Purifier containing a photocatalytic filter

i

MEDIA FOR PHOTOCATALYTIC FILTER

The invention relates to a filter medium with a fibrous structure, the fibers of which are coated with a coating with photocatalytic action, for the purification of the ambient air and more particularly the elimination of organo-volatile compounds contained in the ambient air.

The so-called Advanced Oxidation techniques oxidize organo-volatile compounds (VOCs). The most effective Advanced Oxidation Techniques (TAO) are those which lead to the formation of OH 'hydroxyl radicals, which have an oxidizing power greater than that of traditional oxidants. This is the case with heterogeneous photocatalysis. The fundamental principle of the phenomenon is the absorption of a photon by a solid semiconductor, leading to the promotion of an electron from the valence band to the conduction band by releasing a gap, and thus giving the solid properties oxidizer and reducer. Most organovolatile compounds as well as many pesticides, herbicides, surfactants and dyes are completely oxidized to less toxic products by this technique.

A PCO (oxidation photocatalysis) reactor for the purification of ambient air generally comprises a pre-filter to trap dust and particles, a UV source, a PCO filter. The UV source is generally placed between the pre-filter and the PCO filter. The air to be purified is generally pulsed or sucked through the PCO filter using a turbine or a fan.

To be operational, a PCO filter must be optimized on the following points:

- UV power received,

- flow rate of the purifier,

- speed of passage of pollutants through the medium,

- inertia of the media and the PCO coating to the action of UV rays and hydroxyl radicals,

- pressure drop generated by the PCO media,

- limitation of the creation of potentially toxic intermediate compounds also known under the name of by-products or by-products.

In air treatment applications, the sizing of the various elements, fans, ducts, motor power are directly linked to the pressure drop, the pressure drop depending on the various filtration elements of the system, including the PCO media. This point is fundamental both from the point of view of the cost of the air handling unit and of its energy operating cost. It is the present inventors who have noted the importance of the issue of the pressure drop generated by the filter media.

The filters already proposed for this type of application often cause too great a pressure drop, so that they require the use of more powerful and more energy-intensive fans. To overcome this drawback, it was then proposed to lower the density of the filter by inserting elements such as honeycomb, fabric with a high porosity rate, mosquito net or ceramic foam, but then real preferential channels were created and the efficiency of the filter for the oxidation of organo-volatile compounds was reduced because of the little effective material in contact with the air flow.

W003010106 teaches the deposition of photocatalytic coating on the surface of silica webs or felts with a specific surface area of ​​at least 10 m²/ g, in particular at least equal to 30 m²/ g. This document does not suggest the concept of low pressure drop combined with sufficient efficiency in the intended application.

As documents of the prior art, mention may also be made of US4732879A1. This document teaches the deposition of a porous catalytic coating on a flexible fibrous substrate composed of glass or ceramic fibers. This document suggests the use of such a substrate in “filter bag” applications.

The invention relates to an essentially mineral filtering medium, stable, insensitive to UV and to PCO oxidation, this medium combining a pressure drop compatible with the requirements of air treatment systems and high efficiency with regard to atmospheric pollutants due to of its active surface and of a PCO effect in its volume and not only a surface effect as is usually encountered according to the prior art.

The filter medium according to the invention is obtained after depositing a coating with photocatalytic action on a nonwoven of the felt type.

The invention relates firstly to a filter media with photocatalytic action at least 2 mm thick, homogeneous and without opening visible to the naked eye, comprising a felt of inorganic fibers, the fibers of which are coated with a coating comprising a catalyst with photocatalytic action, said felt having a basis weight of between 30 and 80 g / m², said coating representing 5 to 80% of the mass of said media, said media exhibiting a gas pressure drop of less than 150 Pa at 1 m / s in non-pleated condition.

The invention also relates to the use of this medium in various applications, its shaping in order to increase the frontal active surface as much as possible, its shaping in order to reduce as much as possible the problems of pressure drop.

The invention also relates to a method and a device for modulating the UV intensity and the speed at the level of the substrate at the start of a scrubber and / or in the event of a pollution peak, so as to reduce the formation of reaction intermediates which may be toxic.

Finally, other subjects of the invention are the applications of the PCO media and of the PCO scrubber system in the treatment of gaseous ozone effluents in indoor, domestic or industrial air atmospheres, of alcohol and solvent vapors in industries that are strong users of these products (composites, perfume manufacturing, etc.).

The media according to the invention can be used to purify the atmosphere of premises for domestic use (housing), or of premises in the tertiary sector (building containing offices). In general, it is possible to use a felt with a basis weight of up to 300 g / m². However, the felt used in the context of the present invention, due to its weight per unit area of ​​between 30 and 80 g / m², offers a very low pressure drop to the gas passing through it. The felt and the media according to the invention are more suitable for purification in a domestic environment. Note that for the tertiary or industrial sector, substrates of greater surface density may be necessary, such as, for example, 200 to 300 g / m². An alternative for the tertiary and industrial sectors is the use of several media according to the invention placed in series one behind the other. For these sectors, it is also possible to use a single filter medium comprising a felt on which the catalytic coating has been applied as explained in the present application, except that the felt has a basis weight greater than 80 g / m², for example 80 to 300 g / m². You can also put several of these media in series one behind the other.

The felt to be used as a substrate may have a density of less than 30 kg / m³ The felt to be used as a substrate generally has a density ranging from 0.5 to 60 kg / m³ and more generally from 1 to 30 kg / m³.

The photocatalytic coating formed according to the invention on the surface of the fibers of the felt used as a substrate represents 5 to 80% and generally 10 to 50% of the mass of the filter medium.

The catalyst with photocatalytic action generally comprises at least one oxide from the group of the following oxides: T1O2, ZnO, CeO2. It preferably comprises at least partially crystallized titanium oxide.

Felt is a fibrous structure made from mineral fibers. These fibers can be silica-based such as glass (generally containing at least 30% by weight of silica, glass can be of the E, C, R, S, D, AR type), washed glass (leached glass fiber chemically then possibly thermally stabilized, generally containing more than 90% by weight of silica, and in a standard manner between 96% and 99% by weight of silica), ceramic (we can cite mullite-based fibers of which UNIFRAX.THERMALS CERAMICS are well-known suppliers, NEXTEL fibers from 3M, pure alumina fiber marketed under the trade name SAFFIL) or pure silica (also called quartz and comprising at least 99% of SiO₂ amorphous).

Some glass compositions suitable within the scope of the present invention are given in Table 1 below:

<td></td><td>Type E glass</td><td>Type C glass</td><td>glass type AR</td>

<td>SIO2</td><td> 53-55%</td><td> 60-65%</td><td> 61%</td>

<td>AI2O3</td><td> 14-15%</td><td> 3,5- 6 %</td><td> /</td>

<td>CaO</td><td> 17-23%</td><td> 14%</td><td> 5%</td>

<td>MgO</td><td> 1%</td><td> 3%</td><td> /</td>

<td>NâjOg</td><td> 0.8%</td><td> 10%</td><td> 17%</td>

<td>B2O3</td><td> 0-8%</td><td> 5%</td><td> /</td>

<td>F02O3</td><td> 0,3%</td><td> 0,5%</td><td> 0,3%</td>

<td>TiO₂</td><td> 0,5%</td><td> /</td><td> /</td>

<td>ZrO₂</td><td> /</td><td> /</td><td> 10%</td>

Table 1

Metal fiber can also be used (generally based on 316 or 316 L stainless steel, the main suppliers of which are Bekaert and UGITECH). The material used is preferably glass and even more preferably silica in order to be as transparent as possible to UV illumination in the application, because UV then penetrates better into the heart of the filtering medium to make it more active.

To make a felt of fibers comprising silica, one can for example proceed by stretching rods of fused silica with a diameter of less than 7 mm in an oxy-propane burner in order to bring them to a filament diameter of less than 5/10 mm. . This filament can then be re-stretched by flame stretch-blowing in a second burner and projected onto a receiving belt or drum. The filaments thus obtained generally have a diameter of less than 50 μm, and optimally centered on 9 μm, for example between 7 and 15 μm. Larger filaments generally cause the felt to lose flexibility. By this process, several tens of filaments can be drawn simultaneously. The stretched material may be of the quartz, silica or glass type, and more generally any type of thermo-fusible inorganic material, which includes alumina and mullite.

The felt thus obtained is a nonwoven, the basis weight of which is adjustable as a function of the speed of the receiving system (such as a rotating drum). The reception system is adjusted so as to obtain a density between 30 and 80 g / m². These felts have a thickness ranging from 1 to 200 mm and a density less than 60 kg / m³. The final medium has a thickness generally less than that of the felt used, and generally ranging from 1 to 50 mm and more generally between 2 and 30 mm.

Alternatively to this drawing process, it is possible to start from already existing fibers with a diameter of 7 to 14 μm which are cut to lengths less than 150 mm and generally greater than 45 mm. The cut fibers are then shaped into a web either by pneumatic lapping or by carding-lapping. The web thus formed then undergoes pre-needling followed by needling at around 100 strokes / m². Using this methodology, slicks with a surface mass of between 60 g / m² and 2000 g / m²can be achieved. In the PCO applications concerned by the present invention, products with a grammage of less than 80 g / m² will be privileged. These products have thicknesses generally less than 30 mm, and generally densities less than 70 kg / m³ and even less than 60 kg / m³The density and thickness are adjustable by those skilled in the art according to the number of strokes / m² of substrate exerted by needling, which densifies the felt to a greater or lesser extent.

The media can also be prepared by the papermaking route (dispersion of the fibers in a pulper followed by shaping by the papermaking wet route) by using, in order to keep an essentially mineral structure, a precursor ceramic binder preferably of the sol type. gel, in particular with a precursor, for example of the TEOS (Tetraethyl orthosilicate), MTES (Methyltriethoxysilane) type which, after calcination, will ceramize. This binder can be deposited locally by point or according to a predefined pattern in order to preserve the flexibility of the felt.

With the processes which have just been mentioned, a felt is obtained without a hole visible to the naked eye.

The preferred fiber as a support felt for the catalyst with photocatalytic action is a quartz fiber (at least 99% silica) because it well supports the ceramization of the silica sol-gel (between 400 and 600 ° C), it is very pure, free of alkalis, and therefore particularly inert with respect to the catalyst, and moreover, it conducts UV rays very well without absorbing them.

The finished felt is then impregnated with a solution comprising an organic silica precursor (such as TEOS, MTES see a mixture of several precursors of alkoxysilane type of chemical formula R '_xIf (OR)₄-_x in which R and R 'are organic radicals and x an integer ranging from 0 to 3), and a dispersion of a compound with photocatalytic action, such as TiO₂ photocatalytic action or Zinc oxide (ZnO), titanium oxide nevertheless remaining the preferred catalyst due to its high efficiency in PCO applications. The invention also relates to a method of manufacturing a medium comprising a step of impregnating the felt of inorganic fibers with a composition comprising tetraethyl orthosilicate (TEOS) and at least one alkoxysilane of formula R '._xIf (OR)₄-x in which R and R 'are organic radicals and x is an integer ranging from 0 to 3, the amount of alkoxysilane representing 10 to 40% and preferably 15 to 25% of the weight of TEOS.

The impregnation solution can be prepared according to the indications contained in WO9710186 and W003087002. By way of example, the impregnation solution can be prepared by premixing a solution A (silica precursor) and a solution B (surfactant), a dispersion of titanium oxide then being added to said premix. By way of example, it can be prepared on the basis of the ingredients indicated in Table 2 below:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td rowspan="3">Solution A</td><td>TEOS</td><td>PROLABO ref 24 004.290</td><td> 5</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 8,34</td>

<td>H₂O demineralized pH 1.25 (1M HCl)</td><td>PROLABO ref 30 024.290</td><td> 4,29</td>

<td rowspan="2">Solution B</td><td>Polymer block propylene oxide and ethylene oxide</td><td>BASF PE6200</td><td> 3,85</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 40,28</td>

<td>Adding A to B</td><td>A + B</td><td></td><td> 61,76</td>

<td>Catalyst C</td><td>P25 (TiO₂at 19.3% in water)</td><td>DEGUSSA</td><td> 33,33</td>

<td>Adding C to (A + B)</td><td>C + (A + B)</td><td></td><td> 95,09</td>

Table 2

The amount of water is adjusted to obtain a volume of 100 liters at the level of the final solution. Two solutions A and B are therefore prepared which are mixed, then a suspension of the TiO catalyst is added.₂ in water to this mixture of A + B. The 33.33 kg of C is the mass of suspension of the 19.3% catalyst (and not of pure catalyst).

Table 3 below gives a second example of the preparation of an impregnation solution:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td></td><td>TEOS (d = 0.93)</td><td>PROLABO ref 24 004,290</td><td> 9,90</td>

<td>Solution A</td><td>Absolute ethanol (d = 0.79)</td><td>PROLABO ref 20 821,467</td><td> 8,34</td>

<td>(Ingredients are mixed until limpid, then we exercise a heating to 60 ° C for 1 hour or at 50 ° C more long time)</td><td>H₂O demineralized pH 1.25 (HCl 1M ref 30 024.290)</td><td>PROLABO</td><td> 4,29</td>

<td></td><td>Polymer Oxide block</td><td>BASF</td><td> 3,85</td>

<td>Solution B</td><td>propylene and oxide ethylene</td><td>PE6800</td><td></td>

<td>(Ingredients are mixed until dissolution of PE6800)</td><td>Absolute ethanol (d = 0.79) ref 20 821.467</td><td>PROLABO</td><td> 40,28</td>

<td>Adding A to B</td><td>A + B</td><td></td><td> 66,67</td>

<td>Catalyst C</td><td>TiO₂at 19.3% in water</td><td>MILLENNIUM S5 300A</td><td> 33,33</td>

<td>Adding C in (A + B)</td><td>C + (A + B)</td><td></td><td> 100</td>

Table 3

A composition particularly suitable for depositing the coating involves, as silica precursor, a mixture of MTES and TEOS. In fact, the sol-gel obtained from this mixture is more flexible and less subject to powdering when compared to a 100% TEOS or 100% MTES precursor. Preferably, a mixture of 15-30% MTES for 85-70% TEOS is used.

The felt is impregnated in full bath with the impregnation solution, the latter being sucked through the felt, which is then expressed (which means: pressed to remove the impregnation juice) and dried.

The felt obtained is then calcined at a temperature of from room temperature to 550 ° C., in particular at approximately 450 ° C., which then makes it possible to convert the silica precursor into silica. Preferably, the temperature rise to the maximum temperature is carried out with a moderate speed, preferably less than 6 ° C. per minute. By way of example, this heat treatment can be that indicated in table 4 below:

<td>Temperature</td><td>Bearing</td><td>Temperature rise rate up to the level</td>

<td>ambient</td><td></td><td></td>

<td>100 ° C</td><td>2h</td><td>3 ° C / min</td>

<td>150 ° C</td><td>2h</td><td>3 ° C / min</td>

<td>175 ° C</td><td>2h</td><td>2 ° C / min</td>

<td>200 ° C</td><td>10 minutes</td><td>3 ° C / min</td>

<td>300 ° C</td><td>1h</td><td>2 ° C / min</td>

<td>450 ° C</td><td>1h</td><td>1 ° C / min</td>

Table 4

Cooling can be natural cooling in the ambient air.

The filter medium with photocatalytic action according to the invention is thus obtained. This media can be sucked up by a suction table in order to remove particles (micron and sub micron) from coating with low adhesion. This makes it possible to avoid significant dusting of the PCO media and generation of particles during the first start-ups of the PCO scrubber.

It can be mounted in cassette and photocatalytic reactor systems.

The mass of catalyst (such as TiO₂) is generally less than or equal to 40% by weight and if possible less than 30% by weight, optimally about 15% by weight on the final product (media) obtained. Preferably, the mass of catalyst is greater than or equal to 1% by weight of the final medium.

In certain types of application (bactericidal application, destruction of ozone and type H sulfur compounds₂S or DMDS (Dimethyl2919811 ίο disulfide of formula CH₃-SS-CH₃)) the composition can be doped with at least one compound such as MnO, Mn₂O₃, dicyanoanthracene (DCA) or a compound comprising at least one of the elements of the group of elements V, Cr, Mn, Mo, In, Sn, Fe, Ce, Co, Cu, Nd, Zn, W, Nb, Ta, Bi, Ni, Ru, Ag, said compound being in a concentration of less than 0.5% by mass of the mass of catalyst, in order to accentuate the efficiency of the media.

The felts prepared as indicated above have the following properties:

- they are essentially mineral in nature;

- They exhibit a pressure drop of less than 150 Pa at 1 m / s, and more generally less than 50 Pa at 1 m / s and even less than 20 Pa at 1 m / s of gas;

- They are homogeneous and therefore without a preferential path for the gas passing through it;

- they do not have a hole visible to the naked eye.

The production of the photocatalytic coating can sometimes pose problems of adhesion to the fiber, in particular when the latter is subjected to mechanical stresses, even low, for example during handling. Detachment of the coating results in the formation of an unwanted powder. This detachment is also called “powdering”.

To reduce this powder formation, the thickness of the coating can be reduced. The coating can also be fixed using a polymer. The latter must however resist oxidation under the combined effect of UV and the PCO effect of the catalyst, the powers received very often being between 2 and 40 mW / cm² of UVA, UVB or UVC.

It has been discovered that polymers comprising fluorine, such as polytetrafluroethylene (PTFE) or a fluorinated silane (such as the fluorosilanes sold under the reference F8820, F8810, F8263 by the company DEGUSSA), and to a lesser extent a polysiloxane polymer (such as a silicone ), have sufficient UV and PCO reaction stability in this type of application. The polymer can be deposited on the fibers of the media in the state of dispersion in a liquid, in particular using an aqueous dispersion. Preferably, an aqueous dispersion of the polymer free of surfactant or containing as little surfactant as possible is used. Indeed, with certain type of surfactant used for these dispersions, for example to disperse PTFE, a strong odor may appear in the application at the start of the use of the filter medium, due to the degradation of the surfactant. under the PCO action. Suitable polymer dispersions are, for example, the PTFE dispersions sold under the references TEFLON 30 B, TEFLON 304 A, TEFLON B, TEFLON-3823, sold by the company DUPONT DE NEMOURS. Mention may also be made of silicone polymers of Rhodia silicone such as Rhodorsil Resin 20 B at 83%, Rhodorsil Resin 6405, siloxane polymers from Wacker such as SILRES H62 C. PTFE is a preferred polymer.

The polymer dispersion is applied to the medium after the ceramization heat treatment which has led to the formation of the photocatalytic action coating. Generally 0.1 to 5% by weight of polymer relative to the mass of the final media is deposited on the media. The deposition of the polymer can be carried out either by spraying on one side or on both sides of the suspension, or by immersion-soaking in the suspension followed by squeezing. These impregnations can generally be carried out at ambient temperature, in particular at a temperature between 10 and 40 ° C. For the case where the dispersion of the polymer comprises a surfactant, preferably, a heat treatment is carried out generally between 45 ° C and 250 ° C (rather between 150 and 250 ° C in the case of a fluoropolymer (not of polysiloxane type), for example a few minutes at 230 ° C and rather between 100 and 180 ° C in the case of a fluorinated polysiloxane) or UV (in this case at high UV intensity, in particular between 15 and 100 mW / cm²) after the application of the polymer dispersion and before the actual use in order to better remove the surfactants or surfactants used to disperse the polymer in the dispersion, in particular the fluoropolymers in aqueous dispersion.

Fortuitously, it has also been discovered that the PCO substrates whose coating comprises a hydrophobic polymer, in particular fluorinated or of the polysiloxane type, can float on the surface of the water. Such media are of great interest for purifying the atmosphere emanating from a settling basin, a treatment plant, a lagoon (factories), etc. ... Indeed, the media can be cut into pieces of surface ranging from a few mm² a few cm², poured on the surface of the water to be treated. Due to its floating nature, the medium is easily distributed on the surface of the water (without adding significant additional costs such as floating tarpaulins mounted on a float). The media then adsorbs the pollutants emanating from the polluted water and oxidizes them under the action of solar UV rays. This principle is very economical in order to very appreciably reduce the nauseating and sometimes dangerous fumes in terms of chemical compounds of this type of installation. Thus, the invention also relates to a process for purifying the air above water containing impurities and generating organo volatile compounds in the air above said water, by placing it on the surface of the water. a filter media with photocatalytic action, self-floating (according to the invention), by means of a suitable coating allowing it to float. This coating preferably comprises a hydrophobic polymer applied to the fibers of said media.

The media according to the present invention combines an active and homogeneous surface (with no apparent preferential path for the air) over the entire surface of the media with a very low pressure drop, in particular due to its very low basis weight (or surface weight) and of its associated low bulk density. In addition, since the medium is very thick, it makes it possible to have photocatalytic oxidation efficiency (PCO efficiency) throughout its thickness.

A simple way to characterize the photocatalytic activity of a medium is to test in cross mode the percentage of degradation of a specific pollutant, such as methanol, in a laboratory reactor. To this end, a reactor developed by the team of Professor PICHAT from the Ecole Centrale de Lyon is commonly used in universities and laboratories. This reactor generally consists of a stainless steel body inside which is placed a media disc, for example with a diameter of 47 mm. In the upper part of the reactor, UV illumination from a 125 W HPK lamp is produced through a silica slit. The illumination power is regulated by adjusting the Media lamp distance. A power of 5 mW of UVA per cm² of media, measured at 365 nm measured at the media level, is generally used. Upstream of the reactor, a constant flow of filtered air containing 300 ppm of the pollutant (in particular methanol) is introduced at a rate of 350 ml / min. Downstream of the reactor after PCO treatment, the pollutant concentration is then measured, generally by chromatography. It is important to ensure mineralization (conversion to CO₂ and H₂O) of the pollutant by checking the chemical balance so as not to have only pure adsorption phenomena as can be found with systems of the activated carbon type. This test applied to methanol is called “methanol test” hereinafter.

The filter media according to the invention, in non-pleated condition, causes a pressure drop of less than 150 Pa at 1 m / s of gas, and even generally less than 50 Pa at 1 m / s and even less than 20 Pa at 1 m / s of gas, which is remarkably low, while providing excellent purification.

In the event of a high concentration of pollutant in the atmosphere to be treated (for example during pollution peaks or at the start of the depollution treatment by the filtering medium according to the invention, which can easily be detected by sensors of organovolatil compounds) , the formation of intermediate products such as formaldehyde, acetaldehyde or acetone is all the more marked the higher the flow rate and / or the UV power. These derivatives being for some particularly toxic, in order to mitigate their formation, it is then recommended (if these particular conditions occur), momentarily, to:

- greatly reduce the UV intensity and / or

- greatly reduce the flow rate of the purifier, that is to say the speed of passage of the gas to be treated through the filtering medium.

By combining these two actions, a photocatalytic scrubber allows efficient air purification without increasing the levels of harmful intermediates during the first minutes of device start-up or the flow of the pollutant peak. Subsequently, the UV intensity and the flow of the device can be returned to their nominal value in order to ensure a maximum PCO effect.

In order to further increase the efficiency of the photocatalytic reactor system according to the invention, it is possible to play on the increase in the surface area of ​​active media and the reduction in the pressure drop. If the installation of several filtering media in series makes it possible to increase the active surface, the pressure drop is however increased correspondingly. In order to achieve this objective, it is possible to combine the increase in the surface area of ​​active photocatalytic media with an increase in the frontal surface, the pressure drop being all the lower the greater the frontal surface in contact with the air flow. . To this end, the medium according to the invention can be placed in a filtration cassette so as to provide a longer surface area for the gas to be treated. Thus, instead of being arranged in a simple linear thickness transversely with respect to the direction of the gas, it can be given a shape comprising at least one angle, such as a V, W, etc. "Accordion") or give it a pleated structure. The media can also be placed in articulated cassettes following the previous designs allowing the cassette to be placed in a reactor with the minimum wasted space. This point is particularly interesting in domestic air conditioning systems. In fact, very often, the suction ducts are bent very quickly behind the dust filtration elements. As the PCO scrubber systems are placed in the dust filtration zone, the size of the PCO reactor must be limited. Such an articulated cassette system makes it possible to dispense with the bulk of an angle system (s) for its installation while taking advantage of the angle shape (s) once in the working position, which makes it possible to reduce the pressure drop in the system. The cassette can therefore be inserted straight (without an angle) into the slot allowing it to be introduced into the PCO reactor and the angle shape (s) is automatically taken inside the reactor at the time of insertion. FIGS. 3a and 3b show PCO filters inside which the PCO medium has a V or W shape. Thus, the invention also relates to a filter cassette comprising at least one angle and containing a PCO medium, said angle being if necessary articulated.

The PCO scrubber according to the invention is intended in particular for domestic air purification applications. One of the major applications is ozone reduction in domestic environments. Thanks to the invention, an ozone reduction efficiency of 90% can be achieved.

The PCO scrubber according to the invention is also used for the purification of air in a tertiary, commercial or industrial environment. In this type of application, it is recommended to use media according to the invention in series to generate a higher density compared to what is suitable for the domestic environment. For example, in the context of use in an industrial catering environment equipped with a grease cleaning system (from ozone), a media at 50 g / m² does not generally allow the reduction of sufficiently high ozone levels up to 300 ppb in one pass at 1 m / s. It is then necessary to use media according to the invention in series (that is to say one after the other, where appropriate in contact), generally between 2 to 10 media, more particularly 3 to 6 media, which makes it possible in one pass to oxidize for example 150 ppb of the 300 ppb of ozone present in the inlet gas, the UV power received by the filter being 50 mW / cm² UVC illumination. This type of process can be envisaged in particular at the level of industrial kitchen appliances in which ozone is generated to eliminate the grease deposited at the level of the collection hoods of the kitchens. This results in a strong odor and concentration of ozone which can be destroyed by the PCO system according to the invention.

The PCO system according to the invention can also be used in industrial applications such as sheds or refrigerators for storing fragile plant products (such as fruits, vegetables, flowers). In this context, it is important to reduce the ethylene concentration in the shed to slow down the ripening of the fruits or the wilting of the flowers. The invention also relates to the use of the medium or of the purifier or of the device according to the invention for purifying the air of a shed or of a refrigerator containing a plant, in particular a fruit or vegetable or a flower.

The PCO system according to the invention is also very effective on the degradation of alcohols (methanol, ethanol, propanol) and of solvents, for example used in the industry of resins, composites or the manufacture of perfumes. In this type of application, it is necessary to work under ATEX regulated conditions (the ATEX expression coming from “Explosive ATmospheres”) in order to avoid any risk of explosion. One of the issues is the nature of the PCO filter media which must be essentially mineral in order to avoid any risk of inflammation. In particular, preferably, for ATEX applications, polymer post-impregnation is not applied to the medium in order to limit dusting. The medium of the present invention is then composed of a mineral substrate (felt) with a mineral coating doped with titanium oxide and perfectly meets the specifications of PCO applications in ATEX environment.

The PCO system according to the invention contains a light source necessary for the catalytic activation of the titanium oxide coating. This source can be a UVA, UVB or UVC mercury or xenon vapor lamp.

Furthermore, the invention also relates to devices for the particular illumination of a PCO medium, suitable for the PCO medium according to the invention or any other PCO medium. These devices are particularly interesting from the point of view of energy savings, reduction in maintenance costs or ATEX compliance.

The device for illuminating the fibrous media can be produced with a UVA, UVB or UVC LED with an illumination power of at least 1 mW / cm². Such a system makes it possible to combine minimal energy consumption with significant efficiency. In addition, this type of lighting system allows very specific designs with optimization of the lighting of the media. Thus, the invention also relates to a gas purifier comprising a filtering medium with photocatalytic action (according to the invention or not) and a system for illumination by UV of said medium, said illumination system comprising an LED, preferably UV, generating an intensity received by the media at least equal to 1 mW / cm² of media.

The device for illuminating the fibrous media can be produced by a light guide, for example an optical fiber: this system makes it possible to move the source away from the illumination zone and thus relatively easily create an ATEX zone in the PCO reactor. . Thus, the invention also relates to a gas purifier comprising a filtering medium with photocatalytic action (according to the invention or not) and a system for illumination by UV of said medium, said illumination system comprising at least one light guide ( like an optical fiber) to bring light to said media. In industrial applications, it is not uncommon to find ATEX zones (outlets, capture). To date, conventional UV lamps are not ATEX approved because of the fragility of their casing. A light guide lighting system allows the lamp to be taken out of the ATEX zone and thus makes the system compliant with the requirements of ATEX zones. The following systems can be considered:

• from a UV source it is possible to bring several strands of light guide (for example of the optical fiber type) into the reactor. These strands serve as a guide to bring light energy into the reactor. For example, we can consider a toron every cm² of substrate so as to distribute the UV energy as homogeneously as possible in the reactor. The principle of such a system is shown in figure 14.

• from a source, a single strand of light guide (like optical fiber) can be brought into the reactor. This strand then illuminates a reflector or a mirror provided with a suitable curvature and the UV light is reflected by this mirror or this reflector as homogeneously as possible in the reactor. The principle of this system is shown in figure 15. The use of any other diffuser system can also make it possible to achieve this objective.

The device for illuminating the fibrous media can also be centralized with respect to several PCO reactors. This makes it possible to have a single UV generation zone relayed by an illumination system by light guide (for example of the optical fiber type) of different PCO media. This system provides a significant energy gain by avoiding the need to have multiple sources, reducing the consumption of ballasts and the inevitable losses due to multi-source systems. The principle of this system is shown in FIG. 16. Thus, the invention also relates to a device for purifying the air comprising several air purifiers each comprising a filtering medium with photocatalytic action (according to the invention or not), and comprising a single media illumination source from scrubbers.

Thus, the invention also relates to a gas purifier comprising a filtering medium with photocatalytic action (according to the invention or not) and a system for illumination by UV of said medium, said illumination system comprising light guides (for example fiber optic type) and / or cold light.

The device for illuminating the fibrous media can be produced by a flat lamp. This system allows extremely homogeneous illumination of the entire surface of the PCO media and at the same time increases the oxidation efficiency and therefore the efficiency of the system. Thus, the invention also relates to a gas purifier comprising a filtering medium with photocatalytic action (according to the invention or not) and a system for illumination by UV of said medium, said illumination system comprising a flat lamp.

When operating the PCO system in an atmosphere polluted with VOCs, the concentration of these VOCs can be quite high at the start of operation. This high VOC concentration can result in the unwanted formation of intermediate compounds (formaldehyde, acetaldehyde, acetone) which are also harmful following the operation of the PCO system according to the invention. This is why it is recommended, in the event of a supposedly high VOC concentration, to start the operation of the PCO system according to the invention in attenuated mode, either by reducing the UV power, or by reducing the gas flow, or both. . After a while, when the VOC concentration is lower, the operating power can be increased. A UV attenuated illumination (for a start of operation) is for example less than 8 and even less than 7.5 mW / cm². An attenuated gas flow rate is for example less than 60% and even 50% of the nominal gas flow rate. Table 5 below gives the concentrations of certain VOCs commonly measured in living rooms. These values ​​are the results of several hundred measurements. The right column “critical concentration” of Table 5 indicates, by way of indication, the concentrations from which it is recommended to reduce the operating regime of the PCO scrubber according to the invention, by reducing the gas flow through it and / or by reducing the UV intensity illuminating the PCO media. The invention therefore relates to a process for purifying gas using a scrubber comprising a filtering medium with photocatalytic action (according to the invention or not) and a system for illumination by UV of said medium, so that when the concentration of a compound in the gas is greater than a value V1, the operating speed of the purifier is lower than its speed when the concentration of the compound in the gas is less than a value V2, V2 being less than or equal to V1 . In the case of formaldehyde (very common impurity), it is recommended to reduce the operating speed of the scrubber when the formaldehyde concentration is greater than 30 pg / m3. The operating speed can be increased when the formaldehyde concentration is less than 30 pg / m3. More generally, the scrubber can be operated with a reduced operating speed when the formaldehyde concentration is greater than a V1 value of between 0.3 and 80 pg / m3 then increase the operating speed when the formaldehyde concentration is lower. at a V2 value between 0.3 and 80 pg / m3, V2 being less than or equal to V1.

<td rowspan="3"></td><td colspan="3">Usual values ​​(living rooms)</td><td></td>

<td>Median</td><td>Minimum</td><td>Maximum</td><td>Concentration critical</td>

<td>ug / m³</td><td>ug / m³</td><td>ug / m³</td><td>ug / m³</td>

<td>Formaldehyde</td><td> 24,0</td><td> 2,0</td><td> 74,8</td><td> 30,0</td>

<td>Hexaldehyde</td><td> 17,0</td><td> 0,7</td><td> 138,0</td><td> 22,0</td>

<td>Toluene</td><td> 15,6</td><td> 3,6</td><td> 145,2</td><td> 20,0</td>

<td>Acetaldehyde</td><td> 12,0</td><td> 1,4</td><td> 78,0</td><td> 15,0</td>

<td>Limonene</td><td> 8,9</td><td> 1,5</td><td> 71,2</td><td> 11,0</td>

<td>Isobutyraldehyde / Butyraldehyde</td><td> 8,8</td><td> 0,7</td><td> 24,0</td><td> 11,0</td>

<td>Undecane</td><td> 6,9</td><td> 1,1</td><td> 146,2</td><td> 8,0</td>

<td>a-Pinene</td><td> 5,9</td><td> 0,7</td><td> 262,1</td><td> 7,0</td>

<td>Decane</td><td> 5,9</td><td> 0,7</td><td> 105,5</td><td> 7,0</td>

<td>Valeraldehyde</td><td> 5,0</td><td> 0,7</td><td> 27,0</td><td> 6,0</td>

<td>(m + p) -Xylenes</td><td> 4,7</td><td> 1,6</td><td> 76,7</td><td> 6,0</td>

<td>1,2,4-Trimethylbenzene</td><td> 2,4</td><td> 0,7</td><td> 55,4</td><td> 4,0</td>

<td>Isovaleraldehyde</td><td> 2,1</td><td> 2,1</td><td> 3,0</td><td> 4,0</td>

<td>Ethylbenzene</td><td> 2,0</td><td> 0,7</td><td> 24,5</td><td> 4,0</td>

<td>o-Xylene</td><td> 1,8</td><td> 0,7</td><td> 24,6</td><td> 4,0</td>

<td>Benzene</td><td> 1,8</td><td> 0,7</td><td> 14,1</td><td> 4,0</td>

<td>1-Methoxy-2-propanol</td><td> 1,7</td><td> 0,7</td><td> 32,1</td><td> 4,0</td>

<td>Tetrachlorethylene</td><td> 1,4</td><td> 0,7</td><td> 73,6</td><td> 4,0</td>

<td>Butyl acetate</td><td> 1,4</td><td> 0,7</td><td> 40,9</td><td> 4,0</td>

<td>1,4-Dichlorobenzene</td><td> 1,4</td><td> 0,7</td><td> 293,2</td><td> 4,0</td>

<td>2-Ethyl-1-hexanol</td><td> 1,0</td><td> 0,7</td><td> 12,1</td><td> 3,0</td>

<td>2-Butoxyethanol</td><td> 0,7</td><td> 0,7</td><td> 14,0</td><td> 2,0</td>

<td>1,1,1-Trichloroethane</td><td> 0,7</td><td> 0,7</td><td> 6,1</td><td> 2,0</td>

<td>Trichlorethylene</td><td> 0,7</td><td> 0,7</td><td> 41,8</td><td> 2,0</td>

<td>Styrene</td><td> 0,7</td><td> 0,7</td><td> 5,3</td><td> 2,0</td>

<td>2-Ethoxyethanol</td><td> 0,7</td><td> 0,7</td><td> 7,6</td><td> 2,0</td>

<td>2-Ethoxyethyl acetate</td><td> 0,7</td><td> 0,7</td><td> 2,2</td><td> 2,0</td>

<td>Benzaldehyde</td><td> 0,7</td><td> 0,7</td><td> 2,0</td><td> 2,0</td>

Table 5

In order to be able to detect whether the gas to be purified (generally air) exceeds the values ​​for which it is recommended to reduce the power of the purifier, the purifier according to the invention is advantageously provided with an organovolatil compound analyzer. . The purifier can operate in a fully automated manner depending on the contents of organovolatil compound transmitted by the analyzer: high speed when the content is below a certain value, low speed when the content is greater than a certain value.

Thus, the invention also relates to a gas purifier (generally air) comprising a filtering medium with photocatalytic action (according to the invention or not) comprising a means for varying the flow of gas passing through it or (which means and / or) variation of the intensity of the UV illumination. The scrubber may include an organo volatile compound analyzer and a means for automatically adjusting the speed of the gas passing through it or for adjusting the intensity of the UV illumination as a function of the content of organo volatile compound analyzed by the analyzer. . The scrubber can analyze the incoming gas or the outgoing gas, but usually analyzes the incoming gas.

The adjustment of the gas speed and / or the light intensity can also be quite simply modulated as a function of time. For example, when starting a scrubber in a room containing pollutants, it is recommended to work with a low gas speed and / or low UV illumination for example for 2 hours, the time to have sufficiently purified the room, then to switch to nominal speed. Such a system prevents the formation of by-products, for example when the purifier is started. The scrubber can therefore include a timing means (that is to say a means measuring or determining the time or triggering a device after a certain time) making it possible to control the moderate or higher speed of the scrubber. . The purifier can therefore comprise a timing means and a means for automatically adjusting the speed of the gas passing through it and / or for adjusting the intensity of the UV illumination as a function of the time determined by the timing means. This time-based system can be called upon, when a pollution peak is detected by a system independent or not of the scrubber, such as for example an information communicated to the radio, to put the system in standby mode. reduced speed (low gas speed and / or low UV illumination) for a predefined time, the higher purification mode then automatically started at the end of the predefined time.

FIG. 1 very schematically represents the structure of a PCO scrubber according to the invention, containing two layers 2 of PCO media. The gas flow is represented by thick arrows, the left arrow representing the incoming gas, the right arrow representing the outgoing gas. Between the two layers 2 of PCO media are placed UV lamps 3. A fan 5 ensures the air circulation. All these elements are placed in a stainless steel box 1. The distance 4 between the UV lamp and the media can be 20 mm. Such a purifier could also include a particle pre-filter as soon as the air arrives, that is to say placed to the left of the first PCO media.

FIG. 2 represents the structure of a PCO scrubber according to the invention, containing a single layer of PCO 2 media. The air flow is represented by thick arrows. A UV lamp 3 illuminates the medium 2. A fan 5 ensures the air circulation. All these elements are placed in a stainless steel box 1. The distance 4 between the UV lamp and the media can be 20 mm. Such a purifier could also include a particle pre-filter as soon as the air arrives, that is to say placed to the left of the first PCO media.

FIGS. 3 show PCO filter modules inside which the PCO media has a V or W shape. The module comprises a generally metallic casing 6 (stainless steel, zinc-plated steel or aluminum) containing a particle pre-filter 7, a UV lamp 8, a cassette 9 with photo catalytic media, articulated or not. The cassette is returned to the assembly through an opening 10. Depending on the space available for opening the envelope, it is decided whether the cassette should be articulated or not. For example, an articulated cassette can be retracted straight into the module through the opening 10 (FIG. 3c) and then folded in a V by means of the articulation 11 (see FIG. 3a). The cassette can include three joints 12 to take a W shape as in Figure 3b.

FIGS. 4 to 13 give the results of purification of air polluted by various molecules by means of a medium according to the invention. Figures 4 to 11 correspond to the results of Examples 24 to 31 and Figures 12 and 13 correspond to the results of Examples 33 and 34.

FIG. 14 represents the principle of the illumination of the filtering medium by means of several light guides (for example optical fibers) brought to the PCO reactor 15. In FIG. 14 a), it can be seen that from the light source UV 13, several strands of light guide 14 bring the light into the reactor 15 in order to illuminate the PCO media. In FIG. 14 b), we see the distribution of the arrival of eight light guides 14 on the section of the reactor 15 so as to distribute the UV energy as homogeneously as possible in the reactor 15.

FIG. 15 represents the principle of the illumination of the filtering medium by means of a single light guide (for example optical fiber) brought to the PCO reactor 21. From the UV source 16, a single strand 17 of light guide brings the UV light into the reactor 21. In the case shown, the light guide passes through the medium 18 to the point of illumination 19 at the end of the light guide. This strand then illuminates a mirror 20 provided with a suitable curvature and the UV light is reflected (arrows) by this mirror as homogeneously as possible in the reactor towards the medium 18.

FIG. 16 represents the principle of the illumination of several PCO media contained in several PCO reactors 22, by means of light guides (for example optical fibers) 23 connected to a single UV generator 24. The illumination device is therefore centralized with respect to several PCO reactors. This makes it possible to have a single UV generation zone relayed by an illumination system by light guide of different PCO media. This system avoids the need to have multiple sources.

EXAMPLES 1 to 13 (evaluation of powder coatings)

Felts are made as follows. Rods of fused silica with a diameter of 4.4 mm are drawn in an oxy-propane burner in order to bring them to a filament diameter of 0.2 mm. This filament is then re-stretched by flame stretch-blowing in a second burner in order to obtain an average diameter of 9 μm and projected onto a receiving belt or drum. The speed of the drum is adjusted so as to obtain the weight per unit area of ​​the felts shown in the table below (2nd table). The felt obtained is then impregnated with the preparation obtained by the recipe indicated in Table 6 below:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td rowspan="4">Solution A (Ingredients are mixed until limpid, then we exercise a heating to 60 ° C for 1 hour or at 50 ° C more long time)</td><td>TEOS</td><td>PROLABO ref 24 004.290</td><td>X</td>

<td>MTES</td><td>DEGUSSA</td><td>Y</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 8,34</td>

<td>H₂O demineralized at pH 1.25 (1M HCl)</td><td>PROLABO ref 30 024.290</td><td> 4,29</td>

<td rowspan="2">Solution B (Ingredients are mixed under heating at 50 ° C iusau'at dissolution of PE6800)</td><td>Polymer Oxide block propylene and oxide ethylene</td><td>BASF PE6800</td><td> 3,85</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 40,28</td>

<td>August from A to B</td><td>A + B</td><td></td><td></td>

<td>Catalyst C</td><td>TiO₂ at 19.3% in the water</td><td>MILLENNIUM S5 300A</td><td>Z</td>

<td>August of C in ÎA + B1</td><td></td><td></td><td>To be adjusted with water for a total of 100 liters.</td>

Table 6

Different tests were carried out with different amounts of TEOS, MTES and TiO catalyst₂ as reported in Table 7 below.

<td>Example</td><td>X (TEOS)</td><td>Y (MTES)</td><td>Z (TÎO2)</td><td>Other parameters</td><td>Efficiency PCO (ppm)</td><td>Powdering (mg / m²)</td>

<td>ΝΊ (comparative)</td><td></td><td></td><td></td><td>Reference: none impregnation</td><td> 0</td><td> 0,2</td>

<td>No. 2</td><td></td><td></td><td></td><td>Example 10 where the solution impregnation was diluted 5 times in the water</td><td> 35</td><td> 0,6</td>

<td>No. 3</td><td> 9,9</td><td></td><td> 10,6</td><td></td><td> 120</td><td> 0,7</td>

<td>No. 4</td><td> 9,9</td><td></td><td> 15,15</td><td></td><td> 180</td><td> 0,8</td>

<td>No. 5</td><td> 9,9</td><td></td><td> 22,72</td><td></td><td> 200</td><td> 2,9</td>

<td>No. 6</td><td> 9,9</td><td></td><td> 22,72</td><td>Aspirated 90 s on a vacuum table with a speed suction of 1 m / s</td><td> 200</td><td> 1,3</td>

<td>No. 7</td><td></td><td> 9,9</td><td> 22,72</td><td></td><td> 180</td><td> 1,3</td>

<td>No. 8</td><td> 3,96</td><td> 5,94</td><td> 22,72</td><td></td><td> 160</td><td> 1</td>

<td>No. 9</td><td> 7,62</td><td> 2,27</td><td> 22,72</td><td></td><td> 200</td><td> 0,75</td>

<td>ΝΊ0</td><td> 9,9</td><td></td><td> 33,33</td><td></td><td> 170</td><td> 2,6</td>

<td>ΝΊ1</td><td> 9,9</td><td></td><td> 22,72</td><td>With post impregnation of silane DYNASILAN 8820 from Degussa to 0.4% height</td><td> 150</td><td> 0,95</td>

<td>ΝΊ2</td><td> 9,9</td><td></td><td> 22,72</td><td>Spraying Rhodorsil on the 2 media sides to 0.3% height</td><td> 170</td><td> 0,8</td>

<td>No. 13</td><td> 9,9</td><td></td><td> 22,72</td><td>Spraying PTFE on both sides media up to 0.3%</td><td> 230</td><td> 0,1</td>

Table 7

The impregnated felt then undergoes a heat treatment under the conditions of Table 4 already seen above. The final media obtained has a basis weight after impregnation of approximately 120 g / m², an apparent thickness of 20 mm, and its titanium oxide content is of the order of 20% by weight (except case ΝΊ: no catalyst and No. 2: less than 4% of catalyst).

Measurements to evaluate the dusting tendency of the coating are then carried out from samples of 100 x 100 mm² PCO media. The samples are placed in a FRITSH / Labogerdebau type sieve for 30 minutes with an amplitude of 4 (machine specific value). At the end of the 30 minutes, the residue is weighed and the loss of mass is reported to 1 m² of substrate. The values ​​are averaged over 5 samples. The results are reported in a comparative manner in Table 7. The results are expressed in “dusting”, that is to say the quantity of powder formed per unit area of ​​media (in mg / m²), and in PCO efficiency on the basis of the “methanol test” already described above. This efficiency is expressed as a quantity of oxidized methanol in ppm. In particular, test No. 13 is excellent because it combines very good PCO activity with very low dusting.

EXAMPLES 14 to 23 (oxidation of methanol)

A reactor is used consisting of a stainless steel body inside which is placed a media disc with a diameter of 47 mm. In the upper part of the reactor, UV HPK 125 W illumination is produced through a silica slit. The illumination power is regulated by adjusting the Media lamp distance. A power of 5 mW / cm² at 365 nm (of media) of UV measured at the media level is used. Upstream of the reactor, a constant flow of filtered air containing 300 ppm of methanol is introduced at a rate of 350 ml / min. Downstream of the reactor after PCO treatment, the concentration of methanol is measured by gas phase chromatography. We ensure the mineralization of the pollutant (conversion into CO₂ and H₂0) by checking the chemical balance so as not to have only pure adsorption phenomena as can be found with systems of the activated carbon type. Table 8 gives the more precise operating conditions for producing the media as well as the efficiency observed on various media in the context of the “methanol test” already explained above.

<td>Example No.</td><td>Weight felt</td><td>TEOS</td><td>MTES</td><td>Origin TiO₂</td><td>TiO₂</td><td>Other settings</td><td>Efficiency PCO (ppm)</td>

<td> 14</td><td>200 g / m²</td><td> 9,9</td><td></td><td>Millennium S5 300 A</td><td> 33,33</td><td></td><td> 240</td>

<td> 15</td><td>80 g / m²</td><td> 9,9</td><td></td><td>Millennium S5 300 A</td><td> 33,33</td><td></td><td> 200</td>

<td> 16</td><td>80 g / m²</td><td> 9,9</td><td></td><td>Millennium S5 300 A</td><td> 33,33</td><td>Aspiration of the preparation of catalyst 90 s on a table aspirant with a speed suction of 1 m / s</td><td> 200</td>

<td> 17</td><td>65 g / m²</td><td> 9,9</td><td></td><td>Millennium S5 300 A</td><td> 33,33</td><td></td><td> 170</td>

<td> 18</td><td>80 g / m²</td><td> 9,9</td><td></td><td>Degussa P25</td><td> 33,33</td><td></td><td> 120</td>

<td> 19</td><td>80 g / m²</td><td> 9,9</td><td></td><td>Millennium S5 300 A</td><td> 33,33</td><td>Spraying PTFE on the 2 media faces to the height of 0.3%</td><td> 230</td>

<td> 20</td><td>80 g / m²</td><td> 7,62</td><td> 2,27</td><td>Millennium S5 300 A</td><td> 33,33</td><td></td><td> 200</td>

<td> 21</td><td>65 g / m²</td><td></td><td> 9,9</td><td>Millennium S5 300 A</td><td> 33,33</td><td></td><td> 180</td>

<td>22 (comparative)</td><td colspan="5">Media marketed by Toshiba with a density of 0.7 gr / cm3 in 10 mm thickness.</td><td>Foam Ceramic PCO</td><td> 170</td>

<td>23 (comparative)</td><td colspan="5">PCO paper + activated carbon, reference Alhstrom 1054</td><td>Felts Polyester PCO + Activated carbon</td><td> 110</td>

Table 8

EXAMPLES 24 to 31 (oxidation of organic molecules at different flow rates and intensity of illumination)

Rods of fused silica with a diameter of 4.4 mm are drawn in an oxy-propane burner in order to bring them to a filament diameter of 0.25 mm. This filament is then re-stretched by flame stretch blow molding in a second burner to obtain an average diameter of 9 µm and projected onto a receiving drum. The speed of the drum is adjusted so as to obtain a weight per unit area of ​​the felt of 80 g / m². The felt is then impregnated in accordance with the recipe in Table 9 below:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td></td><td>TEOS</td><td>PROLABO ref 24 004.290</td><td> 7,00</td>

<td></td><td>MTES</td><td>DEGUSSA</td><td> 2.9</td>

<td>Solution A</td><td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 8,34</td>

<td>(Ingredients are mixed until limpid, then we exercise a heating to 60 ° C for 1 h)</td><td>H₂O demineralized at pH 1.25 (1 M HCl)</td><td>PROLABO ref 30 024.290</td><td> 4,29</td>

<td></td><td>Polymer oxide block</td><td>BASF</td><td> 3,85</td>

<td>Solution B</td><td>propylene and oxide ethylene</td><td>PE6800</td><td></td>

<td>(Ingredients are mixed under heating_to 50 ° C up to dissolution of PE6800)</td><td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 40,28</td>

<td>August from A to B</td><td>A + B</td><td></td><td> 66,67</td>

<td>Catalyst C</td><td>TiO₂ (19.3% in water)</td><td>MILLENNIUM S5 300A</td><td> 33,33</td>

<td>August of C in (A + B)</td><td>A + (A + B)</td><td></td><td> 100</td>

Table 9

The impregnated felt then undergoes a heat treatment under the conditions of Table 4 already seen above.

The filter media obtained has an apparent thickness of 20 mm. The felt has a total mass after impregnation of 120 g / m², the level of titanium oxide being 20% ​​of the total mass of the media.

The efficiency of the photocatalytic medium was measured by placing it in a PCO scrubber with a flow rate of 130 m³/ h, the frontal speed being 1 m / s, the illumination power received of 15 mW of UVC per cm² media (these values ​​were measured by a BIOBLOCK VLX-3W radiometer with a 254 nm probe). The enclosure is made of stainless steel and measures 1 m³. The scrubber is made of stainless steel. It is fitted with 3 Philips 36 W TUV lamps placed 20 mm from the PCO media (s). The media area is 270X420 mm². The PCO scrubber contains one or two media as shown in Figures 1 and 2. The fan is placed behind the PCO filter (s).

Using a permeameter, a mixture of pollutant is introduced into the chamber at a rate of 1.951 / min. This mixture consists of benzene, toluene, o-xylene, decane, limonene and formaldehyde.

New filtered air is introduced at a rate of 21 l / min and an outlet system pumps 23 l / min of the atmosphere in order to simulate the rate of renewal of new air existing in any building. In the event of a high concentration of VOCs, and in order to reduce the formation of reaction intermediates that can be harmful such as formaldehyde, acetaldehyde, acetone, it is important to work with UV illumination rates that are not too much. important as well as moderate flow rates in order to increase the reaction time within the substrate and to allow a more complete oxidation of the organic compounds (which includes these possible undesired intermediate compounds) within the substrate.

The meaning of the various abbreviations is as follows:

1F: -1 PCO Media

2F: - 2 PCO media on either side of the UV lamp

Dmax: - Maximum flow (130 m³/ h)

D1 / 2: - Maximum flow divided by 2

UV Max: - Maximum UV illumination

UV / 2: - Maximum UV illumination divided by 2

Min UV: - UV illumination received 2 mW / cm².

The results are given by FIGS. 4 to 11. The moment at which the purifier is operating is indicated in the figures by the double-arrow “purifier in operation”.

In view of the various curves, the oxidation of the various benzene, toluene, decane, xylene and limonene compounds by virtue of the PCO filter according to the invention is very clear. Correlatively, it appears that the formation of intermediate products such as formaldehyde, acetaldehyde, acetone is all the more marked the higher the flow rate and the UV power.

EXAMPLE 32 (ozone)

Rods of fused silica with a diameter of 4.4 mm are drawn in an oxy-propane burner in order to bring them to a filament diameter of 0.2 mm. This filament is then re-stretched by flame stretch-blowing in a second burner in order to obtain an average diameter of 9 μm and projected onto a receiving drum. The speed of the drum is adjusted so as to obtain a felt weight per unit area of ​​65 g / m². The product is then impregnated with the preparation obtained according to the recipe in Table 10 below:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td rowspan="4">Solution A (Ingredients are mixed until limpid, then we exercise a heating to 60 ° C for 1 h)</td><td>TEOS</td><td>PROLABO ref 24 004.290</td><td> 5,00</td>

<td>MTES</td><td>DEGUSSA</td><td> 4.9</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 8,34</td>

<td>H₂O demineralized at pH 1.25 (1 M HCl)</td><td>PROLABO ref 30 024.290</td><td> 4,29</td>

<td rowspan="2">Solution B (Ingredients are mixed under heating_to 50Ό iusau'à dissolution of PE6800)</td><td>Polymer oxide block propylene and oxide ethylene</td><td>BASF PE6800</td><td> 3,85</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 40,28</td>

<td>August from A to B</td><td>A + B</td><td></td><td> 66,67</td>

<td>Catalyst C</td><td>TiO₂ at 19.3% in the water</td><td>MILLENNIUM S5 300A</td><td> 33,33</td>

<td>August of C in (A + B)</td><td>A + (A + B)</td><td></td><td> 100</td>

<td colspan="2">Tab</td><td colspan="2">water 10</td>

The impregnated felt then undergoes a heat treatment under the conditions of Table 4 already seen above.

The filter media obtained has an apparent thickness of 20 mm.

The felt has a total mass after impregnation of 100 g / m², the level of titanium oxide being 20% ​​by weight of the total weight of the media.

The tests were carried out in an experimental house. The purifier was that described in Examples 24 to 31, equipped with 2 media.

The test conditions were as follows:

- office of 30 m³

- Air renewal rate (TRA) between 0.6 and 1 volume / h

- Quartzel brand fused silica fiber felts (registered trademark of Saint-Gobain Quartz SAS) with a basis weight of 65 g / m²(media mass 100 gr / m²)

- Nominal flow rate, scrubber 130 m³/ h.

- UV illumination received 15 mW / cm²

The measurements were taken one week before the installation of the purifier, one week during operation of the purifier and one week after stopping the purifier. The results are expressed as a ratio of indoor to outdoor ozone concentration. Indeed, in full-scale, an air renewal rate still existing, new air loaded with polluting enters the room and stale air loaded with pollutant leaves the room. To compare efficiencies, it is therefore useful to be able to work in relative indoor air pollutant concentration / outdoor air pollutant concentration. Without PCO scrubber, this ratio is 0.14. With the PCO scrubber, this ratio is 0.01.

EXAMPLES 33 and 34

5.5 mm diameter fused silica rods are drawn in an oxy-propane burner to bring them to a filament diameter of 0.2 mm. This filament is then re-stretched by flame stretch-blowing in a second burner in order to obtain an average diameter of 9 μm and projected onto a receiving drum. The speed of the drum is adjusted in such a way as to obtain a felt per unit area of ​​50 g / m²The felt is then impregnated with the preparation made according to the recipe in Table 11 below:

<td></td><td>Reagent</td><td>Supplier and reference</td><td>Mass (kg)</td>

<td rowspan="3">Solution A (Ingredients are mixed until limpid, then we exercise a heating to 60 ° C for 1 h)</td><td>MTES</td><td>PROLABO ref 24 004.290</td><td> 9,90</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 8,34</td>

<td>H₂O demineralized at pH 1.25 (1M HCl)</td><td>PROLABO ref 30 024.290</td><td> 4,29</td>

<td rowspan="2">Solution B (Ingredients are mixed under heating_to 50Ό iusau'à dissolution of PE6800)</td><td>Polymer oxide block propylene and oxide ethylene</td><td>BASF PE6800</td><td> 3,85</td>

<td>Absolute ethanol</td><td>PROLABO ref 20 821.467</td><td> 40,28</td>

<td>August from A to B</td><td>A + B</td><td></td><td> 66,67</td>

<td>Catalyst C</td><td>TiO₂ at 19.3% in the water</td><td>MILLENNIUM S5 300A</td><td> 33,33</td>

<td>August of C in (A + B)</td><td>C + (A + B)</td><td></td><td> 100</td>

<td colspan="2">Tab</td><td colspan="2">water 11</td>

The impregnated felt then undergoes a heat treatment under the conditions of Table 4 already seen above. The filter media obtained has an apparent thickness of 20 mm. The felt has a total mass after impregnation of 85 g / m², the level of titanium oxide being 20% ​​of the total weight of media.

The media is then placed in a scrubber identical to that described for Examples 24 to 31 (a single PCO media) with the following parameters:

Nominal flow rate in the purifier: 130 m³/ h;

UV illumination received: 15 mW / cm².

The scrubber to be tested is placed in an enclosure of one m³ in plexiglass.

Prior to the test, the chamber is purged with ultra pure and humidified air in order to eliminate the presence of pollutant before the introduction of the mixture of model molecules. A liquid mixture of the various pollutants is introduced through a septum via a syringe into a glass weighing shoe. Two mixtures were tested, one containing propionaldehyde, heptane, acetone, toluene, acetaldehyde, ethylene, styrene, o-xylene (example 33) and the other containing toluene, heptane, butyraldehyde, acetone, methoxyethanol (example 34) . After evaporation, the concentration of the various compounds is of the order of ppmv. CO monitoring₂ is carried out by a micro-gas chromatograph equipped with a thermal conductivity detector (pGC-TCD), the other pollutants are analyzed by a gas chromatograph equipped with a photoionization detector (PID). The PID makes it possible to analyze ionizable organo-volatile compounds (VOCs) in the ppbv range. The possible presence of degradation by-products in the gas phase is detected by adsorption on an adsorbent cartridge (flow rate 100 ml / min, time 20 minutes) followed by thermal desorption analysis coupled with a gas chromatograph and detection by mass spectrometry. The results are shown in Figures 12 and 13. There is remarkable efficiency of the PCO system according to the invention on the elimination of the various solvents as soon as the UV illumination is triggered (the moment of illumination is indicated by the arrow “UV on”). In the case of Example 34 (FIG. 13), acetaldehyde is formed momentarily upon UV illumination and then is itself oxidized. The methoxyethanol peak between 40 and 70 min corresponds to a second injection of this product into the chamber. The affinity of methoxyethanol for the medium is such that the latter is immediately adsorbed.