WO2010102592A1 - Matériau de filtration multicouche et dispositif pour la purification d'un milieu gazeux - Google Patents

Matériau de filtration multicouche et dispositif pour la purification d'un milieu gazeux Download PDF

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Publication number
WO2010102592A1
WO2010102592A1 PCT/CZ2010/000026 CZ2010000026W WO2010102592A1 WO 2010102592 A1 WO2010102592 A1 WO 2010102592A1 CZ 2010000026 W CZ2010000026 W CZ 2010000026W WO 2010102592 A1 WO2010102592 A1 WO 2010102592A1
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WO
WIPO (PCT)
Prior art keywords
radiation
filtration
layers
photocatalyzer
inert
Prior art date
Application number
PCT/CZ2010/000026
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English (en)
Inventor
Jiri Duchoslav
Lukas Rubacek
Original Assignee
Elmarco S.R.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elmarco S.R.O. filed Critical Elmarco S.R.O.
Publication of WO2010102592A1 publication Critical patent/WO2010102592A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents

Definitions

  • the invention relates to a layered filtration material containing a photocatalyzer from the group of metal oxides or semimetal oxides, especially TiC> 2 , ZnO, ZrO 2 or Si ⁇ 2, in a form of inorganic nanofibres and/or nanoparticles.
  • the invention also relates to a device for purification of gaseous medium, especially of air, comprising the, above mentioned layered filtration material.
  • metal oxides and semimetal oxides e.g. of TiO 2 , ZnO, ZrO 2 or SiO 2 is their catalytic activity under the action of UV radiation, which causes oxidation and degradation of organic substances on their surface or in its vicinity.
  • These oxides may be prepared in a form' of nanoparticles or nanofibres with high specific surface, ;while the specific surface is important parameter for the speed and efficiency of catalytic process, as with increasing specific surface also the speed and efficiency of catalytic process increases.
  • Ai - discloses a self-cleaning filtration membrane comprising a plate or a mat containing fibres and photocatalytic nanoparticles in vicinity or on surface of the fibres, while the fibres may contain microfibres and/or nanofibres and the nanoparticles may comprise the nanoparticles of TiO 2 .
  • the description of the application T also mentions layers of nanofibres produced from colloid solutions of inorganic materials such as TiO 2 , ZrO 2 or SiO 2 , while these nanofibres may be mixed with glass or inorganic microfibres to increase their mechanical strength.
  • This document further describes a cleaning device with self- cleaning nanofibrous membrane fastened in a body of the device in vicinity of inlet of contaminated air or liquid, which are delivered through the device by means of a fan or a pump, while they pass through the nanofibrous membrane, in which the contaminants are adsorbed on the surface of nanofibres. Behind the nanofibrous membrane there is arranged . a source of UV radiation, which continually or in interrupted manner radiates the nanofibrous membrane in ordef to decompose the contaminants adsorbed on the, surface of nanofibres.
  • the described self-cleaning filtration membrane contains polymeric microfibres and/or nanofibres,; on whose surface or inside the fibres in vicinity of their surface are photocatalytid nanoparticles, during the photo-catalysis and during irradiation by UV radiation, the ⁇ decomposition of polymer and overall destruction of such membrane occurs. At the same time there is a great danger of releasing the photocatalytic nanoparticles into the medium being purified.
  • the self-cleaning filtration membranes formed of nanofibres from inorganic materials such as TiO 2 , ZrO 2 or SiO 2 are very fragile and therefore are not capable of permanent operation at industrial utilisation, and there occurs breaking of nanofibres during installation, maintenance and also due to vibrations during operation and subsequently flying off or flushing off of these fragments into the medium being purified.
  • the fragility of the described inorganic nanofibres and their breaking is not eliminated even when they are mixed with inorganic or glass microfibres, which are of similar properties, and moreover they may be breaking during manipulation with the membrane or operation of the purification device.
  • the increasing quantity of microfibres deteriorates catalysing abilities of membrane.
  • US 2007/02844303 A1 discloses a nanofibrous structure or a membrane containing nanofibres of polymer insoluble in water, while the polymer fibres are enwrapped by TiO 2 , ZnO, SnO 2 .
  • the nanofibrous structure or membrane is designed for filtration and it cannot be utilised at exposure to UV radiation even for photocatalysis, because in this case degradation of polymeric nanofibres and destruction of the whole nanofibrous structure or membrane occurs.
  • WO 2008/034190 describes a ceramic filter for purification of water, which contains ceramic nanofibres applied onto a ceramic porous substrate, while the filter may be used also as a photocatalytic one.
  • the disadvantage of this solution are great pressure gradients, respectively very small flow rates of fluids through the filter due to small porosity of ceramic carrying substrate. The described flow rate is
  • Published patent application KR 1020080086066 A describes a photocatalytic filter using the nanofibres of metal oxide produced through electrostatic spinning and calcination process, production method of the photocatalytic filter and an air cleaner using the photocatalytic filter.
  • the nanofibres of metal oxide are formed of ZnO nanofibres or TiO 2 nanofibres.
  • the production method of photocatalytic .filter consists of following steps: creation of a first substrate in which a plurality of holes is performed; creation of nanofibres of metal oxide on the first substrate through electrostatic spinning; calcination of nanofibres of metal oxide created on the 'first substrate; and covering of calcinated nanofibres of metal oxide by a second substrate, in which a plurality of holes is performed.
  • the step of creation of nanofibres from metal oxide on the first substrate by means of electrostatic spinning consists of: electrostatic spinning of first nanofibres of metal oxide arranged in lateral or longitudinal direction on the first substrate; and electrostatic spinning of second nanofibres of metal oxide on the first nanofibres of metal oxide so that the second nanofibres of metal oxide are arranged in perpendicular direction to the direction of arrangement of the first nanofibres of metal oxide.
  • the disadvantage of this solution is complexity of production process and a very thin layer of nanofibres of metal oxide, which becomes after calcination even thinner. Maximum thickness of layer of nanofibres of metal oxide before calcination is 3 micrometers.
  • the holes in the first substrate may be partially clogged, by which the permeability of the filter to the air is worsened.
  • the goal of the invention is to reduce or to totally remove shortcomings of the background art and to, create a layered filtration material containing photocatalyzer suitable for photocatalytic purification of gases, especially of air.
  • a layered filtration material containing a photocatalyzer according to the invention whose principle consists in that the photocatalyzer is arranged between two inert filtration layers, which are inert towards action of the photocatalyzer and action of UV radiation, and at least one of them is permeable for UV radiation, while from outer sides of both inert filtration layers there are arranged polymeric nanofibrous layers.
  • polymeric nanofibrous layers serve only to prevent flying away of nanoparticles and/or nanofibres, possibly of parts of nanofibres of photocatalyzer outside the space of the layered filtration material delimited by polymeric nanofibrous layers.
  • these layers are from the outer side provided by abrasion-resistant layers, while at least that abrasion-resistant layer, which is arranged on " the side of inert filtration layer permeable for UV radiation, is also permeable for UV radiation.
  • the inert filtration layer permeable for UV radiation is formed of textile formation made of glass fibres.
  • one of the inert filtration layers is impermeable for UV radiation, it is formed of filtration paper for the purpose to reduce the costs for the layered filtration material.
  • the principle of the device for purification of gaseous medium, especially of air, containing the above mentioned layered filtration material consists in that, at least one side of the layered filtration material is subjected to action of UV radiation, while all layers' irradiated by UV radiation in front of the photocatalyzer are formed of materials permeable for UV radiation.
  • Exemplary embodiment of the layered filtration material according to the invention is schematically " represented on the drawings, where the Fig. 1 represents distribution of layers of filtration material, the Fig. 2 a view of non-woven textile of glass fibres when magnified 600 times, the-Fig. 3 a view of polymeric nanofibrous layer with 600 times magnification, the Fig. 4 a view of nanoparticles of photocatalyzer with 600 times magnification and the Fig. 5 a view of inorganic nanofibrous layer of photocatalyzer with 600 times magnification.
  • the layered filtration material according to the example of embodiment represented in the Fig. 1 contains first inert filtration layer ⁇ , formed e.g. of a filtration paper or textile formation of glass fibres or other material being resistant towards action of photocatalyzer and action of UV radiation, on which there is applied a layer 2 of photocatalyzer from the group of metals or semimetals especially T ⁇ O2, ZnO, Zr 1 O 2 ,or SiO 2 , in a form of inorganic nanofibres and/or nanoparticles and/or particles, which is covered by second inert filtration layer 3, which is permeable to UV radiation and is formed for example of a textile formation of glass fibres.
  • first inert filtration layer ⁇ formed e.g. of a filtration paper or textile formation of glass fibres or other material being resistant towards action of photocatalyzer and action of UV radiation
  • first polymeric nanofibrous layer 4 On outer side of the first inert filtration layer 1 there is applied first polymeric nanofibrous layer 4, which is from its outer side protected by first abrasion resistant layer 6.
  • second polymeric nanofibrous layer 5 permeable for UV radiation On outer side of the second filtration layer 3 there is applied second polymeric nanofibrous layer 5 permeable for UV radiation, which is from its outer side protected by second abrasion-resistant layer 7, which is permeable for UV radiation.
  • the first and the second polymeric layers 4, 6 prevent flying away of nanoparticles of photocatalyzer from the layer 2 of photocatalyzer both during manipulation with layered filtration material and operation, and they may be made of any suitable polymer, for example of polyacrylonitrile (PAN) or of PA6.
  • PAN polyacrylonitrile
  • the nanoparticles are applied on the first inert filtration layer ⁇ in a dry or wet state.
  • Thickness of the layer 2 of photocatalyzer is chosen taking into account technological conditions, in which the filter with layered filtration material will be operated, especially the size of nanoparticles of photocatalyzer and their specific surface, flow rate. ' . ' of gas being purified, guantity of impurities, which should be removed from the gas being purified and possibilities of penetration of UV radiation through entire thickness of the layer 2 of photocatalyzer.
  • the basis weight of the layer 2 of photocatalyzer varies usually from 20 g/m 2 to 60 g/m 2 .
  • both inert filtration layers are from their outer side overlaid by polymeric nanofibrous Iayersi4, 5, which are from their outer side protected by abrasion-resistant layers 6, 7/
  • polymeric nanofibrous layers 4, 5 are applied on respective abrasion-resistant layers 6, 7 in device for production of nanofibres through electrostatic spinning, e.g. according to WO2005/024101, CZ ' patent 299527, WO2008/028428, eventually WO2009/010020 or through any known method.
  • the layer ; 2 : ⁇ f photocatalyzer is formed of a layer of inorganic nanofibres formed of selected photocatalyzer from the group of metals or semimetals, especially Tidif- ' ZnO, Zr ⁇ 2 or SiC ⁇ 2.
  • the first inert filtration layer ⁇ _ and/or the second inert filtration layer 3 is made of material which is resistant to calcination temperatures at production of inorganic nanofibres, e.g.
  • the layer 2 of photocatalyzer may be created through electrostatic spinning on this substrate and during assembly of the layered filtration material this two-layered textile may be used, on which the nanofibrous layer 2 of photocatalyzer is already to be found, as the first inert filtration layer ⁇ or as the second inert filtrati ⁇ n ⁇ yer 3. If there is need to increase thickness of the layer 2 of photocatalyzer, two two-layered textiles with nanofibrous layer 2 of photocatalyzer may be ? us"ed r : and assembled with nanofibrous layers 2 of photocatalyzer against each f pther.
  • the layer of inorganic nanofibres formed of the selected photocatalyzer from the group of metals or semimetals, especially TiC ⁇ , ZnO, ZrO ⁇ or SiC>2, may be produced through electrostatic spinning also as separate layer
  • nanofibrous layer of photocatalyzer does not show sufficient consistency and strength, it is advantageous to break it into nanofibres and to apply them on the first or the second inert filtration layer 1 or 3 likewise above described nanoparticles of photocatalyzer.
  • UV radiation which side of the layered filtration material the UV radiation will be radiating, as the inert filtration layer on the side reversed from the source of UV radiation may be made of material impermeable or less permeable to UV radiation, e.g. of filtration paper or viscose, while the inert filtration layer from the side of radiating of UV radiation must be sufficiently permeable for UV radiation. Nevertheless in some cases it is advantageous, if UV radiation is radiating from both sides of the layered filtration material. In this case for both inert filtration layers it is necessary to use material sufficiently permeable for UV radiation.
  • the installation of such layered filtration material into filtration device is simplified, as both inert filtration layers are equivalent and it therefore does not matter with which side it is positioned to the source of UV radiation.
  • the polymeric nanofibrous layers 4, 5 may be different, out of which the layer which is in the direction of passage of the purified air the front one may have lower basis weight, which usually lies within an interval of 0,05 to 0,8 g/m 2 , while the rear polymeric nanofibrous layer usually has higher basis weight, which usually lies within an interval of 0,8 to 1 g/m 2 . This prevents flying away of nanoparticles, especially if the layer 2 of photocatalyzer is created of nanoparticles.
  • a reinforcement grid may be inserted between the layers of layered filtration material.
  • the device for purification of gaseous medium, especially air of organic pollutants and other organic substances and/or microorganisms comprises the layered filtration material, which contains the photocatalyzer from group of metal oxides or semimetal oxides,' especially T ⁇ O 2 , ZnO, ZrO 2 or SiO 2 in the form of inorganic nanofibres and/or nanoparticles, and the source of UV radiation.
  • the photocatalyzer is arranged in the layer 2 of photocatalyzer between two inert filtration layers 1, 3, which are inert towards action of photocatalyzer and action of UV radiation, and at least one of them is permeable for UV radiation, while from outer side of inert filtration layers 1, 3 there are arranged polymeric nanofibrous layers 4, 5 and the source of UV radiation is arranged in direction of passage of the purified gaseous medium before and/or behind the layered filtration material, while the source of UV radiation is directed towards the layered filtration material, whose irradiated side is made of, materials permeable for UV radiation up to the photocatalyzer.
  • the source of UV radiation may also be the daylight.
  • the layered filtration material according to the invention is able to remove microorganisms, organic pollutants and other organic substances present in the air or from other suitable gas being purified, both in trace amount or industrial amount very well, and therefore is applicable in photocatalytic devices for purification of air or other gases, for example in the air-conditioning devices. From the purified gas, by means of photo-catalysis, it is possible to eliminate essentially any organic substance from the group of hydrocarbons, alcohols, aldehydes, ketones, organic acids, etc. The result of photocatalysis is CO 2 and H 2 O.

Abstract

L'invention porte sur un matériau de filtration multicouche contenant un photocatalyseur issu d'un groupe d'oxydes métalliques ou d'oxydes semi-métalliques, en particulier constitué de TiO2, ZnO, ZrO2 ou SiO2, sous la forme de nanofibres et/ou nanoparticules inorganiques, alors que le photocatalyseur est disposé entre deux couches de filtration inertes (1, 3), qui sont inertes vis-à-vis de l'action du photocatalyseur et de l'action d'un rayonnement UV, et au moins l'une d'elles est perméable à un rayonnement UV, alors qu'à partir des côtés externes des deux couches de filtration inertes (1, 3), sont disposées des couches de nanofibres polymères (4, 5). L'invention porte également sur un dispositif pour la purification d'un milieu gazeux, en particulier de l'air, comprenant le matériau de filtration multicouche mentionné ci-dessus.
PCT/CZ2010/000026 2009-03-10 2010-03-03 Matériau de filtration multicouche et dispositif pour la purification d'un milieu gazeux WO2010102592A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ20090152A CZ2009152A3 (cs) 2009-03-10 2009-03-10 Vrstvený filtracní materiál a zarízení pro cištení plynného média
CZPV2009-152 2009-03-10

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WO2010102592A1 true WO2010102592A1 (fr) 2010-09-16

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CZ (1) CZ2009152A3 (fr)
WO (1) WO2010102592A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103610431A (zh) * 2013-11-27 2014-03-05 苏州凯丽达电器有限公司 一种复合过滤网
CN111850734A (zh) * 2020-06-28 2020-10-30 浙江真爱毯业科技有限公司 一种可见光驱动净化室内空气的拉舍尔挂毯

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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CZ305320B6 (cs) * 2013-09-13 2015-07-29 Technická univerzita v Liberci Lineární textilní útvar typu jádro-plášť obsahující plášť z polymerních nanovláken a filtrační prostředek pro filtrování plynných médií

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WO2008127406A2 (fr) * 2006-11-08 2008-10-23 Shell Oil Company Membrane de séparation de gaz comportant un substrat avec une couche de particules d'oxyde inorganiques revêtues et une surcouche d'un matériau sélectif de gaz, ainsi que sa fabrication et son utilisation
WO2009010020A2 (fr) 2007-07-17 2009-01-22 Elmarco S.R.O, Procédé servant à filer une matrice liquide, dispositif pour la production de nanofibres par filage électrostatique de matrice liquide et électrode de filage pour un tel dispositif
EP2030674A1 (fr) * 2007-08-31 2009-03-04 The Technical University of Denmark Membrane avec microstructure de taille stable et son procédé de production
CZ2008277A3 (cs) 2008-05-06 2009-11-18 Elmarco S.R.O. Zpusob výroby anorganických nanovláken elektrostatickým zvláknováním

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* Cited by examiner, † Cited by third party
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US20040116025A1 (en) * 2002-12-17 2004-06-17 Gogins Mark A. Air permeable garment and fabric with integral aerosol filtration
WO2005024101A1 (fr) 2003-09-08 2005-03-17 Technicka Univerzita V Liberci Procede de production de nanofibres par filage electrostatique a partir d'une solution polymere et dispositif associe
US20070284303A1 (en) 2004-08-23 2007-12-13 Christopher Drew Nanometer scale structures
EP1674014A1 (fr) * 2004-12-24 2006-06-28 FiberMark Gessner GmbH & Co. Sac à poussières d'aspirateur avec effet d'élimination des odeurs
CZ299537B6 (cs) 2005-06-07 2008-08-27 Elmarco, S. R. O. Zpusob a zarízení k výrobe nanovláken z polymerního roztoku elektrostatickým zvláknováním
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US20070134407A1 (en) * 2005-12-12 2007-06-14 Byd Company Limited Fabrication methods for catalyst coated membranes
US20070151921A1 (en) 2006-01-03 2007-07-05 Ceo Espinex Inc. Self-cleaning filtration nanofiber membrane
WO2008028428A1 (fr) 2006-09-04 2008-03-13 Elmarco S.R.O. Électrode de filage tournante
WO2008034190A1 (fr) 2006-09-21 2008-03-27 Queensland University Of Technology Filtre constitué de nanofibres d'oxyde métallique
WO2008127406A2 (fr) * 2006-11-08 2008-10-23 Shell Oil Company Membrane de séparation de gaz comportant un substrat avec une couche de particules d'oxyde inorganiques revêtues et une surcouche d'un matériau sélectif de gaz, ainsi que sa fabrication et son utilisation
KR20080086066A (ko) 2007-03-21 2008-09-25 인하대학교 산학협력단 금속산화물 나노섬유를 이용한 광촉매 필터, 그 제조방법및 그를 이용한 공기정화장치
WO2008118955A1 (fr) * 2007-03-27 2008-10-02 Danaldson Company, Inc. Tissu composite de haute durabilité
WO2009010020A2 (fr) 2007-07-17 2009-01-22 Elmarco S.R.O, Procédé servant à filer une matrice liquide, dispositif pour la production de nanofibres par filage électrostatique de matrice liquide et électrode de filage pour un tel dispositif
EP2030674A1 (fr) * 2007-08-31 2009-03-04 The Technical University of Denmark Membrane avec microstructure de taille stable et son procédé de production
CZ2008277A3 (cs) 2008-05-06 2009-11-18 Elmarco S.R.O. Zpusob výroby anorganických nanovláken elektrostatickým zvláknováním

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103610431A (zh) * 2013-11-27 2014-03-05 苏州凯丽达电器有限公司 一种复合过滤网
CN111850734A (zh) * 2020-06-28 2020-10-30 浙江真爱毯业科技有限公司 一种可见光驱动净化室内空气的拉舍尔挂毯
CN111850734B (zh) * 2020-06-28 2023-03-03 浙江真爱毯业科技有限公司 一种可见光驱动净化室内空气的拉舍尔挂毯

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