WO2006027659A1

WO2006027659A1 - Process for purifying humid wastes through their treatment with superoxydizing agents in the presence of catalysts and purification plant thereof

Info

Publication number: WO2006027659A1
Application number: PCT/IB2005/002623
Authority: WO
Inventors: Giacoma Silvana Di Giovanni; Maurizio Di Giovanni
Original assignee: Ecoenergy Abiotecnologie S.A.S. Di Di Giovanni Sabrina E C.-Tecnologie Abiotiche Per L'ambiente El'energia
Priority date: 2004-09-07
Filing date: 2005-09-06
Publication date: 2006-03-16

Abstract

The present invention relates to an abiotic process for purifying wet waste, by liberating them from the polluting agents, through their treatment with superoxidizing agents in the presence of proper photocata lysts and microporous inorganic catalysts. The invention further relates to a purifier for carry out said purification process.

Description

PROCESS FOR PURIFYING HUMID WASTES THROUGH THEIR TREATMENT WITH SUPEROXYDIZING AGENTS IN THE PRESENCE

OF CATALYSTS AND PURIFICATION PLANT THEREOF

* * * * *

DESCRIPTION SUMMARY OF THE INVENTION

The present invention relates to an abiotic process for purifying wet waste, by liberating them from the polluting agents, through their treatment with super- oxidizing agents in the presence of appropriate photo- catalysts and microporous inorganic catalysts. The invention further relates to a purifier for carry out said purification process. TECHNICAL FIELD OF THE INVENTION

For the purposes of the present invention, the term wet waste means waste waters, wet solid waste, sludges and polluted air.

The term waste waters, means polluting waste, more or less thick liquids or fluids, such as for example: waste waters deriving from industrial processes and/or productions; sewages deriving from agricultural ac¬ tivities and zootechnical activities, such as drainage waters from breedings, abattoirs, fishing industries; waste waters from civil settlements, such as houses, shops, offices and hospitals; rain waters or washing waters from squares, roads, parking areas, car washes; motorway drainage waters and from refuelling; drainage waters from recycling plants and waste selection, leachates from disposal sites and from garbage cans. By the term solid wet waste, it is understood to mean waste of a different nature such as, for example, do¬ mestic and hospital waste, urban solid waste, pu- trescible organic waste, green waste.

By the term sludges, it is understood to mean solid or semisolid waste deriving from urban, industrial, agri¬ cultural zootechnical waste, or decantation sludges from purification processes, for example of a biologi¬ cal type.

By the term polluted air, it is understood to mean air polluted by toxic or malodorous, gaseous or volatile matters, deriving from human activities, from produc¬ tion processes, from biological purification or from processing plants of solid waste. For example, there may be mentioned the ethylene emitted from decaying fruit and vegetable in the fruit and vegetable ware¬ houses, the ammonia liberated from animal sewages in the breedings, the organic solvents employed in the paints and glues industry and so on.

By the term polluting agents, it is understood to mean each type of toxic or malodorous matter which is harm- ful for the human being and/or the environment, such as, by way of non limiting example: volatile or not volatile organic substances, of a different nature, origin and composition, for example halogenated resi¬ dues, drugs, oils, greases, surfactants, detergents, fertilizers, solvents; inorganic substances, such as metals, in particular heavy metals, salts; nitroge¬ nous, sulfurous and phosphoric residues. In particu¬ lar, among the polluting agents, those harmful sub¬ stances which are not degradable with the known bio¬ logical purification systems are preferred. One of the aims of the treatment of wet waste is the removal from the same of the polluting agents, in or¬ der to eliminate or, at least considerably decrease the possibility of harmful effects on human being and the rest of the ecosystem.

In particular, the purification of the waste water is usually carried out with biological methods in proper tanks, with the separation of the obtained sludges and final sterilization of the purified waters and the re¬ sidual sludges.

Generally, the biological purification process in¬ volves low unit costs, however it is very slow and, above all, is not much effective towards several or¬ ganic products, usually present in the industrial or civil waste waters, which have proved to be bioresis- tent.

In view of the application difficulties of a biologi¬ cal process for the complete purification of the wa¬ ters and to their subsequent sterilization, the tech¬ nology has developed purification processes of a chemical type, for example by proposing the use of hy¬ drogen peroxide in an acid environment with sulphuric acid.

Another proposal from the current technology is the treatment of the waste waters inside of reactors, with a dosage of hydrogen peroxide and UV rays. Such solu¬ tion makes difficult the treatment of even slightly cloudy waters, because the rays do not cross the wa¬ ters to be treated. A further proposal foresees the use of ozone and hydrogen peroxide. However, the cost of this technique is very high.

Furthermore, all these systems can only be used for carrying out a pre-treatment of purification, followed by a secondary biological treatment, or for carrying out the end treatment of_ sterilization and/or disin¬ fection of the waters, previously purified with bio¬ logical methods.

So far, a wholly abiotic process which allows to com¬ pletely and directly purify and sterilize wet waste, such as waste waters of any kind and origin, solid wet waste, sludges and polluted air is then lacking, with¬ out the need to also turn to other types of purifica¬ tion (for example the biological one) .

An aim of the present invention is to give an adequate answer to the need above pointed out.

These and other objects, which will be evident from the following detailed description, have been attained by the Applicant, which has unexpectedly found that it is possible to carry out a process for purifying wet waste including at least a step of contacting said waste with superoxidants in the presence of at least a photocatalyst and at least a proper microporous inor¬ ganic catalyst.

It is an object of the present invention a process for purifying wet waste through a treatment with superoxi- dizing agents in the presence of catalysts, as summa¬ rized in the appended independent claim. It is a further object of the present invention a pu¬ rifier for carrying out said purification process, as summarized in the appended independent claim. Particulary preferred embodiments of the present in¬ vention are summarized in the appendend dependent claims. DESCRIPTION OF THE INVENTION

The process for purifying wet waste according to the present invention includes at least a step of contact¬ ing said waste with superoxidizing agents in the pres¬ ence of at least a photocatalyst and at least a micro- porous inorganic catalyst.

Said wet waste are selected among waste waters, wet solid waste, sludges and polluted and/or malodorous air.

The superoxidizing agents used in the process of the present invention consist of extremely reactive oxi¬ dizing species, comprising, among others, O₂, O₃ (ozo¬ ne) , superoxide anion, singlet oxygen, ^'OH radicals (hydroxyl) ; more preferably, O₃ and ^'OH, or their mix¬ tures.

Said superoxidizing agents are produced in loco at the time of use, that is just before and/or at the same time of the contact step with the waste. In a preferred embodiment, the superoxidizing agents are opportunely dosed in the reaction zone where the purification process takes place.

In another preferred embodiment, the superoxidizing agents are directly produced in the reaction zone, or at a close contact with the same, in the presence of the waste to be purified. In another preferred embodiment, the purification process according to the present invention includes both the solutions above shown.

The superoxidizing agents of the present invention are generated, starting from water and air/oxygen (that is the oxygen of the air, or pure oxygen) , by catalytic photolysis and/or photoelectrolysis of said feed stocks in the superoxidizing species above-mentioned. Said catalytic photolysis and/or photoelectrolysis is preferably carried out in a generator of superoxidants including at least a photocatalyst (that is a catalyst which can be activated following to an exposure to op¬ portune light radiations, in the specific case, ultra¬ violet radiations) and at least a microporous inor¬ ganic catalyst; said generator being able to be irra¬ diated by a source of ultraviolet radiations, in order to activate said photocatalyst.

Preferably, said ultraviolet radiations have wave¬ lengths of about 390 nm; more preferably, similar or lower than 390 nm.

Depending on the type of the selected embodiment, ^' said source of ultraviolet radiations is the sunlight it¬ self, or one or more ultraviolet light lamps of a proper wavelength. In a preferred embodiment, the superoxidants generator uses at the same time both the irradiation from the sunlight and the irradiation from ultraviolet light lamps, as above defined.

The step of contacting the wet waste with the above superoxidizing agents is carried out in the presence of the same photocatalyst and the same microporous in¬ organic catalyst above-mentioned.

Therefore, in a particularly preferred embodiment of the invention, the process for purifying wet waste in¬ cludes at least a step of contacting said waste with superoxidizing agents in the presence of at least a photocatalyst and at least a microporous inorganic catalyst, wherein said step is carried out under the action of (natural and/or artificial) ultraviolet ra¬ diations.

Said photocatalyst includes one or more photoexcitable compounds following to (natural and/or artificial) ultraviolet irradiation, such as, for example, tita¬ nium dioxide (TiO₂) _r mixed silicate of sodium and alu¬ minum (traditionally called, hereinbelow, "blue sili¬ cate", because of its colour) , zinc oxide (ZnO) , tung- stic oxide (WO₃), other metal or semi-metal oxides. For the purposes of the present invention, TiO₂, blue silicate and their mixtures have proved to be pre¬ ferred. Particularly preferred are blue silicate and/or blue silicate/TiO₂ mixtures.

When a blue silicate/TiO₂ mixture is used, the two photocatalysts are generally dosed in a mutual weight ratio of 1:1; however, each type of weight ratio can be used, depending on the preferred application, and as a consequence it is within the ambit of the present invention.

The inorganic catalyst with a microporous structure includes at least a powdery or granulated/microgra- nulated microporous inorganic material, having a po¬ rosity included, on average, between about 250 μm and < about 65 μm. Preferably, the porosity is < to about 63 μm. The single pores can reach a size of 3, 4, 5, 10 Angstrom.

By way of not limiting example, the porosity distribu¬ tion can assume the following values: from 200 μm to 150 μm, 0,03% with respect to the total weight of the microporous inorganic material; from 150 μm to 100 μm, 0,67%; from 100 μm to 71 μm, 2,67%; from 71 μm-to 63 μm, 2,19%; < 63 μm, 94,44%.

If the granular form is used, said at least one micro¬ porous material preferably has a granulometry until 25-30 mm; preferably, between 1 mm to 20 mm; more preferably, from 5 mm to 15 mm. In a particularly preferred embodiment, the granulome- try of said microporous material is of about 8 mm. Preferably, said microporous material is selected be¬ tween: molecular sieves, zeolites, pumices, kaolin, clay and the like and/or their mixtures. Particularly preferred are molecular sieves provided with acid sites (for example, silico-aluminated resi¬ dues) , which increase the catalytic activity thereof, and with mobile Na⁺ ions rich-sites (for example, so- dium-aluminated residues), capable of replacing the calcium ions present in the waters.

Said molecular sieves are, for simplicity, indicated below with the term "dynamic molecule sieves". A non limiting example of dynamic molecule sieves is given from molecular sieves of a vulcanic and/or arti¬ ficial origin having the following composition:

- chabazite-phyllipsite concentration;

- absolute gravity: about 2 g/cm³;

- apparent density: about 0,8 g/cm³;

- chemical composition % by weight (with reference to the oxides) :

SrO 0,04%; Na₂O 0,60%; K₂O 4,91%; SiO₂ 51,80%; Al₂O₃ 18,34%; Fe₂O₃ 3,40%; MgO 0,96%; CaO 4,73%; BaO 0,35%; H₂O 14,87% (-fire loss) . The microporous catalyst according to the present in- vention, in any case, has to contain at least 5% by weight of dynamic molecule sieves, with respect to the total weight of the catalyst; preferably, at least 10% by weight, more preferably, at least 20% by weight. Accordingly, in view of the above, for simplicity, the microporous inorganic catalyst according to the pre¬ sent invention will be conventionally characterized below by the term "dynamic molecule microporous cata¬ lyst".

In a particularly preferred embodiment of the inven¬ tion, the photocatalyst (or the mixture of photocata- lysts) is incorporated/applied to the dynamic mole¬ cules microporous catalyst above mentioned. If used as a powder, the photocatalyst (or the mixture of the photocatalyst powders) is incorporated in the dynamic molecules microporous catalyst, preferably by sintering.

So, by mere way of example, powders of TiC>₂, blue silicate or their mixtures are opportunely mixed with the desired quantity of dynamic molecule microporous catalyst and sintered in a continuous oven at a tem¬ perature between 65⁰C and HO⁰C; preferably,- from 75⁰C to 95⁰C; more preferably, at about 85⁰C. As for the TiC>2, the same can also be used in the form of gel. In this case, TiO₂ can be applied to the dy- namic molecule microporous catalyst by spraying (also with more consecutive applications, depending on the Tiθ₂ guantity that one wishes on support to said cata¬ lyst) , or by bath.

The photocatalyst (or the mixture of the photocata- lysts) is incorporated/applied to the dynamic molecule microporous catalyst in a quantity not lower than 5% by weight based on the weight of said catalyst; pref¬ erably, not lower than 10% by weight; more preferably, not lower than 15% by weight.

In a particularly preferred embodiment, Tiθ₂, blue silicate or their mixtures, are applied to the dynamic molecule microporous catalyst in a quantity between 15% and 40% by weight based on the weight of said catalyst; preferably, between 20% and 30% by weight. In an embodiment of the invention, the photocatalyst above-mentioned (preferably, incorporated/applied on the dynamic molecule microporous catalyst) is applied on the walls (transparent or not to the solar radia¬ tions, possibly perforated for allowing the contact with the outside air) of the generator of superoxidiz- ing agents. Preferably, the application of the photo- catalyst/dynamic molecule microporous catalyst mixture on the generator walls is carried out through seques¬ tration of said mixture within perforated metal sheet having holes between 6 nun and 10 mm; preferably, of about 8 mm.

In a preferred embodiment, the protector tubes of the ultraviolet lamps are coated with TiO₂, in gel, which, being transparent, allows the radiation to freely pass through, by increasing at the same time the effective¬ ness thereof.

In a particularly preferred embodiment of the inven¬ tion, said generator of superoxidizing agents is a photocatalytic generator (of a different shape and size depending ,on the desired application) which ex¬ ploits the synergic combined action of the dynamic molecule microporous catalysts and the photocatalysts activated by the (natural and/or artificial) ultravio¬ let radiations, in order to produce, preferably, O₃ and ^'OH radicals from the photolysis of the water and the O₂ of the air.

In another particularly preferred embodiment, the gen¬ erator of said superoxidizing agents is a photoelec- trocatalytic generator which also synergically com¬ bines, to the photolytic processes above described, the electrolysis of the water.

Also in this embodiment, ^■ the walls (partially trans¬ parent or not) of the generator, those of the electro¬ lytic cells, as well as those of the electrodes (pho- toelectrodes) are preferably coated with the above photocatalysts (as such or, preferably, supported on the dynamic molecule microporous catalyst above men¬ tioned) .

Also in this case, the protector tubes of the ultra¬ violet lamps are preferably coated with TiC>₂ gel, in order to extraordinarily increase the effectiveness of the system.

The photocatalyst supported on the dynamic molecule microporous catalyst is also added in the reaction zone (for example, applied on the walls which delimit it, or inserted in proper permeable containers placed inside the same, or freely mixed with the fluid to be purified) . In this way, it is possible to accelerate at most the times of the degradation reaction of the polluting organic substances (through their conversion in CO2 and H2O) and to allow the dynamic molecule mi¬ croporous catalyst to sequestrate inside its pores some toxic species, such as unwanted heavy metals and ions of a different nature, for example Ca²⁺, by re¬ leasing Na⁺ ions.

In a preferred embodiment, the photoelectrolytic gen¬ erator above described, opportunely dimensioned and modified, can simultaneously act as a superoxidants generator and a process reactor, by allowing, for ex- ample, the stabilization, the sterilization and the concentration of the wet sludges deriving from the first oxidative treatment.

The purifier for carrying out the process according to the invention for purifying wet waste is characterized in that it includes

- at least a generator of superoxidizing agents in¬ cluding at least a photocatalyst and a dynamic mole¬ cule microporous catalyst for generating said super- oxidants from water and air/oxygen, said generator ca¬ pable of being irradiated by a source of (natural or arificial) ultraviolet radiation, in order to acti¬ vate said photocatalyst;

- at least a reaction zone placed in a fluid communi¬ cation with said generator of superoxidants for react¬ ing said wet waste with said superoxidants.

In an embodiment of the invention, said generator of superoxidizing agents further includes at least an ul¬ traviolet lamp for activating said photoactivable catalyst.

Said at least one ultraviolet lamp emits ultraviolet radiations having a wavelength of about 390 niti; more preferably, similar or lower than 390 run. In a preferred embodiment, said generator of superoxi¬ dizing agents includes a retaining body defining a cavity (air- and water permeable) containing said at least one photocatalyst incorporated/applied to said dynamic molecule microporous catalyst, said cavity be¬ ing exposed to the air 'and being wettable with water, and an outlet for the superoxidants.

Said generator above mentioned further includes an ul¬ traviolet lamp within said permeable cavity, in order to activate the production of the superoxidizing agents inside the cavity itself.

In another preferred embodiment of the invention, said generator of superoxidizing agents includes: a retaining body, including a plurality of electro¬ lytic cells, photoelectrodes and ultraviolet lamps; inlets for water, air/oxygen; an outlet for the acque- ous solution of the superoxidizing agents; the walls of the generator, electrolytic cells and of the photo- electrodes being coated with said photocatalyst incor¬ porated/applied to said dynamic molecule microporous catalyst.

Preferably, in said generator, the protector tubes of the ultraviolet lamps are coated with TiO₂ gel. The advantage given from said photoelectrolytic gen¬ erator is that it greatly accelerates the production of superoxidizing species (O₃ and ^'OH radicals) and that it is extremely versatile, capable of simultane- ously being used both as a generator of superoxidants and as a treatment unit for the final inertization and sterilization of the process sludges.

The reaction zone of the purification plant according to the invention can be carried out in different ways depending on the type of plant and the application of the same.

In a preferred emodiment of the invention, said at least one reaction zone of the purifier includes a first housing cavity for containing the fluid to be purified and the superoxidizing agents; said cavity being delimited by a porous septum which put it into contact with a second housing cavity (preferably, co¬ axial to the first one) containing said at least one photocatalyst incorporated/applied to said dynamic molecule microporous catalyst, for accelerating at most the degradation reaction of the polluting organic substances and allowing the dynamic molecule micropor¬ ous catalyst to sequestrate, within its pores, some toxic species, -such as the ^'heavy metals and the un¬ wanted ions, by releasing Na⁺ ions.

Said first housing cavity includes a first inlet for the fluid to be purified^' and the superoxidizing agents. Said second housing cavity allows the passage of the purified liquid (water) , which, after decantation in a third housing zone (external to the two preceding ones) , is recovered and re-used as such, without the need of further purifications, disinfection and/or sterilization treatments.

Preferably, said final liquid is recycled to the gen¬ erator of superoxidizing agents for restoring the oxi¬ dizing species required for the purification process without having to waste clean water.

In another particularly preferred embodiment of the invention, said at least one reaction zone of the pu¬ rifier includes a reactor (or a tank/container) having a first inlet for the fluid to be purified, a second inlet for the superoxidizing agents and an outlet for the purified fluid.

Preferably, the walls of said reactor are coated with said at least one photocatalyst incorporated/applied to said dynamic molecule microporous catalyst, in or¬ der to accelerate at most the degradation reaction of the polluting organic substances and to allow the dy¬ namic molecule microporous catalyst to sequestrate within ^'its pores toxical species, such as the heavy metals and the unwanted ions, by releasing Na⁺ ions. Said photocatalyst incorporated/applied to said dy¬ namic molecule microporous catalyst is preferably se- questrated within perforated sheet metals applied to the walls of said reactor.

Said reactor can further include a third inlet for adding additional quantities of the catalysts above mentioned.

Depending on the embodiments, said reactor can also be irradiated from the sunlight and/or from that emitted by ultraviolet lamps.

Preferably, said reactor also includes mixing means of the fluid to be purified.

The purifier according to the embodiment just de¬ scribed also includes at least a settler for separat¬ ing the liquid fraction (water)purified from the wet fraction (generally, residual sludges) of the purified fluid.

Said purifier also includes a treatment unit of the wet fraction of the purified fluid (or of abiotic sta¬ bilization of the wet sludges) for separating the solid fraction (sludges) from the water contained therein, by simultaneous inertization and steriliza¬ tion thereof.

Said treatment unit above mentioned preferably in¬ cludes a tubular body (blind or, possibly, equipped with windows transparent to the ultraviolet light; said windows being coated with TiC>₂ gel) having a first end including a first inlet for said wet frac¬ tion and at least a second inlet for the air or the oxygen, a second end comprising an outlet for the liq¬ uid sterile fraction of the wet and a plurality of outlets for the solid fraction of the wet; said plu¬ rality of oulets for the solid fraction being periph¬ erally arranged on said tubular body.

Furthermore, said treatment unit includes a plurality of disk photoelectrodes positioned within and trans- versally to said tubular body; said disks being spaced therebetween in order to define a plurality of photo- electrolytic cells and decantatiόn chambers; each de- cantation chamber including one of said outlets for the solid fraction of the wet.

Said disk photoelectrodes of said photoelectrolytic cells inlcude an anode and a cathode; said cathode and said anode being coated with said photocatalyst incor¬ porated/applied in said dynamic molecule microporous catalyst.

Said disk photoelectrodes are equipped with through- holes and transversal septa which force the flow of the sludges to go through the cells with a rotatory circular direction.

Furthermore, said treatment unit includes a transpar¬ ent cylinder for housing the ultraviolet lamps, which is inserted in a central position and axially to the tubular body of the treatment unit.

Also the internal walls of the treatment unit and those of the photoelectrolytic cells are coated with the photocatalyst incorporated/applied to the dynamic molecule microporous catalyst.

Preferably, said treatment unit also includes an elec¬ tronic control system of the stopping potential of the semi-reactions in the photoelectrolytic cells, in or¬ der to reject, through a proper voltage applied to the anode, the electrons produced by the cathode. Said electronic control system of the stopping potential maintains in the electrolyte the semi-reaction regime depending on the flow of water and air/oxygen which passes through the cells.

The treatment unit just described (substantially it is a matter of a generator/photoelectrocatalytic reactor) is characterized by an unexpected increase of photo- voltage and photocurrent, with respect to the sum of the single photolytic and electrolytic actions, thanks to the synergic action exerted by the photocatalyst (preferably, blue silicate, TiO₂, and/or their mix¬ tures) , preferably incorporated/applied to the dynamic molecule microporous catalyst. Said synergic action allows a very high production of superoxidizing agents and a particularly high speed of degradation and removal of the toxic substances (or¬ ganic and not) , well higher than the one obtainable, for example, with the biological purification proc¬ esses (usually, not more than 2 hours against the typical 24-48 of the biological processes) . The purified liquid exiting from said treatment unit is sent to further settling, clarification and recov¬ ery units of the inertized and sterilized waters and sludges.

For example, said liquid can be sent to a clarifier with vertical septa, for the overflow of the particles with a density lower than the water and for the set¬ tling of those with a higher density, with a pneumatic expulsion system of the settled sludges. The treatment unit can also include a thickener of the sludges, with a progressive increase of the pressure in order to promote the thickening of the sludges and the recycle of the separated liquid fraction (purified water) which is sent back to the process reactor. In another preferred embodiment of the invention, the purifier includes a reaction zone comprising a con¬ tainer having windows (and/or the lid) transparent to the ultraviolet radiations; said windows/lid being coated with TiO₂ gel. More preferably, the internal walls of the container are coated with TiO₂, blue silicate or their mixtures, incorporated/applied to dynamic molecule microporous catalysts and an artifi¬ cial ultraviolet source is preferably applied within the lid of the container. In this case, the generator of superoxidizing agents is contained in said con¬ tainer, that is within the reaction zone. This kind of embodiment is particularly useful for pu¬ rifying the urban wet waste, contained in garbage cans and bins, from the bad smells generated from decaying substances.

In another preferred embodiment of the invention, the purifier includes a generator of superoxidizing agents placed inside a suction hood; said suction hood in¬ cluding a passage region of suctioned polluted and malodorous fumes defining said reactione zone. Inside said hood a source of ultraviolet light is po¬ sitioned and the photocatalyst, preferably incorpo¬ rated/applied to dynamic molecule microporous cata¬ lysts is directly applied on the porous filtering sur¬ face of the hood itself, or inside proper filtering interchangeable elements.

The filtering surfaces and/or the filters of said hood are maintained wet and airy in order to allow the pro¬ duction of the superoxidizing agents during the sue- tion of the harmful and/or malodorous gases. In a preferred embodiment, said gases are bubbled through a water seal before being suctioned in said hood.

The enclosed figures from 1 to 6 show, by mere way of non limiting example, some of the preferred embodi¬ ments of the invention. DESCRIPTION OF THE FIGURES

Fig. 1 shows the diagram of a photocatalytic purifier particularly useful for purifying domestic waste wa¬ ters. There are pointed out: the frustoconical-shaped photolytic generator with a double coaxial wall (1), containing the photocatalyst incorporated/applied on the dynamic molecule microporous catalyst (2); the ul¬ traviolet lamp (3); the top water diffuser (4); the reaction zone (5) , including the first housing cavity

(6), the inlet for the fluid to be purified (7), the input for the superoxidants (8), the second housing cavity, coaxial to the first one (9), which contains the photocatalyst incorporated/applied on the dynamic molecule microporous catalyst; the third housing cav¬ ity (10), including the decantation zone (11), the discharge for the sterilized sludges (12) and the out¬ let for the completely purified and sterilized fluid

(water) . Fig. 2 shows two possible applications of the purifier of Fig. 1. The A) solution shows 3 purifiers connected in parallel [(1) = waste waters inlet; (2) = purified and sterilized water outlet] . The B) solution shows two purifiers connected in parallel and, in turn, each one connected in series with other two purifiers, in order to obtain the maximum of the purification with the minimum possible hindrance.

Fig. 3 shows the diagram of a photoelectrocatalytic purifier particularly useful for purifying and steril¬ izing waste waters and sludges deriving from indus¬ trial processings. In particular, there are pointed out: (1) the photoelectrocatalytic generator of super- oxidizing agents, previously described; (2) the treat¬ ment unit of the wet fraction of the purified liquid (or reactor of abiotic stabilization of the sludges), shown in detail in the following Fig. 4, including an inlet for the wet sludges to be concentrated and ster¬ ilized (H) , an outlet for the sterilized sludges (F) , an outlet for the sterile fluid (water) recovered by the sludges (G); (3) the reaction zone, including a tank/reactor comprising a first inlet for the fluid to be purified (A) , a second inlet for the superoxidizing agents (A' ) , a third inlet for adding further quanti¬ ties of catalysts (C) , an outlet for the purified fluid to be settled (C ) , the walls coated with the photocatalyst incorporated/applied to the dynamic molecule microporous catalyst (B) , a source of ultra¬ violet light (D) , mixing means of the fluid to be pu¬ rified; (4) a settling unit for the wet sludges to be concentrated and sterilized deriving from the reaction zone (3) .

Fig. 4 shows a detailed diagram of the treatment unit of the wet fraction of the purified fluid (or reactor of abiotic stabilization of the wet sludges [Fig. 3, (2)]) deriving from the settling unit of the wet sludges [Fig. 3, (4)] . There are pointed out, in par¬ ticular: the inlet of the wet sludges to be stabi¬ lized, concentrated and sterilized (3) ; the outer cy¬ lindrical body (1), equipped with windows transparent to the solar radiation (2), said windows being coated by TiO₂ gel; the transparent cylinder housing the ul¬ traviolet lamps, inserted in a central position (12) ; the electrolytic cells (6), delimited by the outer cylinder (1) and transverse disk photoelectrodes (7), said photoelectrodes being equipped with through-holes and transverse septa, which force the flow of the wet sludges to go through the cells with a circular rota¬ tory direction; system for periodic draining of the settled sterilized solid sludges in the lower zone of the treatment unit (10) and (11); additional settling, clarification and recovery units of the waters and discharge of the sludges (4), (5), (8) and (9) . Fig. 5 shows the diagram of two embodiments, (A) and

(B) , of containers for purifying the urban wet waste from the bad smells generated by decaying substances. There are pointed out, in particular: windows and lids transparent to the ultraviolet light, coated with TiC>₂ gel (2), (4) ; the blind walls internally coated with TiC>₂, blue silicate or their mixtures, incorpo¬ rated/applied to dynamic molecule microporous cata¬ lysts. Fig. 6 shows the diagram of three embodiments, (A),

(B) and (C) , of suction hoods for purifying the air from polluting or malodorous volatile substances. There are pointed out, in particular: the ultraviolet lamps (2); the filter walls impregnated with the photocatalyst incorporated/applied to the dynamic molecule microporous catalyst (3), (4) and (5); the interchangeable filter elements impregnated with the photocatalyst incorporated/applied to the dynamic molecule microporous catalyst. DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention is completely abiotic; that is, it does not need the presence of any biological species in any step thereof. Both the waters and the sludges obtained by the puri¬ fication process of the present invention, besides completely lacking any polluting residue, also result completely sterile.

They do not need, therefore, any further treatment and can be, accordingly, sent to the respective following uses.

The purification of the wet waste through the ozone- radical reaction, catalyzed by photocatalysts and dy¬ namic molecule microporous catalysts, is almost istan- taneous. The dynamic molecule microporous catalyst performs different functions, that is: catalytic ac¬ tion, for accelerating the superoxidative etching against the organic substrates, active molecular ac¬ tion towards bioresistent substances and heavy metals, action of molecular sieve for the production of oxygen O₂, for the purposes of the photoelectrogeneration of the ozone and action of photocatalization, if coated with said photocatalysts.

The generator of superoxidizing agents preferably works with the depurated water exiting from the reac¬ tion zone of the purifier.

The process of the present invention allows to carry out the purification of the wet waste above defined through the superoxidation of the putrescible sub¬ stances, the demolition of the harmful compounds, of long chained fats and the stabilization and steriliza¬ tion of all the substances present in the wet waste, sludges included.

Said process then allows the demolition of liquid, solid or gaseous harmful compounds and the trapping of the heavy metals.

The proposed system generates the superoxidants at a very low cost, because the starting products for the production of said superoxidants are water, air and/or oxygen.

The antibacterial effect of TiO₂ and blue silicate is particularly evident when, exposed to the ultraviolet light, they come into contact with water and air by producing ^'OH hydroxyl radicals and ozone, which de¬ termine the antibacterial effect caused by the absorp¬ tion and the decomposition of the toxins during the photocatalytic reaction.

On average, the antibacterial effect (disinfection) of TiO₂ and blue silicate is three times stronger than the chlorination and 1,5 times stronger than the ozonization alone.

The process of the present invention allows to detox¬ ify the drinking water, to decontaminate and purify the industrial waste water, also if it contains ali¬ phatic chlorinated hydrocarbons which are dechlori- nated and mineralized, giving water and CO₂ as resi¬ dues. Furthermore, said process allows to eliminate as well the substances which are resistant to the normal oxidation reactions. Some organic substances that may be treated with said process are, for example: al- kanes, PCB (polychlorinathed biphenyls), alkenes, di- oxins, alkynes, furans, ethers, antiparasitic agents, aldehydes, herbicides, ketons, alcohols phenols, am- mines, cyanide, ammides, trichloromethane. The arrival of a UV photon on the surface of the particles of TiC>₂ or blue silicate pulls away an electron from the va¬ lence shell of the product, by generating therein some electron lacks (called electron lacks or "holes") . Said holes behave themselves as strongly oxidizing species and rapidly react with the oxygen of the air, by tranforming it in ozone, and with the water, oxi¬ dizing it to oxygen. In turn, the electron extirpated by the UV photon is capable to react with the water by producing, for example, ^'OH radicals.

The photoexcitation can derive from sunlight or from ultraviolet light lamps.

In ai preferred embodiment, the photocatalytic action of the blue silicate is used for generating the super- oxidizing agents and then employing them in the dif¬ ferent possible steps of the purification process, that is pre-treatment, depurative treatment, sludges stabilization, for example through the equipments: photoelectrocatalytic generator, photocatalized proc¬ ess reactor, photoelectrocatalized post-reactor, ver¬ tical septa clarifier, sludges thickener at a progres¬ sive pressure.

Turning again to the disinfection properties of TiO₂ and blue silicate under exposure to UV radiation and by applying a voltage to the electrodes, the integra¬ tion of the photocatalytic and electrolytic action in a single photoelectrochemical system synergically in¬ creases the production of superoxidants and therefore improves the effectiveness and the speed of the degra¬ dation of the acqueous polluting substances. In the process of the present invention with ozone- radical reaction, the cationic metals precipitate as hydroxides, carbonates or phosphates and are seques¬ tered inside the pores of the dynamic molecules micro- porous catalyst.

When the heavy metals are blocked in the catalyst crystals, they can not be re-dissolved in the water. In the presence of metals such as Mn(III) and Fe(III), the use of the superoxidants mixture, catalized by the catalysts above described, starts fast and effective radical processes which allow the superoxidation of phenols, aromatic and chlorinated compounds. The dynamic molecule sieves contain chabazite and are able to absorb Pb, chrome and other heavy metals also in the presence of possible interfering means, such as sodium chloride (NaCl) . Other cations of heavy metals against which the molecular sieves with chabzite have a good affinity are Cd and Cu.

The dynamic molecule microporous catalysts also allow the selective removal of unwanted substances, for ex¬ ample SO2, from CO₂- and gas-containing gaseous mix¬ tures.

Said catalysts have a high adsorbing ability for their great internal transcrystalline surface area, about 95% by volume. Moreover, they are very selective be¬ cause the molecules are separated based on their di¬ mensions and the relative structures, and based on their dimensions and the geometry of the pores opening and therefore molecules of a different dimension have different diffusion properties therein.

Through the abiotic treatment of the waste or drinking waters with the process of the present invention, the following effects can further be obtained: - distruction of thiols groups in enzymes and proteins by the oxidation effect of said groups to disulfides, sulfoxides and disulfoxides;

- degradation of substances which are hardly biode¬ gradable, such as hydrocarbons, animal and vegetal fats, phenols, organo-halogenated compounds, also if present in small quantities; said substances are not degraded by the microrganisms normally present in the biological treatment plants of the waste, they tend to limit the activity of the natural flora, slowing down the degradation processes which allow the biological composting of the waste.

The photoelectrocatalytic generator of superoxidants is innovative because it ads in a synergic way the photocatalytic action of the passive internal sur¬ faces, capable of producing superoxidants at a contact with air and water if hit by UV rays in the presence of photocatalyst incorporated/applied to dynamic mole¬ cule micropporous catalysts, with that relative to the photoelectrocatalytic action feasible thanks to the photocatalyst layer which coats the electrodes. The yield of the photoelectrocatalytic generator dra¬ matically increases by applying an anode polarization. The photocatalytic activity of te blue silicate photo¬ catalyst, used in order to cover an electrode in pho- toelectrolytic cells, increases the effectiveness of electrolytic separation of the water in hydrogen and oxygen. The production of superoxidants through pas¬ sive or active photocatalizing surfaces (photoelec- trodes) , starting from the water and air, allows the completely abiotic treatment of the waters. The abiotic treatment of the present invention re¬ quires extremely reduced volumes, because the reten¬ tion time which usually in the biological system is of 24-48 hours, in the abiotic treatment is not more than 120 minutes. Also the settling system of the sludges needs a lower surface, since the sludges, besides be¬ ing reduced for the greater transformation of the or¬ ganic substances in carbon dioxide and water, remain characterized by a more effective settling ability. Furthermore, in the depuration plants of an abiotic type the section of sterilization of the treated wa¬ ters is absent, since the same automatically remain sterile for the effect of the process itself, which is superoxidative, thanks to the superoxidizing mixture constituted, among others, by ozone and ^'OH hydroxyl radicals.

The waters treated with the process of the present in¬ vention, besides showing reductions very close to 100/100 of COD and BOD₅, show parameters set to zero or almost zero of polluting substances, such as: heavy _ o ι; _

metals, phenols, oils, greases, chlorine and deriva¬ tives.

As for the choice of the materials used for the photo- electrodes, oxides, such as TiO₂, SnO₂, WO₃, are resis¬ tant to the electrochemical corrosion, while ZnO is only stable as a cathode. In particular, TiO₂ is espe¬ cially preferred because its exceptional chemical re¬ sistance in solution. Also mixed oxides, such as SrTiO₃ are advantageously used.

In the simplest form, a photoelectrochemical cell in¬ cludes a semiconductor electrode and a metal counte- relectrode, dipped in an acqueous electrolyte. The processes take place in the cell when the light reaches the semiconductor electrode. When the light hits the semiconductor electrode, this absorbs the part of the light and the electricity generated, giv¬ ing rise to the electrolysis of the water. If, as the electrolyte, water to be depurated is present, the electricity is absorbed in a remarkable extent by the pollutants, at the cost of the production of the su- peroxidizing agents. This is why the generator can use, as the electrolyte, already depurated and clari¬ fied water.

The conductivity of the semiconductor electrodes is expressed by the following equation:

wherein,

A = conductivity of the semiconductor; e = electronic charge; μ = mobility of the bearing element (subscript _n for the electron, _p for the holes) ; n = concentration of the negative bearing elements; p = concentration of the positive bearing elements;

The balance between the energy of the actuating force and the consumption of said electrolysis energy for a single system of the photoelectrode can be write down as follows:

E_g - V_B - (Ce - E_f) = "GZ_nF + a + c + iR + V_H wherein, E₉ is the split of the band, Ce is the posi¬ tion of the edge of the conduction band, E_f is the Fermi level;

"G/_nF represents the energy required for transforming a water molecule in H₂ and O₂ and is equal to 1.2eV; a and c represent sovrapotentials to the anode and the cathode, respectively, while iR represents the ohmic losses and V_H represents the potential drop through the Helmholtz layers in the electrolyte. The left-hand side of the equation represents the net energy avail¬ able to an excited electrone by a photon which has an energy equivalent to the band split. Even if the minimum voltage required for the water electrolysis is 1.23 V, in practice, there are poten¬ tial losses connected with the cathode and the anode and also in the best cases, the electrolysis of the water requires a voltage of 1.5 V.

The relation shows that the effectiveness can be con¬ trolled by operating on the current intensity and the retention time.

When a photoelectron leaves a surface of the metal, it has a kinetic energy.

It is possible to reject the photoelectron from a negatively charged photoelectrode.

The work made by the electrode is = e • V (wherein V is the electrode voltage) .

If the photoelectron is arrested, then e • V = kinetic energy of the electron.

This will occur at a certain voltage called stopping potential (V • s) . Such stopping energy serves to con¬ trol the semi-reactions in the photoelectrochemical cells; in fact, the proper voltage applied to the an¬ ode allows the stream of water and air to pass through the cells in a semireaction regime. It is therefore important to adequately control the stopping poten¬ tial, by allowing the reactive species not to migrate to the electrodes but to stay in the reaction environ- ment destroying the polluting species.

The dimensioning of the continuous electrochemical cells must take into account the need of optimizating the parameters above shown, in order to reduce the plant and the operating costs.

The parameter which expresses in the more significant manner the economic effectiveness of the process is generally the ratio of the power applied to the flow- rate quantity of the treated waste water, expressed in kWh/m³.

For a photoelectrolytic cell, with a total anode sur¬ face (active surface) of 4.5 m², working with a C.C.B.T. 120 A feeding and 12 V - 50 Hz, such ideal value is of 1.5 kWh/m³ • 2 m³ of the waste waters to be treated, that is 3 KWh.

Preferably, the disk electrodes of Ti are sintered with TiC>2 and/or blue silicate. Said electrodes in¬ crease the photovoltage, respectively, from 0.78 V to 0.8 V and the photocurrent from 5 mA to 14 mA per cm². This determines the increase of the quantity of hydro¬ gen-produced per water electrolysis of 1.2 - 1.8 ml. In the photocatalytic process electrochemically as¬ sisted with blue silicate photoelectrodes, the photo- current of the cell is greatly higher than the one ob¬ tainable with traditional electrodes (not less than 25 itiA) . In the photoelectrocatalytic reactor with photo- electrode, the current of the photoelectrochemical cell results greater than the current of the photo- lytic or electrochemical treatment alone and also greater than their sum.

This shows the interactive synergic effect between the photochemical and the electrochemical processes. For example, the photoelectrode with TiC>₂ and/or blue silicate surfaces may present the following propor¬ tions: UV lamp (125 W) ; zone coated with TiO₂ and/or blue silicate of 39.8 cm² (included the surface of the photoelectrodes) ; potential applied to the photoelec- trodes 1.3 V.

In the post-treatment unit of the wet sludges, the en¬ ergy of photoexcitation of the blue silicate which is of 3.2 V is preferably employed. The employed source of irradiation may be an arc lamp of 450 W Xe with a band-pass filter of UV radiations. The UV emission is preferably higher than 290nm with an intensity of 2.202 mW/cm².

In an embodiment, the process of the present invention is carried out in special depurative self-functional moduli, consisted of: generator of superoxidants (so¬ lar or not) , reaction zone or process reactor, filter photocatalized with blue silicate incorporated/applied to the dynamic molecules microporous catalyst, clari- fier.

Said generator includes a preferably frustoconical surface consisted of granular microporous catalysts with dynamic molecules, sinterized with micronized and microporous powdery blue silicate, sequestered inside a perforated sheet metal- or network structure. Such photocatalytic surface is externally excited by the ultraviolet solar radiation and internally excited by that of an UV lamp.

The reaction zone, within which the waters, the sludges or the air to be depurated flow, is developed within a cylinder (possibly a double coaxial cylinder) with the internal wall made of perforated sheet metal with, inside, the photocatalyst incorporated/applied to the dynamic molecule microporous catalyst for a further supply of direct photocatalysis on the efflu¬ ent to be treated.

Such cylinder is open at the bottom, in order to allow the downflow to the clarification zone of the treated fluid. The path of the flow from the top to the bottom determines the separation of the thicker solid parti¬ cles and prevents those lighter from leaving the proc¬ ess reactor before their final superoxidative abiotic demolition. The clarified flow overflows in a duct/- filter, completely filled with additional photocata- lysts. The waters, after such a treatment, result per¬ fectly purified after a retention time not more than 8 hours. Depending on the pollution content of the flow¬ ing fluid, the effluent exiting from the modulus will eventually pass in series through additional moduli in order to ensure the desired purification. The waters purified from each single modulus are recycled in or¬ der to irrigate the photocatalized surfaces of the electric solar frustoconical-shaped generator of su- peroxidants, positioned above the process reactor. Such positioning allows the superoxidants produced by photocatalysis, starting from the recycled purified waters, to flow with gravity in the reaction zone. In¬ side the photocatalyst cone, a strongly oxidizing at¬ mosphere is formed; this allows the demolition of the gaseous polluting substances as well, which are pre¬ sent in the water to be depurated.

The advantages of the process of the present invention are, for example, the following:

1. The superoxidative abiotic depurative process is carried out in complete absence of bacteria.

2. It is possible to effectively work with a wide range of polluting, organic and inorganic substances; preferably, those not biodegradable. 3. The superoxidizing mixture of ozone, superoxide an¬ ion, singlet oxygen and ^'OH hydroxyl radicals, used for the treatment of the wet waste, is economically produced in situ.

4. It is possible to use the solar radiation as a source of energy in order to significantly reduce the purification costs.

5. The purifying process is sterilizing at the same time.

6. The purifying process allows the recycle and the recovery of the purified waters for irrigated or pro¬ ductive purposes.

7. The purifying process is adaptable to any kind of waters.

8. The purifying process requires a minimum consump¬ tion of energy for the production of the superoxidants also when the UV rays are produced by ultraviolet lamps.

9. The purifying process requires limited hindrances of the purifier sections.

10. The purifying process produces a reduced volume of sludges and helps the settling ability thereof.

11. The purifying process is characterized by a per¬ fectly automatic functioning of the components of the purification system. 12. In the purified effluent, suspended coarse sub¬ stances are absent.

13. In the purified effluent, residual colouring sub¬ stances are absent.

14. The purifying process completely eliminates unple- sant smells or toxic depuration by-products.

15. The purifying process is usable in production plants of biogas.

16. The purifying process is usable for the obtaining drinkable waters.

17. The purifying process is usable for the treatment of the plerotic waters.

18. The purifying process is usable in purification systems already existent.

19. The purifying process is usable for treating the waste waters of: dyehouse, tannery, car wash, paper mill, agricultural-industrial plants and abattoirs, dumping ground leachates .

20. The purifying process is usable for the reduction of ammonia and nitrates present in industrial waste water, by transforming them in gaseous nitrogen.

21. The_. purifying process is usable, in particular, for eliminating the water-soluble chlorinated sol¬ vents, which are difficult to treat with the conven¬ tional processes, such as, the adsorption on activated carbons .

22. The purifying process is usable for eliminating perchlorates, benzene, toluene, ethylbenzene and xy¬ lene, carcinogens present in the gasoline, which often appear as polluting agents of the groundwater contami¬ nated by the gasoline.

23. The purifying process is usable for eliminating organic nitrocompounds, such as dinitrotoluene, trini¬ trotoluene and nitroglycerin, present in primitive wa¬ ters and in treated waste waters near to production places of explosives or rifle ranges, and can pene¬ trate into the surface water or the groundwater.

24. The purifying process allows to directly or indi¬ rectly measure (and accordingly to properly dose) ozone and ^'OH radicals through electron paramagnetic resonance (EPR) , method of the hydrogen peroxide and the residues of the probe, such as pCBA.

25. The purifying process is usable for purifying the sea waters polluted by residues, wastes and sewages of a different origin.

Claims

1. Process for purifying wet waste, including at least a step of contacting said waste with superoxi- dizing agents in the presence of at least a photocata- lyst and at least a microporous inorganic catalyst.

2. Process according to claim 1, wherein said wet waste are selected among waste waters, wet solid waste, sludges and polluted and/or malodorous air.

3. Process according to claims 1 and 2, wherein said at least one step is carried out under the action of ultraviolet radiations.

4. Process according to claim 3, wherein said ultra¬ violet radiations have a wavelength of about 390 nm; more preferably, equal to or lower than 390 nm.

5. Process according to claims 3 and 4, wherein said radiations are of a natural and/or artificial origin.

6. Process according to any one of the claims 1 to 5, wherein said superoxidizing agents include O₂, O₃, su¬ peroxide anion, singlet oxygen, ^'OH radicals; more preferably, O₃ and ^'0H, or their mixtures.

7. Process according to claim 6, wherein said super- oxidizing agents are produced in loco immediately, be¬ fore and/or simultaneously at the step of contact with the waste.

8. Process according to claims 6 and 7, wherein said superoxidizing agents are produced through catalytic photolysis and/or photoelectrolysis of waters and air/oxygen.

9. Process according to claim 8, wherein said photolysis and/or photoelectrolysis is carried out in a generator of superoxidants including at least a photocatalyst and at least a microporous inorganic catalyst; said generator capable of being irradiated by a source of ultraviolet radiations, in order to ac¬ tivate said photocatalyst.

10. Process according to any one of the preceding claims, wherein the photocatalyst includes one or more photoexcitable compounds following to an ultraviolet irradiation, such as: TiO₂, blue silicate, ZnO, WO₃, and their mixtures; preferably, TiO₂, blue silicate and their mixtures; more preferably, blue silicate and/or blue silicate/Ti0₂ mixtures.

11. Process according to any one of the preceding claims, wherein the microporous inorganic catalyst is a dynamic molecule microporou^'s catalyst.

12. Process according to claim 11, wherein said dy¬ namic molecule microporous catalyst includes a micro¬ porous material selected from: molecular sieves, zeo¬ lites, pumices, kaolin, clay and the like and/or their mixtures; said microporous material containing at least 5% by weight of dynamic molecule sieves, based on the total weight of the catalyst; preferably, at least 10% by weight, more preferably, at least 20% by weight.

13. Process according to claim 12, wherein said dy¬ namic molecule sieves are molecular sieves having with silico-aluminated acid sites and mobile Na⁺ ions rich- sites.

14. Process according to any one of the preceding claims, wherein the photocatalyst is incorpora¬ ted/applied to the dynamic molecule microporous cata¬ lyst.

15. Process according to claim 14, wherein the photo- catalyst is incorporated/applied to the dynamic mole¬ cule microporous catalyst in a quantity not lower than 5% by weight based on the weight of said catalyst; preferably, not lower than 10% by weight; more pref¬ erably, not lower than 15% by weight.

16.^' Process according to claim 15, wherein Tiθ₂, blue silicate or their mixtures, are incorporated/applied to the dynamic molecule microporous catalyst in a quantity between 15% to 40% by weight based on the weight of said catalyst; preferably, between 20% and 30% by weight.

17. Process according to any one of the claims 14 to 16, wherein the photocatalyst is incorporated, in form of powder, in the dynamic molecule microporous cata¬ lyst by sintering.

18. Process according to any one of the claims 14 to 16, wherein TiO₂ is applied, in form of a gel, to the dynamic molecule microporous catalyst by spraying or bath.

19. Purifier for carry out the process according to any one of the claims 1 to 18, characterized in that it includes:

- at least a generator of superoxidizing agents in¬ cluding at least a photocatalyst and a dynamic mole¬ cule microporous catalyst, for generating said super- oxidants from water and air/oxygen; said generator ca¬ pable of being irradiated by a source of ultraviolet radiations in order to activate said photocatalyst;

- at least a reaction zone placed in a fluid communi¬ cation with said generator of superoxidants to let said wet waste react with said superoxidants.

20. Purifier according to claim 19, wherein said gen¬ erator of superoxidizing agents further ^"includes at least an ultraviolet lamp for activating the photo¬ catalyst.

21. Purifier according to claim 20, wherein said at least one ultraviolet lamp emits ultraviolet radia- tions having a wavelength of about 390 ran; more pref¬ erably, equal to or lower than 390 ran.

22. Purifier according to claim 19, wherein within said generator of superoxidants said at least one photocatalyst is incorporated/applied to said dynamic molecule microporous catalyst.

23. Purifier according to any one of the claims 19 to 22, wherein said generator of superoxidants includes a retaining body defining a cavity containing said photocatalyst and said dynamic molecule microporous catalyst, said cavity being exposed to the air and be¬ ing wettable with water, and an outlet for said super¬ oxidants .

24. Purifier according to any one of the preceding claims, wherein said reaction zone includes a reactor having a first inlet for the fluid to be purified, a second inlet for the superconductors and an outlet for the purified fluid.

25. Purifier according to claim 24, wherein said re¬ actor includes a first housing cavity for containing the fluid to be purified and the superoxidizing agents; said cavity being delimited by a porous septum which put it into contact with a second housing cavity containing said at least one photocatalyst incorpo¬ rated/applied to said dynamic molecule microporous catalyst .

26. Purifier according to claim 25, wherein said re¬ actor further includes a third housing cavity for the decantation of the purified liquid.

27. Purifier according to claim 24, wherein said re¬ actor further includes a third inlet for additional catalysts.

28. Purifier according to claim 27, wherein said re¬ actor further includes mixing means of the fluid to be purified.

29. Purifier according to claim 28, wherein said re¬ actor further includes at least an ultraviolet lamp.

30. Purifier according to any one of the claims 27 to 20, wherein the walls of said reactor are coated with said at least one photocatalyst incorporated/applied to said dynamic molecule microporous catalyst.

31. Purifier according to any one of the claims 19 to

30, further including at least a settler for separat¬ ing the liquid fraction, purified from the wet frac¬ tion, residual sludges, of the purified fluid.

32. Purifier according to any one of the claims 19 to

31, further including a treatment unit of the wet fraction of the purified fluid for separating the solid fraction, sludges, from the water contained therein, by simultaneous inertization and steriliza- tion thereof.

33. Purifier according to claim 32, wherein said treatment unit includes a tubular body having a first end including a first inlet for said wet fraction and at least a second inlet for the air and/or the oxygen; a second end comprising an outlet for the liquid ster¬ ile fraction of the wet and a plurality of outlets for the solid fraction of the wet; said plurality of ou- lets for the solid fraction being peripherally ar¬ ranged on said tubular body.

34. Purifier according to any one of the claims 32 to 33, wherein said treatment unit further includes a plurality of disk photoelectrodes positioned inside and transverse to said tubular body; said disks being spaced therebetween in order to define a plurality of photoelectrolytic cells and decantation chambers; each decantation chamber including one of said outlets for the solid fraction of the wet.

35. Purifier according to claim 34, wherein said disk photoelectrodes inlcude an anode and a cathode; said cathode and said anode being coated with said photo- catalyst incorporated/applied in said dynamic molecule microporous catalyst.

36. Purifier according to claim 34, wherein said disk photoelectrodes further include through-holes and transversal septa which force the flow of the sludges to go through the cells with a circular rotatory di¬ rection.

37. Purifier according to any one of the claims 32 to

36, wherein said treatment unit further includes a transparent cylinder for the housing of the ultravio¬ let lamps, inserted in a central position and axially to the tubular body of the treatment unit.

38. Purifier according to any one of the claims 32 to

37, wherein the internal walls of said treatment unit and those of the photoelectrolytic cells are coated with the photocatalyst incorporated/applied to the dy¬ namic molecule microporous catalyst.

39. Purifier according to any one of the claims 32 to

38, wherein said treatment unit further includes an electronic control system of the stopping potential of the semi-reactions in the photoelectrolytic cells.

40. Purifier according to claim 19, wherein said re¬ action zone includes a container having windows trans¬ parent to the ultraviolet radiations; said generator of superoxidants being contained in said container.

41. Purifier according to claim 19, wherein said gen¬ erator of superoxidants is arranged inside a suction¬ ing hood; said suctioning hood including a passage re¬ gion of suctioned fumes defining said reaction zone.