FR3071494A1 - PROCESS FOR MANUFACTURING POROUS MATERIAL FROM INCINERATION MACHEFERS - Google Patents

Abstract

The invention relates to a method of manufacturing a porous material comprising the following steps of providing incineration slag, providing an aqueous binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid binder mixing said slag with said aqueous binder solution comprising at least one inorganic binder and / or at least one hybrid organic-inorganic binder, heat-treating said obtained mixture and finally recovering the porous material thus produced. The manufacturing process thus makes it possible to recycle and valorize the incineration slag through the production of a porous material. The method is particularly interesting because the porous material can in particular be obtained very quickly and can be used as an insulating material or construction material.

Description

The invention relates to the field of recycling and relates to a method of manufacturing a porous material, said method allowing the recovery and recycling of incineration clinkers.

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 household waste but also to industrial waste.

The incineration process results in a reduction in the volume and mass of solid waste, however this reduction is only apparent. Incineration generates approximately 5,000 m3 of smoke per tonne of waste burned, solid residues and liquid effluents from, for example, smoke treatment or the quenching of bottom ash.

The solid slag collected at the base of incinerator ovens after the combustion of waste is called clinker for the incineration of household waste (MIOM) and / or clinker for the incineration of industrial waste (MIDI). They are composed of ash 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 unburnt and water. Each tonne of incinerated waste producing 250 kg to 300 kg of bottom ash, this represents for French territory alone an annual production of around 3 million tonnes of bottom ash.

Thanks to certain physical characteristics of bottom clinkers, in particular their good bearing capacity, a large part has been valued in road engineering, in particular as a replacement for natural aggregates. In France, for example, more than 2 million tonnes of bottom ash are applied mainly in road underlayments. However, the composition of bottom ash, due to the presence of pollutants such as heavy metals and dioxins, is problematic from an environmental standpoint.

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

In order to limit the environmental impact of bottom ash, it is necessary to determine their leaching rate as well as that of the materials containing them. In this sense, the decree of November 18, 2011, relating to the recycling of non-hazardous waste incineration clinkers in road engineering, introduced additional constraints such as the increase in the number of substances to be taken into account, the reduction the vast majority of pollutant thresholds or even the strengthening of the traceability of these substances. These restrictions lead to a limitation in the recovery of bottom ash in the field of road engineering, thus leading to an increase in landfill storage. There is therefore a need to develop recycling methods in order to reduce pure and simple storage in landfill, all the more so since at present, the possibilities of recovery and recycling of bottom ash are few and the research has mainly focused on processes for treating clinkers in order to facilitate their recycling in the long term. These treatments are also known as inerting processes.

As such, document FR 2 714 625 describes a process for solidifying and stabilizing solid residues resulting from the thermal treatment of toxic waste resulting from destruction by incineration. The method described comprises a first step of prior agglomeration of the waste in the form of an aggregate, followed by a second step of encapsulation for inerting. The encapsulation step is carried out using an inorganic coating of the poly (sialate), poly (sialatesiloxo) or poly (sialate-disiloxo) type. Finally, this encapsulation step is followed by an ultra fast hardening step by infrared heating or by microwave treatment.

However, the coating used in this inerting process is carried out after the agglomeration step. This means that the geopolymer does not integrate the constituents of the bottom ash in the matrix and therefore cannot co-polymerize with some of them, but only allows the creation of a protective capsule against acid leaching around the granules containing the bottom ash. . This process therefore does not make it possible to valorize the clinkers as such because the reactions implemented do not involve the components of the clinkers, but only makes it possible to create a protective geopolymer for long-term storage.

Another process for treating urban or industrial incineration residues (bottom ash, MIOM, MIDI) is also described in document EP 0 922 470. In this process, the waste to be treated is mixed in basic medium with clay, a non-hydraulic inorganic binder. The purpose of this process is to fix the heavy metals contained in the bottom ash, such as lead, by trapping them with clay. In this way, the majority of natural leachable lead was thus fixed in the treated bottom ash. As the tests show, the process is effective in a natural environment, in particular in the case of residues arranged in heaps and therefore subjected to washing under the effect of rainwater. However, this process, although suitable for allowing the bottom ash to be stored outside, is absolutely not designed for recovery of the latter on an industrial scale with a view to obtaining a usable material.

The document WO 89/02766 describes a process for solidifying and storing waste making it possible to give it a stability over time comparable to that of certain archaeological materials. The process consists in preparing and mixing the waste with an alkaline aluminosilicate geopolymer binder having a zeolitic character in proportions such that a mixture containing in situ a geopolymeric matrix of poly (sialate) type, and / or poly (sialate type) is obtained. siloxo) and / or poly (sialate-disiloxo), said geopolymeric matrix jointly achieving the stabilization of toxic elements and solidification into a rigid and durable material. Thus, this document describes, by means of a solidification and storage process, the obtaining of materials based on only inorganic matrices.

As mentioned previously, research has mainly focused so far on methods allowing a treatment of bottom ash with a view to long-term storage, but it is also known that recovery routes through the manufacture of objects , materials, monoliths or even geopolymers from bottom ash, can also be used.

For example, the document FR 2 696 662 describes a method of manufacturing objects which makes it possible to recycle and recycle industrial and household waste. This process is made up of several stages, the first of which consists of dry 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 humidified and kept stirring in order to maintain good homogeneity. Industrial and household waste may possibly be removed by washing the chlorides, bromides and iodides that they are likely to contain, and then be dried. The second step consists in obtaining the desired shape of the object by means of a pressure molding (50 to 1000 bars). However, although this process describes in a very general way the possibility of recovery of bottom ash in the form of products made of massive materials, it does not propose a precise and concrete implementation allowing in particular an effective recovery of bottom ash with industrial scale.

Thus, among the clinker processing routes, some of them tend to neutralize the latter for long-term storage while others tend more to manufacture materials. The first way is not satisfactory in the sense that long-term storage should only be used as a last resort, as for the second, 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 which make it possible to treat incineration clinkers and thus to propose new recovery alternatives, in particular by obtaining material.

It is therefore to the credit of the Applicant to have developed a new process for recovering and recycling clinkers, said process making it possible to manufacture porous material on a large scale in a simple and rapid manner and to respond and the challenges posed by the treatment of millions of tonnes of waste.

Summary of the invention

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

supply of incineration clinkers, supply of an aqueous binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid binder, mixing of said clinkers with said aqueous binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid 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 recycle bottom ash through the production of a material. The process is particularly interesting because the material can in particular be obtained quickly.

A second object of the invention relates to a porous material capable of being 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 clinkers, supply of an aqueous binder solution comprising at least one inorganic compound and / or at least one organic-inorganic hybrid binder, mixing of said clinkers with said binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid binder, taken by heat treatment of said mixture, recovery of the porous material.

In a completely surprising manner, the inventors have found that the method according to the invention, by the use of a specific aqueous binder solution and a heat treatment step, makes it possible to obtain rigid porous materials offering thus a recovery of bottom ash according to a route hitherto never followed.

In fact, the presence of the binder leads to contact with the components of the bottom clinkers, a gaseous release making it possible to generate porosity, but also the setting and consolidation of the materials thus produced by partial dissolution and re-precipitation of the constituents of the bottom clinkers.

Within the meaning of the present invention, the term "bottom ash" is used to designate both bottom ash from industrial incineration (MIDI) as bottom bottom ash from household incineration (MIOM), except when the context allows '' identify that it is precisely one or the other.

The first step of the process according to the invention therefore consists in providing bottom ash for incineration. Advantageously, the supplied incineration clinkers can be dried and ground so as to obtain clinker powder. The powder can then be passed through one or more sieves so as to obtain the desired particle size before the step of mixing 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 very particularly, a particle size of less than 1 mm.

According to one embodiment, the bottom ash can be pretreated before mixing with the aqueous solution. For example, the dried and ground incineration clinkers which are supplied can undergo a dry pretreatment, such as for example a magnetic separation step. Magnetic separation is a dry process technique known to those skilled in the art and makes it possible, by means of fields of variable intensity, to separate certain compounds from clinkers as a function of their respective behaviors with respect to the field. magnetic. The particle size of a bottom ash powder thus pretreated can be between 100 μm and 1000 μm. 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 clinkers.

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 can also comprise a surfactant.

For the purposes of the present invention, the term “inorganic binder” is understood to mean a binder which gives rise in a sol / gel reaction to the creation of an inorganic matrix. Similarly, the term organic-inorganic hybrid binder is understood to mean 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 organic / inorganic hybrid matrix but also to overcome the intrinsic chemical variability linked to the origin of bottom ash. Indeed, there is a chemical variability between MIDI and MIOM, just as between MIDI or MIOM not coming from the same incineration center or coming from the same incineration center but having a different daily or weekly composition just as much that 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 from 1% to 50%, preferably from 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 organic-inorganic hybrid binder. According to this embodiment, the inorganic binder is in particular a silicic or aluminosilicate 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 SiCI ₄ , and their mixtures. Preferably, 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 organic-inorganic hybrid binder. According to this embodiment, the organic-inorganic hybrid binder can consist of at least one 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 ranging 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 one another are H or a non-hydrolyzable group selected from alkyl, in particular C _V4, 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 -io, such as phenyl and naphthyl; methacryl or methacryloxy groups Ci_i ₀ as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group 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; haloC ₂ -C ₁₀ alkyl groups such as 3chloropropyl; mercaptoalkyl groups C ₂ _i ₀ such as mercaptopropyl; C ₂ aminoalkyl groups. ₁₀ as 3-aminopropyl; groups (amino C _{2. 10)} alkylamino (C _{2. 10)} as 3 - [(2-aminoethyl) amino] propyl; the di (C ₂ alkylene. 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 , the C ₂ carboxyalkyl groups. ₁₀

R represents a non-hydrolyzable function chosen from alkylene groups, preferably C ₁₂ , for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups, preferably C ₂ . _i2 , for example, acetylenylene (-C = C-), -C = CC = C-, and -OC-C _s H ₄ -OC-; the groups N, N-di (C ₂ alkylene _i ₀₎ amino such as Ν, Ν-diéthylèneamino; Groups bis [N, N-di (C ₂ alkylene _i ₀₎ amino] such as bis [N- (3-propylene) -N-methyleneamino]; C _{2 O 10} mercaptoalkylene such as mercaptopropylene; groups (C ₂ alkylene _i ₀₎ polysulfide such as propylene or propylene disulfide-tetrasulfide; alkenylene groups, in particular C _{2 groups} . ₄ , such as vinylene; arylene groups, in particular C ₆ _IO such as phenylene; the di (C ₂ alkylene _IO) arylene, C ₆ -io, such as di (ethylene) phenylene; Groups N, N'-di (C ₂ alkylene _i ₀₎ ureido such as N, N'-dipropylèneuréido.

Mention may in particular be made, as examples of organoalkoxysilane of formula (I), of methyltrialcoxysilane (RO) ₃ Si-CH ₃ , 3-aminopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ -NH ₂ , 3 - (2 aminoethyl) aminopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ , la 3- (trialcoxysilyl) 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-mercaptopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ SH; carboxyethylsilanetriol (HO) ₃ Si (CH ₂ ) ₂ C00 'Na ⁺ , 3-trihydroxysilylpropylmethylphosphonate (HO) 3Si- (CH2) 3OP (CH3) OO' Na ⁺ ; (3Glycidoxypropyl) trialcoxysilane; 3-Cyanopropyltrialcoxysilane (RO) 3Si- (CH ₂ ) ₃ CN; oligomers of aminopropylsilsesquioxane and copolymers of aminoethylaminopropylsilsesquioxanemethylsilsesquioxane; R having the same meaning as above.

As examples of bis-alkoxysilane of formula (II), use is preferably made of a bis [trialcoxysilyl] methane (RO) ₃ Si-CH ₂ -Si (OR) ₃ , a bis- [trialcoxysilyl] ethane (RO) ₃ Si- (CH ₂ ) ₂ -Si (OR) ₃ , a bis [trialcoxysilylpropyl] amine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -Si (OR) ₃ , a bis [trialcoxysilylpropyl] ethylenediamine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -Si (OR) ₃ ; a bis [trialcoxysilylpropyljdisulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OR) ₃ , a bis- [trialcoxysilylpropyljtetrasulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₄ - (CH ₂ ) ₃ -Si (OR) ₃ , a bis- [trialcoxysilylpropyl] urea (RO) ₃ Si- (CH ₂ ) ₃ -NH-CONH- (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 can be from 1 to 95 mol%, and preferably from 5 to 50 mol% of the silicic or aluminosilicon species contained in the mixture. The molar percentage is notably defined by the following formula: 100 x hybrid Si / (hybrid Si + inorganic Si) ·

According to another embodiment, the aqueous binder solution only comprises at least one organic-inorganic hybrid binder. In this case, the aqueous binder solution is free of inorganic binder. According to this embodiment, the organic-inorganic hybrid binder can 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 chosen from KOH, NaOH or their mixtures.

The aqueous binder solution may also include a surfactant. The addition of a surfactant advantageously makes it possible to reduce on the one hand the release of dihydrogen and thus limit the associated industrial risks and on the other hand, to achieve better control of the porosity of the material obtained. The surfactant can 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 results, in particular for the construction field. , a reduction in the impact of this sector on the environment. Indeed, the method according to the invention and thus less energy consuming.

The third step of the process according to the invention consists in mixing the bottom ash with the aqueous binder solution.

The mixing can be done according to methods known to those skilled in the art which result in bringing said bottom ash into contact with said aqueous binder solution so as to obtain a suspension. The bringing into contact in particular results in 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.

In fact, bringing the solution into contact with the clinker particles causes the basic attack and the oxidation of the metallic components of the clinkers, 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 hydroxides in the medium and the evaporation of the water molecules makes it possible to control the generation of porosity within the materials during setting. 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 of aqueous binder solution.

The heat treatment step allows solidification of the bottom ash mixture with the aqueous binder solution. Thus, the treatment of the mixture makes it possible to freeze the whole 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 viscosity. Those skilled in the art can easily adapt the conditions of said heat treatment as a function of the mixture of clinkers and of aqueous binder solution which it has. The use of a heat treatment makes it possible to adapt to different shaping processes, such as for example casting, rolling or even extrusion, in order to obtain materials in a dense form or in a form foam. The heat treatment thus makes it possible to rapidly manufacture 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 setting, the skilled person can easily adapt the conditions, in particular in terms of time and power, depending on the composition and the quantity of bottom ash and the final application sought. Thus, the microwave treatment can for example be carried out at a power of between 500 and 1500 Watt, such as for example around 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 the form of foam, said material having an apparent density which can be comprised of 0.5 g / cm ³ and 2 g / cm ³ , preferably from 0.9 g / cm ³ to 1.7 g / cm ³ , for example around 1 g / cm ³ .

According to a particular embodiment, the heat treatment step can be followed by a densification step and then a second heat treatment step. The densification step advantageously makes it possible to eliminate part of the gas bubbles contained in the porous material at the end of the first heat treatment step, this having the consequence of succeeding, once the second heat treatment step has been carried out. on said densified material, obtaining a porous material having a higher density and reduced porosity. This densification step can be carried out according to techniques known to those skilled in the art, such as kneading, compression or even by means of vibrations.

The method according to the invention is particularly advantageous in that it offers a new way of recovering bottom ash, thus making it possible to obtain a porous material which 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 method is advantageous in that it does not generate waste other than gas evolution, mainly water evolution.

Finally, the process according to the invention is a process easily adaptable on an industrial scale and can also be carried out continuously, thus constituting a non-negligible advantage taking into account the processes known from the prior art and the quantity of bottom ash to be treated. .

A second object of the invention relates to a porous material capable of being 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 a hybrid organic-inorganic binder.

The porous material according to the invention comprises an inorganic binder and / or a hybrid organic-inorganic binder as defined above. The amounts of inorganic and / or organic-inorganic hybrid binder in this material can be from 5% to 45% relative to the total dry mass 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 , such as for example about 1 g / cm ³ .

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

EXAMPLES

Example 1: Manufacture of a monolith based on bottom ash of particle size less than 1 mm and inorganic binder (Na ^ SiOj.SH ^ O)

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 so as to obtain a powder whose particle size is less than 1 mm. In a second step, the inorganic binder is obtained by mixing, using an ultrasonic bath, 4.35 g of Na ₂ SiO ₃ .5H ₂ O to 7.4 mL of distilled H ₂ O. A third step consists in adding the inorganic binder drop by drop to the 10 g of bottom ash previously prepared and with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 3 minutes at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 20% by mass of the final porous material obtained and an apparent density of 0.9 g / cm ³ .

Example 2: Manufacture of a monolith based on bottom ash 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 so as 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 with a solution containing 0.4 g of KOH and 0.85 mL of distilled H ₂ O. The mixture is then stirred with magnetic stirring and at room temperature until a transparent solution is obtained. A third step consists in adding the 10 g of bottom ash to the inorganic binder with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 30 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 10% by mass of the final porous material obtained and an apparent density of 1.07 g / cm ³ .

Example 3: Manufacture of a monolith based on bottom ash of particle size less than 1 mm and of 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 so as 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 room temperature until a transparent solution is obtained. A third step consists in adding the 10 g of bottom ash to the hybrid binder with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of

2.5 minutes at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 32% by mass of the final material obtained and an apparent density of 1.04 g / cm ³ .

Example 4: Manufacture of a monolith based on bottom ash with a particle size of less than 1 mm and of an organic-inorganic hybrid 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 so as 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 room temperature until a transparent solution is obtained. A third step consists in adding the 10 g of bottom ash to the hybrid binder with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 40 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 8% by mass of the final material obtained and an apparent density of 1.0 g / cm ³ .

Example 5: Manufacture of a monolith based on bottom ash of particle size less than 1 mm and of organic-inorganic hybrid binder containing sodium 3-trihvdroxvsilvlpropylméthvlphosphonate.

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 so as 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 room temperature until a transparent solution is obtained. A third step consists in adding the 10 g of bottom ash to the hybrid binder with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 70 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 17.5% by mass of the final material obtained and an apparent density of 1.03 g / cm ³ .

Example 6: Manufacture of a monolith based on bottom ash of particle size less than 1 mm and of 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 so as 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 with a solution containing 0.36 g of KOH and 0.9 mL of distilled H ₂ O , this mixture being left under magnetic 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 in a gradual manner with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification is carried out by a microwave treatment (MW) of 40 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 10.4% by mass of the final porous material, the latter then having an apparent density of 0.93 g / cm ³ after drying.

It is also possible to add, using the same protocol, the 10 g of bottom ash to solutions containing either 3.55 g of Ludox HS-40, 0.62 g glycidoxypropyltrimethoxysilane, 0.82 g of KOH and 2.0 mL of distilled H ₂ O i.e. 6.09 g of Ludox HS-40, 1.07 g glycidoxypropyltrimethoxysilane, 1.40 g of KOH and 3.45 mL of distilled H ₂ O 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 mass of the porous materials, the latter then having an apparent density of 0.92 and 1.06 g / cm ³ respectively. It is also possible to interrupt the microwave treatment to carry out a mixing step to increase the apparent density.

Example 7: Manufacture of a monolith based on bottom ash of particle size less than 1 mm and of 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 so as 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 room temperature until a transparent solution is obtained. A third step consists in adding the 10 g of bottom ash to the hybrid binder with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold, and the solidification of the sample is carried out by a microwave treatment (MW) of 70 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 15.4% by mass of the final material obtained and an apparent density of 1.0 g / cm ³ .

Example 8: Manufacture of a monolith based on bottom ash with a particle size of less than 1 mm and an 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 so as 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. A third step consists in adding 0.7 g of a surfactant solution prepared from 0.1 g of Brij®58 and 0.6 ml of distilled water to the 10 g of bottom ash. The bottom ash / surfactant mixture is then added to the inorganic binder gradually with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 80 s at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 20% by mass of the final porous material, the latter then having an apparent density of 1.12 g / cm ³ after drying. It is also possible to interrupt the microwave treatment to carry out a mixing step to increase the apparent density.

Example 9: Manufacture of a monolith based on bottom ash with a particle 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 so as 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 consists in adding the 10 g of bottom ash to the inorganic binder gradually with mechanical stirring until a viscous suspension is obtained. This suspension is then poured into a mold and the solidification of the sample is carried out by a microwave treatment (MW) of 80 seconds at 900 watts. The porous materials appear after drying in the form of non-friable monoliths. The binder in dry extract represents 20% by mass of the final porous material, the latter then having an apparent density of 1.17 g / cm ³ . It is also possible to interrupt the microwave treatment to carry out a mixing step to increase the apparent density. This step is all the more effective as the mass percentage of water in the binder is important.

Claims (16)

1. A method of manufacturing a porous material comprising the following steps of: supply of incineration clinkers, supply of an aqueous binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid binder, mixing of said clinkers with said aqueous binder solution comprising at least one inorganic binder and / or at least one organic-inorganic hybrid binder, taken by heat treatment of said mixture obtained, recovery of the porous material. 2. Method according to claim 1, characterized in that the supplied incineration slag is dried, ground and undergoes a pretreatment in the dry process such as a magnetic separation. 3. Method according to claim 1 or 2, characterized in that the quantities of binder in the aqueous binder solution are selected so that the porous material recovered has an amount of binder from 1% to 50% by mass of 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 or aluminosilicate binder. 5. Method according to claim 4, characterized in that the inorganic binder is a silicic binder chosen from the group comprising silicic acid, silicon alkoxides, silicates, colloidal silica, silicon tetrachloride SiCI ₄ , and their mixtures, and preferably chosen from the group comprising, silicates, colloidal silica and their mixtures. 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 organicinorganic hybrid binder. 7. Method according to claim 6, 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 ranging 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 one another, H, a non-hydrolyzable group chosen from alkyl groups, in particular C ₄ . 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 . ₄₀ , such as phenyl and naphthyl; methacryl or C ₁₄₀ methacryloxyalkyl groups such as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group is linear, branched or cyclic, C ₁₄₀ , and the alkoxy group contains from 1 to 10 carbon atoms, such as glycidyl and glycidyloxyalkyl Ci-10; C ₂ haloalkyl groups. ₁₀ as 3-chloropropyl; C ₂ mercaptoalkyl groups. ₁₀ as mercaptopropyl; C ₂ aminoalkyl groups. ₁₀ as 3-aminopropyl; groups (amino C ₂ _i ₀₎ alkylamino (C ₂ _IO) as 3 - [(2-aminoethyl) amino] propyl; the di (C ₂ alkylene .i ₀₎ 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 , the C ₂ carboxyalkyl groups. ₁₀ R represents a non-hydrolyzable function chosen from alkylene groups, preferably C ₄ . ₁₂ , for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups, preferably C ₂ . ₁₂ , for example, acetylenylene (-C = C-), -C = CC = C-, and -OC-C _s H ₄ -OC-; N, N-di (C ₂ alkylene _i ₀₎ amino such as N, Ndiéthylèneamino; bis [N, N-di (C _{2 O 10} alkylene) amino] groups such as bis [N- (3-propylene) N-methyleneamino]; C ₂ mercaptoalkylene. ₁₀ such as mercaptopropylene; groups (C ₂ alkylene _i ₀₎ polysulfide such as propylene or propylene disulfide-tetrasulfide; alkenylene groups, in particular C _{2 groups} . ₄ , such as vinylene; arylene groups, in particular C ₆ _IO such as phenylene; the di (C ₂ alkylene _i ₀₎ arylene, C ₆ -io, such as di (ethylene) phenylene; the groups N, N'-di (C ₂ alkylene. ₁₀₎ ureido such as N, N'dipropylèneuréido. 8. The method of claim 7, wherein the hybrid organic-inorganic precursor of formula (I) is chosen from the group comprising methyltrialcoxysilane (RO) ₃ Si-CH ₃ , 3 aminopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ -NH ₂ , 3- (2-aminoethyl) aminopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ , 3- (trialcoxysilyl) 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-mercaptopropyltrialcoxysilane (RO) ₃ Si- (CH ₂ ) ₃ SH, carboxyethylsilanetriol (HO) ₃ Si- (CH ₂ ) ₂ COO ^_ Na ⁺ , 3trihydroxysilylpropylmethylphosphonate (HO) 3Si- (CH2) 3OP (CH3) OO ^_ Na ⁺ ; (3glycidoxypropyl) trialcoxysilane, 3-Cyanopropyltrialcoxysilane (RO) 3Si- (CH ₂ ) ₃ CN, oligomers of aminopropylsilsesquioxane and copolymers of aminoethylaminopropylsilsesquioxanemethylsilsesquioxane, R representing H or an alkyl group preferably comprising 1 or 4 alkyl groups preferably comprising 1 or 4 alkyl groups preferably comprising 1 or an alkyl group preferably comprising 1 or 4 alkyl groups preferably comprising 1 or alkyl group preferably 1 to 1 carbon, 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 a H ; 9. The method of claim 7, wherein the hybrid organic-inorganic precursor of formula (II) is chosen from the group comprising bis- [trialcoxysilyl] methane (RO) ₃ Si-CH ₂ Si (OR) ₃ , bis - [trialcoxysilyl] ethane (RO) ₃ Si- (CH ₂ ) ₂ -Si (OR) ₃ , bis [trialcoxysilylpropyl] amine (RO) ₃ Si (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -Si ( OR) ₃ , bis- [trialcoxysilylpropyl] ethylenediamine (RO) ₃ Si- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH (CH ₂ ) ₃ -Si (OR) ₃ ; bis- [trialcoxysilyl propyl] disulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₂ - (CH ₂ ) ₃ -Si (OR) ₃ , bis [trialcoxysilylpropyl] tetrasulfide (RO) ₃ Si- (CH ₂ ) ₃ -S ₄ - (CH ₂ ) ₃ -Si (OR) ₃ , bis- [trialcoxysilylpropyl] urea (RO) ₃ Si- (CH ₂ ) ₃ -NH-CO-NH- (CH ₂ ) ₃ -Si (OR), R representing H or an alkyl group preferably comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, nbutyl, s-butyl or t-butyl group, preferably H, a methyl or ethyl group, and more preferably a methyl group or an H; 10. Method according to any one of the preceding claims, characterized in that the incineration clinkers are incineration clinkers of industrial origin (MIDI) or clinkers for the incineration of household waste (MIOM). 11. Method according to one of the preceding claims, characterized in that the heat treatment step is a setting step by microwave treatment. 12. Method according to claim 11, characterized in that the setting by microwave treatment is carried out for approximately 3 minutes at a power of approximately 900 Watts. 13. Porous material comprising incineration slag and at least one inorganic binder and optionally at least one organic-inorganic hybrid binder, characterized in that it has an apparent 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. Porous material according to claim 13, characterized in that the inorganic binder is a silicic binder chosen from the group comprising silicic acid, silicon alkoxides, silicate, colloidal silica, silicon tetrachloride SiCI ₄ , and their mixtures, and preferably silicate, colloidal silica or their mixtures. 15. Porous material according to claims 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 ranging 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 one another, H, a non-hydrolyzable group chosen from alkyl, in particular C _{M groups} , 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 -io, such as phenyl and naphthyl; methacryl or methacryloxy groups CI_ ₁₀ as methacryloxypropyl; epoxyalkyl or epoxyalkoxyalkyl groups in which the alkyl group 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 O} _i such as 3-chloropropyl; C ₂ mercaptoalkyl groups. ₁₀ as mercaptopropyl; C ₂ aminoalkyl groups. ₁₀ as 3-aminopropyl; groups (amino C _{2. 10)} alkylamino (C _{2. 10)} as 3 - [(2-aminoethyl) amino] propyl; the di (C ₂ alkylene. 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 , the C ₂ carboxyalkyl groups. ₁₀ R represents a non-hydrolyzable function chosen from alkylene groups, preferably C ₁₂ , for example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene and dodecylene; alkynylene groups, preferably C ₂ . ₁₂ , for example, acetylenylene (-C = C-), -C = CC = C-, and -OC-C _s H ₄ -OC-; the groups N, N-di (C ₂ alkylene _i ₀₎ amino such as Ν, Ν-diéthylèneamino; Groups bis [N, N-di (C ₂ alkylene _i ₀₎ amino] such as bis [N- (3-propylene) -N-methyleneamino]; C _{2 O 10} mercaptoalkylene such as mercaptopropylene; groups (C ₂ alkylene _i ₀₎ polysulfide such as propylene or propylene disulfide-tetrasulfide; alkenylene groups, in particular C _{2 groups} . ₄ , such as vinylene; arylene groups, in particular C ₆ _IO such as phenylene; the di (C ₂ alkylene _IO) arylene C ₆ _IO, such as di (ethylene) phenylene; Groups N, N'-di (C ₂ alkylene. ₁₀₎ ureido such as N, N'-dipropylèneuréido. 5 16. Porous material according to one of claims 13 to 15, characterized in that it comprises an amount of inorganic binder and / or organic-inorganic hybrid binder from 5% to 45% relative to the dry mass of the porous materials . FRENCH REPUBLIC National registration number FA 844271 FR 1758839 irai - I NATIONAL INSTITUTE PROPERTY INDUSTRIAL PRELIMINARY SEARCH REPORT based on the latest claims filed before the start of the search EPO FORM 1503 12.99 (P04C14) DOCUMENTS CONSIDERED AS RELEVANT Relevant claim (s) Classification attributed to the invention by ΙΊΝΡΙ Category Citation of the document with indication, if necessary, of the relevant parts Y, D Y, D A, D A, D FR 2 714 625 Al (CORDI GEOPOLYMERE SA [FR]; DIVERGENT SA) July 7, 1995 (1995-07-07) * page 4, line 5 - page 5, line 17; claims 1-4 * W0 89/02766 Al (DAVIDOVITS JOSEPH [FR]) April 6, 1989 (1989-04-06) * claims 1-9 * FR 2 696 662 Al (TOSAN JEAN LUC [FR]) April 15, 1994 (1994-04-15) * claims 1-8 * EP 0 922 470 Al (GEH AND MINING RESEARCH B R G M [FR]) June 16, 1999 (1999-06-16) * claims 1-10 * 1-16 1-16 1-16 1-16 C04B18 / 06 C04B28 / 00 ΒΘ9Β3 / ΘΘ C04B111 / 40 TECHNICAL AREAS SOUGHT (IPC) C04B Research Completion Date Examiner May 15, 2018 Burtan, M CATEGORY OF DOCUMENTS CITED T: theory or principle underlying the invention E: patent document with an earlier date X: particularly relevant on its own at the filing date and which was not published until that date Y: particularly relevant in combination with a deposit or at a later date. other document of the same category D; cited in request A: technological background L: cited for other reasons O: unwritten disclosure P: interlayer document &: member of the same family, corresponding document