WO2019058086A1

WO2019058086A1 - Process for manufacturing a porous material from incineration clinkers

Info

Publication number: WO2019058086A1
Application number: PCT/FR2018/052361
Authority: WO
Inventors: Clément Sanchez; Cédric BOISSIERE; Lionel Nicole; Hiva BARADARI; Xavier Chaucherie; Bruno GILARDIN
Original assignee: Sarp Industries; College De France
Priority date: 2017-09-25
Filing date: 2018-09-25
Publication date: 2019-03-28
Also published as: FR3071494A1; FR3071494B1

Abstract

The invention relates to a process for manufacturing a porous material comprising the following steps of providing incineration clinkers, providing an aqueous binder solution comprising at least one inorganic binder and/or at least one organic-inorganic hybrid binder, mixing said clinkers with said aqueous binder solution comprising at least one inorganic binder and/or at least one organic-inorganic hybrid binder, setting said mixture obtained by heat treatment and finally recovering the porous material thus manufactured. The manufacturing process thus makes it possible to recycle and upgrade the incineration clinkers by means of the production of a porous material. The process is particularly advantageous since the porous material may in particular be obtained very rapidly and may be used as insulating material or construction material.

Description

PROCESS FOR MANUFACTURING POROUS MATERIAL FROM INCINERATION MACHEFERS

The invention relates to the field of recycling and relates to a method of manufacturing a porous material, said process for the recovery and recycling of incineration slag.

Technological background

At present in France, incineration is the second mode of disposal of household waste. The treatment of waste by incineration is a process not only applied to domestic waste but also to industrial waste. The incineration process results in the reduction of the volume and mass of solid waste, but this reduction is only apparent. In fact, the incineration generates about 5000 m3 of smoke per ton of burnt waste, solid residues and liquid effluents resulting for example from the treatment of fumes or the quenching of slag.

The solid slag collected at the base of incinerator furnaces at the end of the combustion of waste is called slag incineration waste (MIOM) and / or slag incineration industrial waste (MIDI). They consist of ashes generally in the form of granules, various incombustibles such as for example mixtures of ferrous and non-ferrous metals, glasses, silica, alumina, limestone, lime, as well as imbricated and water. Each ton of waste incinerated producing 250 kg to 300 kg of slag, this represents for the French territory alone an annual production of about 3 million tons of bottom ash.

Thanks to certain physical characteristics of the slag, in particular their good bearing capacity, a large part has been valued in road engineering, in particular in substitution of natural aggregates. In France, for example, more than 2 million tons of bottom ash are applied mainly in road sub-layers. However, the composition of the bottom ash, by the presence of polluting elements such as heavy metals and dioxins, is problematic from the environmental point of view.

Indeed, water from rainwater runoff or percolation can lead to the dispersion of pollutants and thus contaminate the surrounding soil and groundwater.

In order to limit the environmental impact of the slag, it is necessary to determine their leaching rate as well as that of the materials containing them. In this sense, the decree of 18 November 2011 on the recycling of non-hazardous waste incineration ash in road transport introduced additional constraints, such as the increase in the number of substances to be taken into account, the reduction of a large majority of pollutant thresholds or the reinforcement of the traceability of these substances. These restrictions lead to a limitation of the recovery of the slag in the field of road techniques thus leading to an increase in landfill disposal. There is therefore a need to develop recycling routes in order to reduce the amount of landfill disposal, especially as there are currently few opportunities for upgrading and recycling slag and Research has focused on processes for treating slag to facilitate their long-term recycling. These treatments are also known as inerting processes.

In this respect, document F 2714625 describes a solidification and stabilization process for solid residues resulting from the thermal treatment of toxic waste resulting from destruction by incineration. It is an inerting process which aims to transform a waste, in particular slag, into a hard and mechanically resistant monolithic mass in which the toxic elements contained in said waste have become stable and resistant to leaching by acidic waters. . Thus, this document describes a process for inerting toxic waste, particularly slag, comprising a first step of shaping the waste by granulation, pelletizing, pelletizing, shredding or extrusion, so as to obtain individualized figurative elements, and a second step of encapsulation of said elements with a coating of geopolymeric chemical nature. The first step is carried out with a prior addition of hydraulic binder, preferably a traditional cement. The second encapsulation step is carried out using a purely inorganic coating of the poly (sialate), poly (sialate-siloxo) or poly (sialate-disiloxo) type, no organic component is thus put in place. implemented. The coating being carried out after shaping, this has the disadvantage of resulting in a geopolymer that does not integrate the constituents of the slag in its matrix and co-polymerization can not take place with them. In addition, the binder used being a hydraulic binder, it does not react chemically with the waste and thus does not allow the creation of a porous material. Therefore, this process only makes it possible to create a protective cap around the slag against acid leaching.

This document therefore describes only an inerting process for creating a geopolymer of protection around the slag for their long-term storage and the reactions implemented in this process do not involve the components of slag. The inerting process according to this document therefore does not make it possible to manufacture a porous material and to value the bottom ash as such. Another method for treating municipal or industrial incineration residues (slag, MIOM, MIDI) is also described in document EP 0 922 470. In this process, the waste to be treated is mixed in a basic medium with clay, a non-hydraulic inorganic binder. The purpose of this process is to fix the heavy metals contained in the slag, such as lead, by trapping them with clay. In this way, the majority of the leachable natural lead was thus fixed in the treated slag. As shown by the tests, the process is effective in the natural environment, especially in the case of residues disposed in piles and thus subjected to washing under the effect of rainwater. However, this method, although adapted to allow storage outdoors slag, is absolutely not dimensioned for a valuation of the latter on an industrial scale to obtain a usable material.

The document WO 89/02766 describes a process for the solidification and storage of waste making it possible to confer on them a stability comparable to that of certain archaeological materials over time. The process consists in preparing and mixing the waste with an alkaline aluminosilicate geopolymer binder having a zeolitic character in such proportions that a mixture containing in situ a poly (sialate) type geopolymeric matrix and / or poly (sialate) is obtained. siloxo) and / or poly (sialate-disiloxo), said geopolymeric matrix jointly achieving the stabilization of toxic elements and solidification in a rigid and durable material. Thus, by means of a solidification and storage process, this document describes the production of materials based on only inorganic matrices and does not concern the manufacture of a material in which the waste participates from a point structural view with porous appearance.

As mentioned above, research has so far mainly focused on processes for the treatment of slag for long-term storage, but it is also known that recovery methods through the manufacture of objects , materials, monoliths or geopolymers from slag, can also be implemented.

For example, the document F 2 696 662 describes an object manufacturing process that makes it possible to recycle and reclaim industrial and household waste. This process consists of several steps, the first of which consists in producing a homogeneous mixture from industrial or household waste and a binder such as cement, lime, mineral or organic resins, sand, aluminates, zirconates, hafnates or silicates. The mixture obtained is then moistened and kept under agitation in order to maintain good homogeneity. Industrial and household waste may be washed out of chlorides, bromides and iodides that they may contain and then dried. The second step is to obtain the desired shape of the object by means of pressure molding (50 to 1000 bar). However, although this method describes in a very general manner the possibility of recovering bottom ash in the form of products made of massive materials, it does not propose precise and concrete implementation allowing in particular an effective valuation of slag at the industrial scale.

Thus, among the clinker treatment routes, some of them tend to neutralize them for long-term storage while others tend to manufacture materials. The first is unsatisfactory in that long-term storage should only be used as a last resort, as for the latter, the processes are not necessarily adaptable on an industrial scale with the possibility of being carried out continuously. There is therefore a real need to develop new recycling processes for treating incineration slag and thus to propose new recovery alternatives, in particular by obtaining material.

It is therefore the merit of the Applicant to have developed a new process of recovery and recycling of slag, said method for making large scale in a simple and fast manner a porous material from slag and meet the challenges of treating millions of tons of waste.

Summary of the invention

The invention relates to a method of manufacturing a porous material comprising the following steps of:

supply of incineration slag,

supply of an aqueous binder solution comprising at least one inorganic binder and / or at least one hybrid organic-inorganic binder,

mixing said bottom ash with said aqueous binder solution comprising at least one inorganic binder and / or at least one hybrid organic-inorganic binder,

taken by heat treatment of said mixture obtained,

- recovery of the porous material.

The manufacturing process thus makes it possible to recycle and / or valorize the slag through the production of a material. The method is particularly interesting because the material can in particular be obtained quickly. A second subject of the invention relates to a porous material that can be obtained by the above method.

DETAILED DESCRIPTION According to the first object, the invention relates to a method of manufacturing a porous material comprising the following steps of:

supply of incineration slag,

providing an aqueous binder solution comprising at least one inorganic compound and / or at least one hybrid organic-inorganic binder,

mixing said bottom ash with said binder solution comprising at least one inorganic binder and / or at least one hybrid organic-inorganic binder,

taken by heat treatment of said mixture,

recovery of the porous material.

Surprisingly, the inventors have found that the process according to the invention, by the implementation of a particular aqueous binder solution and a heat treatment step, made it possible to obtain rigid porous materials which offer thus a valuation of the slag in a way never used before.

Indeed, the presence of the binder causes contact with the components of the slag gas release to generate porosity, but also the capture and consolidation of the materials thus produced by partial dissolution and re-precipitation of the constituents of slag.

For the purposes of the present invention, the term "slag" is used to designate both incineration slag of industrial origin (MIDI) and slag incineration of household waste (MIOM), except when the context will allow identify that it is precisely one or the other. The first step of the process according to the invention therefore consists in providing incineration slag. Advantageously, the incineration slag provided can be dried and milled to obtain a bottom ash powder. The powder can then be passed through one or more sieves so as to obtain the desired particle size before the mixing step with the aqueous binder solution. Thus, the bottom ash powder may in particular have a particle size of less than 5 mm, preferably less than 3 mm, and most particularly, a particle size of less than 1 mm.

According to one embodiment, the slag may be pretreated before mixing with the aqueous solution. For example, the dried and ground incineration slags that are supplied may suffer pretreatment in the dry process, such as a magnetic separation step. Magnetic separation is a dry technique known to those skilled in the art and allows, through fields of varying intensity, to separate certain compounds of the bottom ash according to their respective behavior vis-à-vis the field magnetic. The particle size of a slag powder thus pretreated can be between 100 μιτι and 1000 μιτι. The magnetic components thus separated constitute a fraction which can advantageously be reused in the process according to the invention in order to overcome the intrinsic variability of certain incineration slag.

The second step of the process according to the invention consists in providing an aqueous binder solution comprising at least one inorganic binder and / or at least one hybrid organic-inorganic binder. This solution is advantageously a basic solution which may further comprise a surfactant.

For the purposes of the present invention, the term "inorganic binder" means a binder which gives rise in a sol / gel reaction to the creation of an inorganic matrix. Likewise, the term "organic-inorganic hybrid binder" means a binder which gives rise in a sol / gel reaction to the creation of an organic / inorganic hybrid matrix.

The aqueous binder solution makes it possible to contribute to the creation of an inorganic or hybrid organic / inorganic matrix but also to overcome the intrinsic chemical variability related to the origin of the bottom ash. Indeed, there is a chemical variability between MIDI and MIOM, as well as between MIDI or MIOM not coming from the same incineration center or from the same incineration center but having a different daily or weekly composition as well than different levels of maturity.

The amounts of binder used in the aqueous solution are selected so as to obtain in the porous material at the end of the process according to the invention, an amount of binder of 1% to 50%, preferably 5% to 45%. The percentages being expressed by mass of dry extract relative to the total mass of the porous material.

According to one embodiment, the aqueous binder solution comprises at least one inorganic binder. In this case the aqueous binder solution is free of hybrid organic-inorganic binder. According to this embodiment, the inorganic binder is in particular a silicic or aluminosilicic binder, and preferably a silicic binder. When the binder is silicic, it is advantageously chosen from the group consisting of silicic acid, silicon alkoxides, silicates, colloidal silica, silicon tetrachloride SiCl ₄ , and mixtures thereof. In a preferred manner, the inorganic binder is chosen from silicates, colloidal silica or their mixtures. According to another embodiment, the aqueous binder solution comprises at least one inorganic binder as defined above and at least one hybrid organic-inorganic binder. According to this embodiment, the hybrid organic-inorganic binder may consist of at least one hybrid precursor of formula (I) or (II): R ' _x Si Z ₄ . _x (I)

Z ₃ Si-R "-SiZ ₃ (II) in which:

x is an integer from 1 to 3;

Z represents, independently of one another, a halogen atom, or a group -OR, and preferably a group -OR;

R represents H or an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl group, preferably H, a methyl or ethyl group, and more preferably a methyl group or an H;

R 'represents, independently of each other, H or a non-hydrolyzable group selected from alkyl groups, especially C ₁₄ , for example, methyl, ethyl, propyl or butyl; alkenyl groups, in particular C ₂ . ₄ , such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C ₂ _-4 , such as acetylenyl and propargyl; aryl groups, in particular C ₆ _10, such as phenyl and naphthyl; methacryl or methacryloxy groups Ci_i ₀ as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl in which the alkyl groups is linear, branched or cyclic Ci_i _0, and the alkoxy group contains from 1 to 10 carbon atoms, such as glycidyl glycidyloxyalkyl in Ci_i _0; haloalkyl groups, C ₂ _i ₀ such as 3-chloropropyl; mercaptoalkyl groups C ₂ _i ₀ such as mercaptopropyl; aminoalkyl groups, C ₂ .i ₀ such as 3-aminopropyl; (C ₂ -C ₁₀ amino) amino (C ₂ -C ₁₀ ) alkyl groups such as 3 - [(2-aminoethyl) amino] propyl; the di (alkylene C ₂ _ ₁₀₎ triamino (C _2. ₁₀₎ such as 3- [diéthylènetriamino] propyl and imidazolyl groups in C _2. ₁₀ ; C2-10 cyanoalkyl groups, C ₂ phosphonatoalkyl groups. ₁₀ , C ₂ carboxyalkyl groups. ₁₀

R "represents a non-hydrolyzable function chosen from alkylene groups preferably at ₁₂ , for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene, alkynylene groups preferably of C ₂ _i ₂ , for example acetylenylene (-C≡C-), -C≡C-C≡C-, and -C≡CC ₆ H ₄ -C≡-; N, N-di (C ₂ -C ₁₀ ) alkylene amino groups; such as Ν, Ν-diéthylèneamino; groups bis [N, N-di (C ₂ alkylene _i ₀₎ amino] such as bis [N- (3-propylene) -N-methyleneamino] mercaptoalkylene C ₂ _i ₀ such as mercaptopropylene, (C ₂ -C ₁₀ ) alkylene polysulfide groups such as propylene disulfide or propylene tetrasulfide, and especially C _{2 to} C ₄ alkenylene groups, such as than vinylene; arylene groups, in particular C ₆ -C ₁₀ , such as phenylene; the di (alkylene C ₂ -io) arylene C ₆ .i _0, such as di (ethylene) phenylene; N, N'-di (C ₂ -C ₁₀ ) ureido groups such as N, N'-dipropyleneurido.

As examples of organoalkoxysilane of formula (I), there may be mentioned in particular methyltrialkoxysilane (O) ₃ Si-CH ₃ , 3-aminopropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) 3 -NH 2, 3 - (2-aminoethyl) aminopropyltrialkoxysilane (O) ₃ Si- (CH 2) 3 -NH- (CH ₂ ) 2 -NH 2, 3- (trialkoxysilyl) propyl-diethylenetriamine (O) ₃ Si- (CH 2) 3 -NH - (CH 2) 2-NH- (CH ₂ ) 2 -NH 2; 3-chloropropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) ₃ Cl, 3-mercaptopropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) ₃ SH; carboxyethylsilanetriol (HO) ₃ Si- (CH ₂ ) ₂ ∞O ^" Na ⁺ , 3-trihydroxysilylpropylmethylphosphonate (HO) ₃ Si- (CH ₂ ) ₃ OP (CH ₃ ) O- ^" Na ⁺ ; (3-glycidoxypropyl) trialkoxysilane; 3-Cyanopropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) ₃ CN; oligomers of aminopropylsilsesquioxane and aminoethylaminopropylsilsesquioxane-methylsilsesquioxane copolymers; R having the same meaning as above.

Examples of bis-alkoxysilane of formula (II), preferably used is a bis- [trialcoxysilyljméthane (RO) ₃ Si-CH ₂ -Si (OR) _3, a bis- [trialkoxysilyl] ethane (RO) ₃ Si- ( CH ₂ ) ₂ -Si (OR) ₃ , a bis [trialkoxysilylpropyl] amine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -Si (OR) ₃ , a bis (tri)

[trialkoxysilylpropyl] ethylenediamine (RO) ₃ Si- (CH 2) ₃ -NH- (CH 2) 2 -NH- (CH ₂ ) ₃ -Si (OR) ₃ ; a bis- [trialkoxysilylpropyl] disulfide (RO) ₃ Si- (CH 2) ₃ -S _{2 -} (CH ₂ ) ₃ -Si (OR) ₃ , a bis- [trialkoxysilylpropyl] tetrasulfide (RO) ₃ Si- (CH ₂ ) ₃ - S ₄ - (CH ₂ ) ₃ -Si (OR) ₃ , a bis- [trialkoxysilylpropyl] urea (RO) ₃ Si- (CH ₂ ) ₃ -NH-CO-NH- (CH ₂ ) ₃ -Si (OR) ₃ ; R having the same meaning as above. The content of organic-inorganic hybrid compound in the aqueous binder solution comprising at least one inorganic compound and at least one organic-inorganic hybrid compound as defined above may be from 1 to 95 mol%, and preferably from 5 to 50 mol% of the silicic or aluminosilicic species contained in the mixture. The molar percentage is in particular defined by the following formula: ## EQU1 ## In another embodiment, the aqueous binder solution comprises only at least one hybrid organic-inorganic binder. In this case the aqueous binder solution is free of inorganic binder. According to this embodiment, the hybrid organic-inorganic binder may consist of at least one hybrid precursor of formula (I) or (II) as defined above.

The aqueous binder solution according to the invention is advantageously a basic solution. Preferably, the pH of the aqueous binder solution is between 10 and 14. Thus, the pH can be adjusted by the addition of a strong mineral or organic base, preferably by a base selected from KOH, NaOH or mixtures thereof. The aqueous binder solution may also comprise a surfactant. The addition of a surfactant advantageously makes it possible, on the one hand, to reduce the release of dihydrogen and thus to limit the associated industrial risks and, on the other hand, to lead to better control of the porosity of the material obtained. The surfactant may be a nonionic surfactant such as, for example Brij 58 ^® (Croda International PLC) or can also be cetyltrimethylammonium bromide (CTAB). The use of an aqueous binder solution in the process for manufacturing a material according to the invention makes it possible to obtain materials based on a binder other than the cement conventionally used, and this entails, in particular for the field of construction. , a decrease in the impact of this sector on the environment. Indeed, the process according to the invention and thus less energy. The third step of the process according to the invention consists in mixing the slag with the aqueous solution of binder.

The mixing can be done according to the methods known to those skilled in the art which result in bringing said slag into contact with said aqueous binder solution so as to obtain a suspension. The bringing into contact entails in particular a gaseous release of dihydrogen which serves to generate a controlled porosity, but also the setting and consolidation of the materials thus produced by partial dissolution and re-precipitation of the constituents of the bottom ash.

Indeed, bringing the solution into contact with the bottom ash particles leads to the basic attack and the oxidation of the metal components of the bottom ash generating in particular a local decrease in pH and the condensation of the binder. The competition between the condensation of the binder, induced by the consumption of the hydroxides in the medium and the evaporation of the water molecules make it possible to control the generation of porosity within the materials during the setting. Contrary to what is implemented in the prior art, the bottom ash particles are thus consolidated by the action of the binder and a porous material is thus obtained.

The fourth step of the process according to the invention consists in carrying out a heat treatment of the mixture of bottom ash and aqueous binder solution.

The heat treatment step allows the mixture of bottom ash to become solid with the aqueous binder solution. Thus, the treatment of the mixture makes it possible to freeze the assembly in order to trap the gas bubbles and to develop rigid porous materials of variable density.

The heat treatment advantageously makes it possible to accelerate the setting and drying phenomena and to generate a rapid increase in the viscosity. Those skilled in the art can easily adapt the conditions of said heat treatment according to the mixture of slag and aqueous binder solution it has. The use of a heat treatment makes it possible to adapt to different shaping processes, such as, for example, pouring, rolling or still extrusion, in order to obtain materials in a dense form or in a form of foam. The heat treatment thus makes it possible to manufacture very rapidly materials having a perfectly controlled rheology.

According to a particular embodiment, the heat treatment is a microwave treatment. According to this embodiment, in order to vary the final properties of the material obtained and to accelerate the caking, the skilled person can easily adapt the conditions, especially in terms of time and power, depending on the composition and the amount of slag and the final application sought. Thus, the microwave treatment may for example be performed at a power of between 500 and 1500 Watt, such as about 900 Watt. Regarding the treatment time, it can be between 30 seconds and 5 minutes.

The method according to the invention thus makes it possible to obtain a porous material in a rigid form or in a foam form, said material having an apparent density which may range from 0.5 g / cm ^{3 to} 2 g / cm ³ , preferably from 0.9 g / cm ³ to 1.7 g / cm ³ , for example about 1 g / cm ³ . According to a particular embodiment, the heat treatment step may be followed by a densification step and then a second heat treatment step. The densification step advantageously makes it possible to eliminate a part of the gas bubbles contained in the porous material at the end of the first heat treatment step, this having the consequence of being achieved once the second heat treatment stage has been completed. on said densified material, to obtain a porous material having a higher density and a reduced porosity. This densification step can be carried out according to the techniques known to those skilled in the art such as kneading, compression or by means of vibrations.

The method according to the invention is particularly advantageous in that it proposes a new recovery pathway for slag making it possible to obtain a porous material that can for example be used for various applications in the building industry. Indeed, thanks in particular to its density properties, the material according to the invention can be used as an insulating material or as a construction material.

Then, the process is advantageous in that it does not generate waste other than gaseous releases, mainly water releases. Finally, the process according to the invention is a process that is easily adaptable on an industrial scale and can also be carried out continuously, thereby constituting a significant advantage, taking into account the processes known from the prior art and the amount of slag to be treated. . A second subject of the invention relates to a porous material that can be obtained by the process according to the invention as such, that is to say prepared from bottom ash and an aqueous binder solution comprising at least one inorganic binder and / or an organic-inorganic hybrid binder. The porous material according to the invention comprises an inorganic binder and / or an organic-inorganic hybrid binder as defined above. The amounts of inorganic binder and / or organic-inorganic hybrid in this material may be from 5% to 45% based on the total dry weight of the porous material.

Advantageously, the apparent density of the porous material is from 0.5 g / cm ³ to 2 g / cm ³ , preferably from 0.90 g / cm ³ to 1.7 g / cm ³ , for example about 1 g / cm ^3. cm ³ .

The invention will be better understood with the aid of the examples which follow, which are intended to be purely illustrative and in no way limit the scope of the protection.

EXAMPLES

EXAMPLE 1 Manufacture of a monolith based on slugs of particle size less than 1 mm and inorganic binder (Na 2 SiO 3 .Sh 2).

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the inorganic binder is obtained by mixing using a ultrasonic bath 4.35 g of Na ₂ Si0 ₃ .5H ₂ 0 in 7.4 ml of distilled H ₂ 0. A third step consists in adding the inorganic binder dropwise to the 10 g of previously prepared slag and stirring mechanically until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) of 3 minutes at 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 20% by weight of the final porous material obtained and a bulk density of 0.9 g / cm ³ .

EXAMPLE 2 Manufacture of a monolith based on slugs of particle size less than 1 mm and inorganic binder (Ludox HS-40).

In a first step, 10 grams of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the inorganic binder is obtained by mixing 1.9 g of Ludox HS-40 to a solution containing 0.4 g of KOH and 0.85 mL of distilled H ₂ 0. The mixture is then stirred with magnetic stirring and at ambient temperature until a transparent solution is obtained. A third step is to add the 10 g of bottom ash to the inorganic binder under mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) from 30 seconds to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 10% by weight of the final porous material obtained and a bulk density of 1.07 g / cm ³ . EXAMPLE 3 Manufacture of a Monolith Based on Mufflers of Particle Size Less Than 1 mm and Organic-inorganic Hybrid Binder Containing Methyltrimethoxysilane

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the hybrid binder is obtained by mixing 7.25 g of Ludox HS-40, 0.73 g of methyltrimethoxysilane, 1.7 g of KOH and 4 ml of distilled H ₂ O. The mixture is then stirred with magnetic stirring and at ambient temperature until a transparent solution is obtained. A third step is to add the 10 g of bottom ash to the hybrid binder under mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is produced by a microwave treatment (MW) of 2.5 minutes at 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 32% by weight of the final material obtained and a bulk density of 1.04 g / cm ³ .

Example 4: Manufacture of a monolith based on slugs of particle size less than 1 mm and hybrid organic-inorganic binder containing aminopropylsilsesquioxane.

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the hybrid binder is obtained by mixing 1.18 g of Ludox HS-40, 0.52 g of aminopropylsilsesquioxane, 0.27 g of KOH and 0.7 ml of distilled H ₂ O. The mixture is then stirred with magnetic stirring and at ambient temperature until a transparent solution is obtained. A third step is to add the 10 g of bottom ash to the hybrid binder under mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) from 40 seconds to 900 watts. The porous materials are presented after drying in the form of non friable monoliths. The binder in dry extract represents 8% by weight of the final material obtained and a bulk density of 1.0 g / cm ³ .

EXAMPLE 5 Manufacture of a Monolith Based on Slugs of Grading Below 1 mm and Organic Hybrid-Inorganic Binder Containing 3-Trihydroxy Silylpropylmethylphosphonate

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the hybrid binder is obtained by mixing 2.7 g of Ludox HS-40, 1.14 g of sodium 3-trihydroxysilylpropylmethylphosphonate, 0.62 g of KOH and 1.5 ml of distilled H ₂ O . The mixture is then stirred with magnetic stirring and at ambient temperature until a transparent solution is obtained. A third step is to add the 10 g of bottom ash to the hybrid binder under mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) from 70 seconds to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 17.5% by weight of the final material obtained and a bulk density of 1.03 g / cm ³ .

EXAMPLE 6 Manufacture of a monolith based on slugs having a particle size of less than 1 mm and organic-inorganic hybrid binder containing glycidoxypropyltrimethoxysilane.

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the hybrid binder solution is obtained by mixing 1.58 g of Ludox HS-40 and 0.28 g glycidoxypropyltrimethoxysilane in a solution containing 0.36 g of KOH and 0.9 ml of distilled H ₂ O this mixture being left stirring at 500 rpm until a transparent solution is obtained. A third step consists in adding the 10 g of clinker to the hybrid binder progressively with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the caking is carried out by a microwave treatment (MW) from 40 seconds to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 10.4% by weight of the final porous material, the latter then having a bulk density of 0.93 g / cm ³ after drying.

It is also possible to add, following the same protocol, the 10 g of bottom ash to solutions containing either 3.55 g Ludox HS-40, 0.62 g glycidoxypropyltrimethoxysilane, 0.82 g KOH and 2.0 mL of distilled H ₂ 0 is 6.09 g of Ludox HS-40, 1.07 g glycidoxypropyltrimethoxysilane, 1.40 g of KOH and 3.45 mL of distilled H ₂ 0. The microwave treatments at 900 watts are respectively 100 and 130 seconds. The binder in dry extract then represents respectively 20.7% and 30.9% by weight of the porous materials, the latter then having a bulk density of 0.92 and 1.06 g / cm ³ respectively. It is also possible to interrupt the microwave treatment to perform a mixing step to increase the bulk density.

EXAMPLE 7 Manufacture of a monolith based on slugs of particle size less than 1 mm and organic-inorganic hybrid binder containing sodium carboxyethylsilanetriol.

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the hybrid binder is obtained by mixing 2.5 g of Ludox HS-40, 1.28 g of sodium carboxyethylsilanetriol, 0.57 g of KOH and 1.4 ml of distilled H ₂ O. The mixture is then stirred with magnetic stirring and at ambient temperature until a transparent solution is obtained. A third step is to add the 10 g of bottom ash to the hybrid binder under mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold, and the bulk of the sample is made by a microwave treatment (MW) from 70 seconds to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 15.4% by weight of the final material obtained and a bulk density of 1.0 g / cm ³ .

Example 8 Manufacture of a monolith-based particle size of less than 1 mm Bottom ash and inorganic binder (Ludox HS-40) containing a nonionic surfactant (brii ^® 58)

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the inorganic binder is obtained by mixing 4.26 g of Ludox HS-40 to a solution containing 0.88 g of KOH and 1.9 ml of distilled H ₂ 0. A third step is to add 0.7 g of a surfactant solution prepared from 0.1 g of Brij ^® 58 and 0.6 mL of distilled water to 10 g of slag. The slag / surfactant mixture is then added to the inorganic binder progressively with mechanical stirring until a viscous slurry is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) of 80 s to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder in dry extract represents 20% by weight of the final porous material, the latter then having a bulk density of 1.12 g / cm ³ after drying. It is also possible to interrupt the microwave treatment to perform a mixing step to increase the bulk density. EXAMPLE 9 Manufacture of a Monolith Based on Maskblers with a Grain Size of Less Than 1 mm and an Inorganic Binder (Ludox HS-40) Containing a Surfactant (CTAB)

In a first step, 10 g of bottom ash are dried in an oven for 24 hours at 95 ° C and then ground and sieved to obtain a powder whose particle size is less than 1 mm. In a second step, the inorganic binder is obtained by mixing 4.26 g of Ludox HS-40 with a solution containing 0.88 g of KOH and 1.9 ml of distilled H ₂ O to which 0.7 g is added. of a surfactant solution prepared from 0.1 g of CTAB and 0.6 ml of distilled water. A third step is to add the 10 g of bottom ash to the inorganic binder in a progressive manner with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the bulk of the sample is made by a microwave treatment (MW) of 80 seconds to 900 watts. The porous materials are after drying in the form of non-friable monoliths. The binder dry extract represents 20% by weight of the final porous material, the latter then having a bulk density of 1.17 g / cm ³ . It is also possible to interrupt the microwave treatment to perform a mixing step to increase the bulk density. This step is even more effective than the mass percentage of water in the binder is important.

Claims

A method of manufacturing a porous material comprising the following steps of:

supply of incineration slag,

supplying an aqueous binder solution comprising at least one inorganic binder which gives rise in a sol / gel reaction to the creation of an inorganic matrix and / or at least one hybrid organic-inorganic binder which gives rise in a soil reaction / gel to the creation of an organic / inorganic hybrid matrix,

taken by heat treatment of said mixture obtained,

recovery of the porous material.

2. Method according to claim 1, characterized in that the incineration slag provided are dried, crushed and undergo dry pretreatment such as magnetic separation.

3. Method according to claim 1 or 2, characterized in that the amounts of binder in the aqueous binder solution are selected so that the recovered porous material has a binder amount of 1% to 50% by weight of binder. dry extract relative to the total mass of said material.

4. Method according to one of claims 1 to 3, characterized in that the inorganic binder is a silicic binder or aluminosilicic.

5. Method according to claim 4, characterized in that the inorganic binder is a silicic binder selected from the group consisting of silicic acid, silicon alkoxides, silicates, colloidal silica, silicon tetrachloride SiCl ₄ , and their mixtures, and preferably selected from the group consisting of silicates, colloidal silica and mixtures thereof.

6. Method according to any one of the preceding claims, characterized in that the aqueous binder solution comprises at least one inorganic binder and at least one hybrid organic-inorganic binder.

7. Process according to claim 6, characterized in that the hybrid organic-inorganic binder consists of at least one hybrid organic-inorganic precursor of formula (I) or (II) below:

Z ₃ Si-R "-SiZ ₃ (II)

in which : x is an integer from 1 to 3;

R 'represents, independently of each other, H, a non-hydrolyzable group selected from alkyl, particularly CI_ _4, for example, methyl, ethyl, propyl or butyl; alkenyl groups, in particular C ₂ . ₄ , such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, in particular C ₂ . ₄ , such as acetylenyl and propargyl; aryl groups, in particular C ₆ .i _0, such as phenyl and naphthyl; methacryl or C _1-10 methacryloxyalkyl groups such as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C _1-10 , and the alkoxy group has 1 to 10 carbon atoms, such as glycidyl and glycidyloxyalkyl in QL-10; haloalkyl groups, C ₂ .i ₀ such as 3-chloropropyl; C ₂ -C 10 mercaptoalkyl groups such as mercaptopropyl; C ₂ aminoalkyl groups. w such as 3-aminopropyl; (C ₂ -C ₁₀ amino) amino (C ₂ -C 10) alkyl groups such as 3 - [(2-aminoethyl) amino] propyl; the di (C ₂ alkylene _i ₀₎ triamino (C _2- io) such as 3- [diéthylènetriamino] propyl and imidazolyl groups C ₂ _i _0; cyanoalkyl groups 2-10, the groups C ₂ phosphonatoalkyle _IO, carboxyalkyl groups C ₂ _IO

R "represents a non-hydrolysable functional group chosen from alkylene groups preferably C _1-12, for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups preferably C _2. ₁₂ for example, acétylénylène (-C≡C-), -C≡CC≡C-, and -C≡CC ₆ H ₄ -C≡C-; N, N-di (C ₂ alkylene _i ₀₎ amino such as N, N-diethyleneamino; bis [N, N-di (C ₂ -C ₁₀ ) alkylene] amino groups such as bis [N- (3-propylene) -N-methyleneamino]; C ₂ -mercaptoalkylene. such as mercaptopropylene, (C ₂ -C ₁₀ ) alkylene polysulfide groups such as propylene disulfide or propylene tetrasulphide, especially C ₂ -C ₄ alkenylene groups, such as vinylene, arylene groups in particular C 6 -C 10 groups; such as phenylene; the di (C ₂ alkylene. ₁₀₎ arylene C ₆ .i _0, such as di (ethylene) phenylene; groups N, N'-di (. C ₂ alkylene ₁₀₎ uréid o such that Ν, Ν'-dipropyleneurido.

8. Process according to claim 7, in which the hybrid organic-inorganic precursor of formula (I) is chosen from the group comprising methyltrialkoxysilane (RO) ₃ Si-CH ₃ , 3-aminopropyltrialkoxysilane (O) ₃ Si (CH ₂₎ ) 3-NI-12, 3- (2-aminoethyl) aminopropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) 3 -NH- (CH ₂ ) ₂ -NH ₂ , 3- (trialkoxysilyl) propyldiethylenetriamine (RO) ₃ Si- (CH ₂₎ ₃ -NH- (CH ₂₎ ₂ - NH- (CH ₂₎ ₂ -NH _2, 3-chloropropyltrialcoxysilane (RO) ₃ Si- (CH ₂₎ ₃ CI, 3-mercaptopropyltrialkoxysilane (RO ) ₃ Si- (CH ₂ ) ₃ SH, carboxyethylsilanetriol (HO) ₃ Si- (CH ₂ ) ₂ COO ^" Na ⁺ , 3-trihydroxysilylpropylmethylphosphonate (HO) ₃ Si- (CH ₂ ) ₃ OP (CH ₃ ) 00 ^" Na ⁺ ; (3-glycidoxypropyl) trialkoxysilane, 3-cyanopropyltrialkoxysilane (RO) ₃ Si- (CH ₂ ) ₃ CN, the oligomers of aminopropylsilsesquioxane and the copolymers of aminoethylaminopropylsilsesquioxan-methylsilsesquioxane, where R is H or an alkyl group preferably comprising 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl, preferably H, methyl, or ethyl, and preferably another methyl group or H;

The process according to claim 7, wherein the hybrid organic-inorganic precursor of formula (II) is selected from the group consisting of bis [trialkoxysilyl] methane (RO) ₃ Si-CH ₂ -Si (OR) ₃ , bis- [trialkoxysilyl] ethane (RO) ₃ Si- (CH ₂ ) ₂ -Si (OR) ₃ , bis [trialkoxysilylpropyl] amine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ - Si (OR) ₃ , bis [trialkoxysilylpropyl] ethylenediamine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -Si (OR) ₃ ; bis- [trialkoxysilylpropyl] disulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OR) ₃ , bis- [trialkoxysilylpropyl] tetrasulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₄ - (CH ₂ ) ₃ -Si (OR) ₃ , bis [trialkoxysilylpropyl] urea (RO) ₃ Si- (CH ₂ ) ₃ -NH-CO-NH- (CH ₂ ) ₃ -Si (OR), wherein R is H or an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl group, preferably H, methyl, or ethyl, and more preferably methyl or H;

10. Process according to any one of the preceding claims, characterized in that the incineration slag are incineration slag of industrial origin (MIDI) or slag incineration of household waste (MIOM).

11. Method according to one of the preceding claims, characterized in that the heat treatment step is a step of setting by microwave treatment.

12. The method of claim 11, characterized in that the capture by microwave treatment is performed for about 3 minutes at a power of about 900 Watts.

13. Porous material comprising incineration slag and at least one inorganic binder and optionally at least one hybrid organic-inorganic binder, characterized in that it has a bulk density of 0.5 g / cm ³ to 2 g / cm. ³ , preferably from 0.90 g / cm ³ to 1.7 g / cm ³ .

14. A porous material according to claim 13, characterized in that the inorganic binder is a silicic binder selected from the group consisting of silicic acid, silicon alkoxides, silicate, colloidal silica, SiCl ₄ silicon tetrachloride, and mixtures thereof, and preferably, silicate, colloidal silica, or mixtures thereof.

15. A porous material according to claim 13 or 14, characterized in that the organic-inorganic hybrid binder consists of at least one organic-inorganic hybrid precursor of formula (I) or (II) below:

R'xSi Z ₄ . _x (I) Z ₃ Si-R "-SiZ ₃ (II) in which:

x is an integer from 1 to 3;

R 'represents, independently of each other, H, a non-hydrolyzable group selected from alkyl, particularly CI_ _4, for example, methyl, ethyl, propyl or butyl; alkenyl groups, especially C ₂ _-4 , such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl groups, especially C ₂ _-4 , such as acetylenyl and propargyl; aryl groups, in particular C ₆ -C ₁₀ , such as phenyl and naphthyl; methacryl or methacryloxy groups Ci_i ₀ as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl in which the alkyl groups is linear, branched or cyclic Ci_i _0, and the alkoxy group contains from 1 to 10 carbon atoms, such as glycidyl glycidyloxyalkyl C _1-10; haloalkyl groups, C ₂ .i ₀ such as 3-chloropropyl; C ₂ -C ₁₀ mercaptoalkyl groups such as mercaptopropyl; C ₂ aminoalkyl groups. ₁₀ as 3-aminopropyl; groups (amino-C ₂ _ ₁₀₎ alkylamino (C ₂ _10.) such as 3 - [(2-aminoethyl) amino] propyl; the di (alkylene C ₂ _ ₁₀₎ triamino (C _2. ₁₀₎ such as 3- [diéthylènetriamino] propyl and imidazolyl groups in C _2. ₁₀ ; C2-10 cyanoalkyl groups, C ₂ phosphonatoalkyl groups. ₁₀ , C ₂ carboxyalkyl groups. ₁₀

R "represents a non-hydrolysable functional group chosen from alkylene preferably groups CI_ i _2, for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups, preferably C ₂ _12,. for example, acetylenylene (-C≡C-), -C≡C- C≡C-, and -C≡CC ₆ H ₄ -C≡C-; N, N-di (C ₁ -C ₁₀ ) alkylene amino groups such as Ν, Ν-diethyleneamino; bis [N, N-di (C ₂ -C ₁₀ ) alkylene amino] groups such as bis [N- (3-propylene) -N-methyleneamino]; C ₂ -C 10 mercaptoalkylene such as mercaptopropylene; (C ₂ -C ₁₀ ) alkylene polysulfide groups such as propylene disulfide or propylene tetrasulfide; alkenylene groups, in particular C ₂ . ₄ , such as vinylene; arylene groups, in particular C ₆ -C ₁₀ , such as phenylene; the di (C ₂ alkylene. ₁₀₎ arylene C ₆ .i _0, such as di (ethylene) phenylene; Groups N, N'-di (C ₂ alkylene. ₁₀₎ ureido such as N, N'-dipropylèneuréido.

16. Porous material according to one of claims 13 to 15, characterized in that it comprises an amount of inorganic binder and / or hybrid organic-inorganic binder of 5% to 45% relative to the dry mass of porous materials. .