the invention is given in Figure 1 .
  • the peak at 1141 cm -1 describes the C - O bond in the same ester group.
  • Electron spin resonance method was used to determine the magnetic properties of polymer matrix composite particles.
  • the basis of the ESR method is the excitation of unpaired electrons in the material using microwave frequencies.
  • the ESR spectrum is created by keeping the frequency of the microwave constant and changing the magnetic field strength.
  • the density graph of the polymer matrix composite particles against magnetic field is given in Figure 2. Materials with magnetic properties become magnetized when placed in a magnetic field.
  • the g factor is the factor expressing the contribution of spin motions to magnetization.
  • h Planck’s constant (6.626 x 10 -27 erg/s)
  • v Frequency (See from data, Hz)
  • the g factor is important for the identification of a material. It is FesC magnetic nanoparticles that impart magnetic properties to polymer matrix composite particles. FesC particles contain Fe 2+ and Fe 3+ ions in their structure. At room temperature, Fe 3+ ions can be easily observed in the ESR spectrum. In the literature, the g factor for Fe 3+ ions is in the range of 1 .4-3 for low spin complexes, and the g factor is between 2-9.7 for high spin complexes. The g factor for the polymer matrix composite [m-poly(EGDMA-2-VP)]- TiO 2 particles synthesized within the scope of the invention is 3.79, which indicates that this material has magnetic properties.
  • the specific surface area of polymer matrix composite particles was determined by BET analysis.
  • the N 2 adsorption-desorption isotherm seen in Figure 3 is classified as type-IV isotherm and there is capillary condensation in the region between 0.58 - 08 and this indicates the uniformity of the distribution of mesopore sizes.
  • the average pore diameter distribution of polymer matrix composite particles is given in Figure 4. According to lUPAC's classification, pores larger than 50 nm in diameter are macropores, pores in the range of 2 - 50 nm are mesopores, and pores smaller than 2 nm are micropores. The pore sizes are in the range of 2.38 - 4.19 nm. It indicates that these particles contain mesopores.
  • XRD images of the synthesized polymer composites are given in Figure 5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des particules composites de matrice polymère magnétiques et photocatalytiques mises au point pour être utilisées dans le traitement des eaux usées générées par l'industrie textile.
PCT/TR2022/050493 2022-05-13 2022-05-26 Utilisation de particules composites de matrice de polymère m-[poly(éthylèneglycol iméthacrylate-2-vinylpyridine)]-tio2 magnétique et photocatalytique dans le traitement d'eaux usées provenant des textiles WO2023219581A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022/007799A TR2022007799A2 (tr) 2022-05-13 2022-05-13 Manyetik-Fotokatalitik m-[poli(etilenglikoldimetakrilat-2-vinilpiridin)]-TiO2 Polimer Martisli Kompozit Partiküllerinin Tekstil Atık Sularının Arıtılmasında Kullanımı
TR2022/007799 2022-05-13

Publications (1)

Publication Number Publication Date
WO2023219581A1 true WO2023219581A1 (fr) 2023-11-16

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PCT/TR2022/050493 WO2023219581A1 (fr) 2022-05-13 2022-05-26 Utilisation de particules composites de matrice de polymère m-[poly(éthylèneglycol iméthacrylate-2-vinylpyridine)]-tio2 magnétique et photocatalytique dans le traitement d'eaux usées provenant des textiles

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TR (1) TR2022007799A2 (fr)
WO (1) WO2023219581A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104624175A (zh) * 2015-02-13 2015-05-20 厦门大学 一种纳米磁性吸附剂及其制备方法
WO2017060311A1 (fr) * 2015-10-05 2017-04-13 Universidad Del País Vasco/Euskal Herriko Unibertsitatea Procédé de préparation de particules composites comprenant un noyau magnétique et un revêtement photocatalytiquement actif, et particules composites pouvant être obtenues par ledit procédé

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104624175A (zh) * 2015-02-13 2015-05-20 厦门大学 一种纳米磁性吸附剂及其制备方法
WO2017060311A1 (fr) * 2015-10-05 2017-04-13 Universidad Del País Vasco/Euskal Herriko Unibertsitatea Procédé de préparation de particules composites comprenant un noyau magnétique et un revêtement photocatalytiquement actif, et particules composites pouvant être obtenues par ledit procédé

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