WO2015145380A2 - Dispositif flottant photocatalytique pour l'éradication de larves, et ses utilisations - Google Patents

Dispositif flottant photocatalytique pour l'éradication de larves, et ses utilisations Download PDF

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Publication number
WO2015145380A2
WO2015145380A2 PCT/IB2015/052213 IB2015052213W WO2015145380A2 WO 2015145380 A2 WO2015145380 A2 WO 2015145380A2 IB 2015052213 W IB2015052213 W IB 2015052213W WO 2015145380 A2 WO2015145380 A2 WO 2015145380A2
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WIPO (PCT)
Prior art keywords
larvae
floating device
catalyst
photocatalytic
oxide
Prior art date
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Ceased
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PCT/IB2015/052213
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English (en)
Portuguese (pt)
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WO2015145380A3 (fr
Inventor
Henrique DOS SANTOS OLIVEIRA
Luiz Carlos ALVES DE OLIVEIRA
Jadson Claudio Belchior
Geison Voga Pereira
Victor AUGUSTO ARAUJO DE FREITAS
Geraldo Magela De Lima
Rodinei AUGUSTI
Marcio GUIMARÃES COELHO
Fabricio Vieira De Andrade
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidade Federal de Minas Gerais
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Universidade Federal de Minas Gerais
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Publication date
Priority claimed from BR132014007098-1A external-priority patent/BR132014007098E2/pt
Priority claimed from BR132014011499A external-priority patent/BR132014011499E2/pt
Application filed by Universidade Federal de Minas Gerais filed Critical Universidade Federal de Minas Gerais
Priority claimed from BR132015006676A external-priority patent/BR132015006676E2/pt
Publication of WO2015145380A2 publication Critical patent/WO2015145380A2/fr
Publication of WO2015145380A3 publication Critical patent/WO2015145380A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C02F1/72—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
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to photocatalyst floating devices consisting of autoclaved cellular concrete or microreticulated polymeric microfiber, such as non-limiting example, TNT (nonwoven fabric), containing separate or combined Fe, Nb, Zn and Ti oxides. among themselves and uses.
  • Applications include photocatalysis, so with the in situ generation of radicals, the hydroxyl radical ( ⁇ ⁇ ), as well as the radicals ⁇ 2 ⁇ " and ⁇ 2 ⁇ . Therefore, the formed radical acts as a strong oxidant, directly attacking the larva, and thus allowing their eradication.
  • This process and method can be used where water may accumulate such as water tanks, house slabs and aquatic systems that allow larvae to develop.
  • This material can be used to degrade microorganisms such as bacteria, fungi, plankton that serve as a food base for insect vector larvae such as dengue, yellow fever, malaria, leishmaniasis, among others.
  • the catalyst when in contact with the aqueous environment under sunlight or artificial illumination in the ultraviolet range produces the hydroxyl radical (OH *) with a standard oxidation potential of 2.8 eV. This radical degrades organic compounds to the level of total mineralization.
  • the present invention has efficiency where there may be water accumulation such as water tanks, house slabs and / or aquatic systems that allow the development of larvae.
  • the density, porosity and mechanical strength of the substrates containing the oxide (s) make them very suitable for use in the process of degradation of dissolved organic material in aquatic environments with strong application potential to prevent the proliferation of disease-transmitting vectors that have as their initial stage of development the aquatic environment.
  • the activity of catalysts determines the operationalization of chemical reactions important for various industrial sectors in the production of substrates, removal of impurities, decontamination of industrial waste, decontamination of environments that accumulate water, among others.
  • addition of the catalyst to the reaction medium should take into consideration physical and chemical aspects, such as the area of contact of the catalyst with the substrates, and the catalyst recovery or disposal process.
  • Photocatalysis is an alternative and / or complement to many known processes for the treatment and decontamination of aquifers and wastewater.
  • an innovative technology is one that meets the principles of green chemistry and presents low cost, particularly, if possible, is able to contemplate the use of solar radiation (D. Robert, S Malato, Sci., Total Environ., 2002, 291, 85-97; D. Ravelli, D. Dondi, M. Fagnoni, A. Albini, Chem. Soc. Rev., 2009, 38, 1999-2011 1).
  • T1O2 is a 3.2 V band-spaced semiconductor (for the anatase polymorph), which is incompatible for visible radiation absorption and is active only for near ultraviolet radiation, specifically at wavelengths. smaller than 385 nm as described by Zhang et al., 1994 (Y. Zhang, JC Crittenden, DW Hand, DL Perram, Environ. Sci. Technol., 1994, 28, 435-442). Iron oxides are promising candidates for the development of photocatalysts sensitive to visible light.
  • Iron (III) oxides are n-type semiconductors with a band spacing of 2.1 V, have high stability under ambient conditions and in aqueous solution with pH 4.3, low toxicity, visible light absorbance, collect up to 45% of the widely available solar radiation spectrum and an affordable source of semiconductor materials.
  • hematite nanoparticles for example with high Specific area value and porous structure were obtained and showed good photocatalytic activity as proposed by Li and Koshizaki, 2010 (L. Li; N. Koshizaki, J. Mater. Chem., 2010, 20, 2972-2978). Therefore, the development of more efficient photocatalysts requires the combination of features such as high radiation absorption capacity, high catalytic efficiency and low cost.
  • photocatalysts Because it has better absorption and photocatalytic activity the most common configuration for photocatalysts is based on the use of solid materials, usually in nanometer scale, dispersed or supported in matrices with high specific area. However, obtaining an efficient photocatalyst presents challenges. The greatest difficulty is associated with the possibility of material reuse cycles. One desirable feature that commonly imposes practical limitations is the tendency of photocatalysts to be easily deactivated after some subsequent reactions. Also, any harmful consequences of the material to the environment must be strictly avoided.
  • Patent application BR0504197-0 "Process of treating aqueous effluents with organic contaminants using catalysts from Iron Ore and Hydrogen Peroxide”
  • Patent application BR0504197-0 "Process of treating aqueous effluents with organic contaminants using catalysts from Iron Ore and Hydrogen Peroxide”
  • Patent application PI0601465-8 "Process for the Preparation of a Physical Impregnated Supported Iron Oxide Catalyst", filed April 27, 2006, describes an iron oxide catalyst material ( III) supported on alumina, ⁇ -zeolite or silica that can be used in catalytic degradation of organic compounds with high resistance to biological degradation.
  • the present invention precisely fills this gap to contribute to the reduction or even elimination of disease vectors whose vector originates from its development in one of its phases in the aquatic phase.
  • the present invention is to utilize the advantages of low density commercially available floating water polymeric material, for example non-limiting polystyrene and / or polyurethane, to support semiconductor materials such as iron oxides, niobium and titanium.
  • the material is activated by the use of electromagnetic radiation in the UV range and visible to generate hydroxyl radicals, which are efficient in the oxidation of organic matter such as those found in the larvae of the mosquito Aedes aegypti or Anopheles in their early phase of development in water.
  • the devices and their uses, objects of the present invention exhibit efficiency, ease and practicality in their manufacturing process, as part of the raw material can be found in commerce.
  • the innovation consists in making use of the fluctuating property of the support that allows a higher incidence of solar radiation, important for light efficiency for photocatalyst activation, as well as its easy recovery at the end of the process and having a high degree of efficiency in attacking the larvae, for example. , not limiting, of Anopheles and Aedes aegypti.
  • Figure 1 presents the images before and after impregnation with iron, niobium and titanium and respective scanning electron microscopy images with the material prepared using the TNT matrix.
  • FIG. 2 shows removal of AM by photocatalysis using TNT-Fe (a) and removal of AM by photocatalysis using TNT-Nb (b).
  • Figure 3 shows the weekly evolution of the average live larvae count of Aedes aegypti in different aquatic environments containing sucrose solution for feeding larvae to TNT-Fe material.
  • Figure 4A shows a schematic representation of the generation of the hydroxyl radical (* OH) by the catalyst.
  • Figure 4B presents optical images indicating the result of the hydroxyl radical attack experiment. (catalyst) to the cell membrane of dengue mosquito larvae before and after the reaction process.
  • Figure 5 shows the 57 Fe Febauer spectroscopy.
  • Figure 6 shows the iron (III) phase distribution, where a) autoclaved cellular concrete and b) Fe2O3 catalyst / autoclaved cellular concrete.
  • Figure 7 shows the weekly evolution of the average live larvae count of Aedes aegypti in different aquatic media containing sucrose feed solution for the catalyst material Fe2O3 / autoclaved cellular concrete.
  • the present invention comprises photocatalyst floating devices consisting of transition metal oxides such as iron (III) oxide (Fe2O3), titanium (T1O2) oxide or niobium (V) (Nb2O6) oxide combined or not that they are attached to the microreticulated polymeric microfiber matrix, for example non-limiting, TNT (nonwoven fabric) or autoclaved cellular concrete.
  • the devices oxidize all organic matter in water, thus consuming food sources for larvae such as suspended organic material and microorganisms, eradicating insect larvae from diseases such as dengue fever, yellow fever, malaria, leishmaniasis, among others, including Aedes aegypti or Anopheles mosquito larva, non-limiting.
  • the material can also promote the degradation of cells of disease vector larvae, such as dengue, yellow fever, malaria, leishmaniasis, among others.
  • the invention may be employed in domestic or industrial aquatic environments with light incidence in household containers.
  • the present invention may also be characterized by not releasing toxic organic compounds into the aquatic environment that harm superior animals such as molluscs, fish, mammalian reptiles, among others.
  • the invention proposed herein is characterized by processes for the application and use of photocatalysis. None of the above described prior art supports apply to reduce or even eliminate organic matter from living beings with a focus on larvae that generate diseases such as yellow or dengue fever or chinkungunya (Aedes aegypti) or West Nile fever, or malaria ⁇ Anopheles). Thus, the present invention precisely fills this gap to contribute to the reduction or even elimination of disease vectors whose vector originates from its development in one of its phases in the aquatic phase.
  • Figure 1 shows the device when the matrix is TNT tissue.
  • TNT tissue Since the TNT tissue was immersed in Ti, Nb and / or Fe oxide solutions, it was subjected to mild heat treatment to form metal oxides.
  • the high photocatalytic activity of this material allows the removal of organic molecules, presenting low toxicity, high absorption of sunlight, versatility by flotation, besides the diffusional ease of contaminants and total elimination of insect larvae such as Aedes aegypti mosquito.
  • the materials were prepared by impregnating with different elements such as Fe, Nb, Zn and / or Ti a screen (eg nonwoven fabric / TNT) using different solutions containing the respective metals.
  • the polymeric support was maintained in contact with a 1.0 mol / l solution of Fe (NO 3 ) 3.9H 2 O, a 1.0 mol / l solution of [NH 4 NbO (C2O4) 2 (H 2 O)] (H 2 O) n and / or a 1.0 mol / l TiCb solution.
  • the screen was left in contact and stirred for 1 hour. After contact time the material was oven dried at 150 ° C for 12 hours.
  • TNT-Fe Polypropylene-based polymeric material (TNT) was purchased commercially and before being impregnated was washed with 1.0 mol / l HCl solution for 24 hours and then with 5.0 mol / l NaOH solution per 24 hours to remove impurities, and finally in distilled water.
  • TNT Polypropylene-based polymeric material
  • the photocatalytic activity of the materials was evaluated by the degradation of 20 mg / l of methylene blue (AM) organic dye at a constant temperature of 298K in a cylindrical photoreactor.
  • a high pressure mercury lamp (HPK 125 W-Philips) with a water-cooled filter served as a light source.
  • the total volume of the reaction solution was 20 mL.
  • AM dye discoloration was monitored over time by UV-Vis spectroscopy using the scan mode.
  • the screen After impregnation, the screen showed a characteristic reddish coloration of iron (III) oxide when the screen was treated with solution of this element. In addition to observing the morphology of the screen with and without iron, it was analyzed by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the screen consists of a floating weft microfiber from the SEM images; After impregnation with iron, niobium and / or titanium solutions, particles of the respective surface-adhered elements can be observed along the microfibres ( Figure 1), with a relatively homogeneous distribution in the material. The images clearly show clumps of sponge-shaped iron oxide particles.
  • the present patent application also deals with a new use of the non-limiting iron oxide (III) catalyst supported on an autoclaved cellular concrete matrix.
  • the method of preparation consists in impregnating a catalyst species precursor into the support matrix and then heat treating in an atmosphere suitable for the formation of the catalyst species (method described and claimed in patent application PM 002600-2).
  • the support matrix can be preformed into spheres or cubic (brick) shapes with a particle size ranging from 1 cm 3 to 10 cm 3 with the reduced size providing greater photocatalytic activity.
  • Catalyst manufacture has two stages: catalyst impregnation and activation.
  • the impregnation process consists of dipping the autoclaved cellular concrete in a solution of ferric chloride with concentration between 0.3 and 1 mol / L, for a period between 10 and 30 minutes.
  • the second step of the catalyst preparation process is to heat the autoclaved cellular concrete soaked in the precursor solution to a temperature between 100 ° C and 500 ° C for 1 to 4 hours with air atmosphere.
  • Table 1 shows the 57 Fe Mössbauer parameters for autoclaved cellular concrete samples before and after impregnation and heat treatment.
  • the determination of the iron content in the cellular concrete before the hematite impregnation process is 1.89% w / w and after the fixation of Fe2O3 in the matrix the iron content is 3.53% w / w.
  • the iron content is only twice that of the pre-existing amount, the catalytic activity of autoclaved cellular concrete is imperceptible, because according to the distribution analysis of iron-containing species, it is observed in Figure 5 that 40% of the iron content.
  • Early iron is in the forms of iron sulfide or metallic iron. Another important feature concerns the spatial distribution of the impregnated iron on the surface of the support matrix.
  • the pre-existing iron is homogeneously mixed in the autoclaved cellular concrete.
  • FIG. 7 shows the weekly evolution of the average amount of larvae developed for each type of solution.
  • the graph in Figure 7 demonstrates the efficiency of the catalyst in consuming organic matter from the aqueous medium, inhibiting insect larval proliferation.
  • the samples with bleach were efficient up to 8 weeks, when the first larvae began to appear, and at week 10 the behavior of these samples became similar to the control sample, without the addition of any oxidizing agent.
  • Example 4 Application test using TNT (nonwoven fabric) catalyst containing Fe, Nb, Zn and Ti oxides for oxidation of organic matter
  • the graph in Figure 3 demonstrates the efficiency of the catalyst in consuming organic matter from the aqueous medium, inhibiting the proliferation of insect larvae.
  • the samples with catalyst from week 6, the formation of some larvae was observed, however the larval population remained stable in a range between 17 to 23 larvae.
  • the samples with bleach were efficient up to 8 weeks, when the first larvae began to appear, and at week 10 the behavior of these samples became similar to the control sample, without the addition of any oxidizing agent.
  • Addition of the TNT-Fe catalyst consistently inhibited the formation of 100% of the larvae that could develop in solution I without loss of efficiency as with solution II.
  • Floating screens are particularly interesting for use in environmental remediation as they do not require agitation and mechanical oxygenation in large reservoirs.
  • the weft morphology of the fibers confers a good lighted area which favors a high rate of hydroxyl radical formation and consequently efficient oxidation.
  • the glass and / or bi-directional polymer, e.g. fiberglass, iron-containing screen was laid out in an ultrasonic bath for 30 min and the liquid was analyzed by atomic absorption spectrometry. The results did not show the presence of iron or its concentration was below the detection limit of the technique.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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Abstract

La présente invention concerne des dispositifs flottants photocatalyseurs, constitués de béton cellulaire autoclavé ou de microfibre polymère microréticulée, comme par exemple, non limitativement, le TNT (tissu non tissé), contenant des oxydes de Fe, Nb, Zn et Ti, séparés ou combinés entre eux, et leurs utilisations. Les applications incluent la photocatalyse, par conséquent avec la production in situ de radicaux, ou d'un radical hydroxyle (OH●), ainsi que les radicaux O2 ●- et HO2 ●. Les dispositifs oxydent toute la matière organique dans l'eau, éradiquant les larves d'insectes, y compris les larves des moustiques Aedes aegypti qui transmettent la fièvre jaune, la dengue ou le chikungunya (Aedes aegypti), ou de ceux qui transmettent la fièvre du Nil occidental ou la malaria (Anopheles). L'invention peut être utilisée dans des récipients domestiques et avec efficacité dans des lieux caractérisés par une accumulation d'eau.
PCT/IB2015/052213 2014-03-25 2015-03-25 Dispositif flottant photocatalytique pour l'éradication de larves, et ses utilisations Ceased WO2015145380A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
BR132014007098-1A BR132014007098E2 (pt) 2014-03-25 2014-03-25 uso de catalisador de óxido de ferro suportado em concreto celular autoclavado para erradicação de larvas de mosquitos
BRBR1320140070981 2014-03-25
BR132014011499A BR132014011499E2 (pt) 2014-05-13 2014-05-13 dispositivo flutuante polimérico fotocatalítico para erradicação de larvas
BRBR1320140114997 2014-05-13
BRBR1320150066766 2015-03-25
BR132015006676A BR132015006676E2 (pt) 2015-03-25 2015-03-25 dispositivo flutuante fotocatalítico para erradicação de larvas e usos

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WO2015145380A2 true WO2015145380A2 (fr) 2015-10-01
WO2015145380A3 WO2015145380A3 (fr) 2016-02-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110528170A (zh) * 2019-08-21 2019-12-03 杭州高烯科技有限公司 一种光催化自清洁的复合无纺布及其制备方法
WO2021027181A1 (fr) * 2019-08-09 2021-02-18 清华大学 Utilisation d'un matériau contenant du fer dans la préparation d'un produit destiné à inhiber la transmission du virus de la dengue

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000325796A (ja) * 1999-05-24 2000-11-28 Japan Organo Co Ltd 光触媒担持体及びその製造方法
US6803023B1 (en) * 1999-10-01 2004-10-12 Showa Denko Kabushiki Kaisha Composite structure for deodorization or wastewater treatment
WO2007043592A1 (fr) * 2005-10-11 2007-04-19 K2R Co., Ltd Appareil de production d’eau au moyen d’une réaction photocatalytique
JP2011156469A (ja) * 2010-01-29 2011-08-18 Daiken Corp 環境浄化材、その製造方法、環境浄化方法及び環境浄化材の回収方法
US20130118995A1 (en) * 2010-07-23 2013-05-16 Uvcleaning Systems, Inc. Solar-activated photochemical purification of fluids

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021027181A1 (fr) * 2019-08-09 2021-02-18 清华大学 Utilisation d'un matériau contenant du fer dans la préparation d'un produit destiné à inhiber la transmission du virus de la dengue
CN110528170A (zh) * 2019-08-21 2019-12-03 杭州高烯科技有限公司 一种光催化自清洁的复合无纺布及其制备方法

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