PREPARATION OF A CLAY-SILICA-CALCARE MINERAL CHARGE

Abstract

PREPARATION OF A CLAY-SILICA-CALCARE MINERAL FILLER The present invention relates to a method for preparing a clay-silica-calcareous mineral filler, comprising the following steps: - a step of measuring the kaolinite content in an aqueous composition of wash water from mineral material washing processes, in particular from limestone material washing processes, said step being characterized in that it is carried out by near infrared spectrometry; - a step of filtering said aqueous composition, if the content measured in the previous step is greater than or equal to 8% by mass, preferably greater than or equal to 10% by mass relative to the total mass of said aqueous composition, to obtain a filter cake; and - a step of breaking up and then drying the filter cake obtained at the end of the filtration step, to obtain a clay-silica-calcareous mineral filler. Figure for the abstract: none

Description

Title of the invention: PREPARATION OF A CLAY-SILICA-CALCARE MINERAL CHARGE

[0001] The present invention relates to a process for preparing a clay-silico-calcareous mineral filler, as well as a process for preparing a calcined clay composition.

[0002] The construction sector represents a significant part of France's economic activity. The significant role of this sector and the construction / renovation of the building stock leads to a continuous and significant consumption of natural resources, a significant release of CO2 and a significant consumption of energy. The public authorities' awareness of the need to reduce greenhouse gas emissions tends to improve the environmental and energy performance of the construction sector, both in terms of materials and the design of structures. In the construction sector, the increase in the price of raw materials, the depletion of natural resources and the administrative difficulties of opening new quarry sites tend to move towards alternative resources such as recycled aggregates or industrial co-products.In the field of industrial co-products, quarry washing fines can be considered as a resource with high potential for recovery in the field of eco-materials, due to their large volumes and their clayey nature.

[0003] Most of the aggregates used in the construction industry come from alluvial or massive quarries. To meet the quality and performance criteria of the materials and products used (concrete, treated gravel, etc.), the aggregates must only contain a small quantity of clayey fines so as not to cause adhesion problems, particularly between the cement matrix and the aggregates for concrete. Therefore, washing units clean the aggregates and remove the fines.

[0004] For alluvial quarries, the washing fines are discharged into old excavations as soon as they leave the facilities. The exploitation of a massive quarry requires mining and reworking of the natural terrain. The production of aggregates leads to the production of by-products which can be unexploited and stored like quarry washing fines.

[0005] However, these fines require significant storage capacities and can be a disadvantage in terms of the exploitation of the deposit. Indeed, the aggregate washing fines, at the outlet of the process, have a more or less significant concentration in the water (150 g / l to 750 g / l). The washing water cannot be discharged into the water table due to these excessive concentrations. Consequently, basins of Decanting allows this sludge to be stored in order to separate the water from the washing fines. Currently, washing fines are not highly valued. The increase in aggregate production generates significant volumes of these fines.

[0006] It is therefore necessary today, in order to preserve natural material resources, to find ways of recovering these fine clay-silico-limestone washes.

[0007] The present invention aims to reduce the storage volumes of the washing sludge fines mentioned above.

[0008] The aim of the invention is therefore to propose a process allowing the recycling of quarry waste, in particular wash water containing fine clay-silico-limestone.

[0009] To this end, the invention relates to a process for preparing a clay-silico-limestone mineral filler, comprising the following steps:

[0010] - a step of measuring the kaolinite content in an aqueous composition of water washing from mineral material washing processes, in particular from limestone material washing processes, said step being characterized in that it is carried out by near infrared spectrometry;

[0011] - a step of filtration of said aqueous composition, if the content measured in step preceding is greater than or equal to 8% by mass, preferably greater than or equal to 10% by mass relative to the total mass of said aqueous composition, to obtain a filtration cake; and

[0012] - a step of breaking up lumps and then drying the filter cake obtained at the end of the filtration stage, to obtain a clay-silico-limestone mineral charge.

[0013] The method of the invention is therefore specifically based on the measurement of the kaolinite content by a near infrared measurement step. However, to date, this method has never been used in this context, and above all it is not usual to use such an analysis method for variable kaolinite contents (extended wavelength range of the near infrared spectrometer (900 - 1700 nm)).

[0014] The method of the invention therefore consists firstly in measuring the kaolinite content in an aqueous composition of wash water from mineral material washing processes, in particular from limestone material washing processes.

[0015] These washing waters (or sludges) are loaded with “undesirable” compounds for certain applications, also called washing fines or clay-silico-calcareous fines, and correspond to the waters obtained and stored after washing the limestone pebbles.

[0016] These wash waters are therefore in the form of a liquid solution, in which different minerals are found, such as clay, limestone or silica.

[0017] According to one embodiment, the aqueous washing water composition used in the context of the present invention comprises:

[0018] - from 8% to 45%, in particular from 12% to 40%, and preferably from 15% to 36%, by mass of SiO2 relative to the total mass of said aqueous composition,

[0019] - from 1% to 20%, in particular from 3% to 15%, and preferably from 6.5% to 15%, by mass of A12O3 relative to the total mass of said aqueous composition, and

[0020] - from 25% to 85%, in particular from 30% to 81%, in particular from 34% to 70%, and preferably from 35% to 62%, by mass of limestone relative to the total mass of said aqueous composition.

[0021] Other minerals may be present in small quantities (goethite, dolomite, rutile, anatase, anorthite, smectite, chlorite 1 A, illite / smectite and illite / chlorite interstratified).

[0022] Preferably, the aqueous wash water composition has a solids concentration of from 100 gL 1 to 800 gL *, preferably from 110 gL 1 to 780 gL *. By solids is meant the above-mentioned minerals, in particular limestone, kaolinite, quartz, etc.

[0023] As indicated above, the first step of the method is a step of measuring the kaolinite content by near infrared.

[0024] This step is carried out for example using a near-infrared spectrometer.

[0025] To determine the kaolinite content, a chemometric model was constructed by associating spectra with reference values. This model makes it possible to determine a mathematical equation associating a factor with each wavelength of the absorption spectrum. Some absorption bands are more specific to certain molecules than others. This is the case for the wavelengths at 7000 cm 1 = 1400 nm and 4500 cm1 = 2200 nm as explained by Maxime Pineau et al. (Estimating kaolinite crystallinity using near-infrared spectroscopy: implications for its geology on Earth and Mars Maxime Pineau, Maximilien Mathian, Fabien Baron, Benjamin Rondeau, Laetitia Le Deit, Thierry Allard, Nicolas Mangold).

[0026] By carrying out parallel studies in the laboratory and under industrial conditions, the inventors were able to demonstrate that there is a good correlation between the kaolinite value indicated on the near infrared spectrometer and the kaolinite content calculated from analyses by X-ray fluorescence spectroscopy (in particular obtaining a good correlation coefficient R2 equal to 0.882).

[0027] According to a preferred embodiment, the step of measuring the kaolinite content of the method of the invention is carried out continuously.

[0028] This measurement step may include the implementation of a near infrared spectrometer.

[0029] For example, the near infrared spectrometer is mounted in particular on the pipeline through which the aforementioned aqueous composition of wash water circulates. This sensor is an optical instrument intended to continuously monitor the kaolinite concentration of the aggregate washing sludge. The flow of material passing in front of a lens and the lamp absorbs and reflects light over the entire wavelength spectrum depending on its chemical composition. The signal reflected by the sample is recorded and analyzed by a spectrometer. The interaction between the sample and the light produces a characteristic spectrum. The data sequences are transferred to a computer via an interface. Software compares the curve of the data sequence with the calibration model and determines the kaolinite content of the sample.

[0030] According to the invention, the method for treating wash water comprises subsequent or non-subsequent steps, after the aforementioned measuring step, depending on the measured values. Thus, if the measured kaolinite content is less than 10% by mass, preferably less than 8% by mass, the treatment method can be interrupted and the wash water is not treated further and is conveyed via a pipeline into a suitable basin following its usual route. On the other hand, if the content is greater than or equal to 10%, then the water is diverted to the ad hoc treatment according to the method of the invention as described below.

[0031] According to the invention, if the content measured at the end of the previous step is greater than or equal to 8% by mass, preferably greater than or equal to 10% by mass, relative to the total mass of the aqueous composition, the method according to the invention then comprises an additional implementation step following this measurement step, namely a step of filtration of said aqueous composition to obtain a filtration cake.

[0032] The filtration step according to the invention can be implemented with a filter press. This filter press is a device used to separate the solid fraction from water by a filtration process.

[0033] Such a filter press may consist of a series of concave plates covered with filter cloths, a support frame, a network of pipes and channels for transporting the washing sludge from the suspended aggregates.

[0034] The solid particles retained by the filter cloths form a cake in the chambers located between the plates. According to one embodiment, membranes compress the cakes to lower the water content of the cakes.

[0035] This filtration step is then followed by a step of breaking up lumps and then drying the filter cake obtained at the end of the filtration step, to obtain a clay-silico-limestone mineral filler.

[0036] The process of the invention makes it possible to obtain a clay-silico-limestone mineral filler.

[0037] By “clay-silico-limestone filler” is meant a mineral filler comprising in particular clay, silica and limestone.

[0038] At the end of the process of the invention, the charges obtained are therefore in particular in solid form, and more particularly in powder form.

[0039] The clay-silico-calcareous fillers thus obtained therefore include in particular clay in various forms, quartz and chalcedony, and limestone (or calcium carbonate).

[0040] According to one embodiment, the clay-silico-calcareous fillers are in the form of a powder whose particle size is less than 200 μm.

[0041] By particle size is meant in particular the average diameter of said particles.

[0042] Preferably, the particle size of this powder is characterized by d50 and / or by d90.

[0043] The values ​​of d50 and / or d90 are in particular measured by laser diffraction granulometry which uses the principle of diffraction and diffusion of a laser beam striking a particle in a liquid or dry process. The values ​​of d50 and / or d90 indicate that 50% and / or 90% of the particles have a size smaller than these values ​​of d50 and / or d90

[0044] The d50 of the particles of the aforementioned powder is preferably less than 50 pm, or even less than 40 pm, or even less than 35 pm. Preferably, the d50 is between 5 and 15 pm. These values ​​of d50 indicate that 50% of the particles have a size smaller than these values ​​of d50.

[0045] The d90 of the particles of the aforementioned powder is preferably less than 200 pm, preferably less than 180 pm, and preferably greater than 20 pm, or even greater than 30 pm, and preferably greater than 35 pm. Preferably, the d90 is from 20 pm to 75 pm, in particular from 20 pm to 50 pm. These d90 values ​​indicate that 90% of the particles have a size less than these d90 values.

[0046] The clay-silico-calcareous fillers obtained by the process of the invention comprise kaolinite, and therefore as indicated above in a content greater than or equal to 8% by mass, preferably greater than or equal to 10% by mass relative to the total mass of said fillers.

[0047] According to one embodiment, the kaolinite content in the clay-silico-calcareous fillers used in the process of the invention is less than 25%, or even less than 22%, by mass relative to the total mass of said fillers.

[0048] Preferably, the clay-silico-calcareous fillers used in the process of the invention comprise from 10% to 30%, preferably from 10% to 25%, preferably from 10% to 22%, by mass of kaolinite relative to the total mass of said fillers.

[0049] The clay-silico-calcareous fillers obtained according to the process of the invention may also comprise silica. Preferably, the silica is in the form of clays.

[0050] The silica content is notably measured by X-ray fluorescence spectrometry. This analytical technique makes it possible to obtain elementary quantitative analyses.

[0051] According to one embodiment, the clay-silico-calcareous fillers used in the process of the invention comprise from 5% to 35% by mass of silica relative to the total mass of said clay-silico-calcareous fillers.

[0052] Preferably, the clay-silico-calcareous fillers used in the process of the invention comprise more than 8%, in particular more than 10%, preferably more than 15% by mass of silica relative to the total mass of said fillers.

[0053] Preferably, the clay-silico-calcareous fillers used in the process of the invention comprise from 5% to 40%, in particular from 8% to 36%, and preferably from 15% to 30%, preferentially from 15% to 25%, by mass of silica relative to the total mass of said fillers.

[0054] The clay-silico-calcareous fillers used in the process of the invention may also comprise alumina or Al2O3.

[0055] The alumina content is notably measured by X-ray fluorescence spectrometry. This analytical technique makes it possible to obtain quantitative elemental analyses.

[0056] According to one embodiment, the clay-silico-calcareous fillers comprise from 1% to 20%, in particular from 3% to 15%, preferably from 6.5% to 15%, or even from 6.5% to 10%, by mass of Al2O3 relative to the total mass of said fillers.

[0057] Preferably, the clay-silico-calcareous fillers comprise more than 3%, preferably more than 6.5%, by mass of A12O3 relative to the total mass of said fillers.

[0058] In particular, the clay-silico-calcareous fillers comprise from 6.6% to 14.6% by mass of A12O3 relative to the total mass of said clay-silico-calcareous fillers.

[0059] The clay-silico-calcareous fillers obtained according to the process of the invention may also comprise limestone.

[0060] The limestone content is estimated in particular from the chemical analysis measured by X-ray fluorescence spectroscopy, according to the equation#:

[0061] • % Calcite CaCO3 = (% CaO - % Dolomite * 56 / 184) * 100 / 56

[0062] With: M(CaO) = 56 g / mol

[0063] M(CaCO3) = 100 g / mol

[0064] % Dolomite CaMg(CO3)2 = % MgO * 184 / 40

[0065] M(MgO) = 40 g / mol

[0066] M(CaMg(CO3)2)=184 g / mol

[0067] Preferably, the clay-silico-calcareous fillers comprise more than 30%, preferably more than 34%, in particular more than 45% or even more than 50%, preferably more than 55%, and preferentially more than 56%, by mass of limestone (or calcium carbonate) relative to the total mass of said fillers.

[0068] According to one embodiment, the clay-silico-limestone fillers comprise from 25% to 85%, in particular from 30% to 70%, preferably from 35% to 65%, and preferentially from 45% to 60%, or even from 35% to 62%, by mass of limestone relative to the total mass of said fillers.

[0069] In particular, the clay-silico-limestone fillers comprise from 30% to 81%, in particular from 34% to 67%, and preferably from 34% to 56%, by mass of limestone relative to the total mass of said fillers.

[0070] According to one embodiment of the process of the invention, the clay-silico-limestone mineral filler obtained comprises:

[0071] - from 8% to 45%, in particular from 12% to 40%, and preferably from 15% to 36%, by mass of SiO2 relative to the total mass of said composition,

[0072] - from 1% to 20%, in particular from 3% to 15%, and preferably from 6.5% to 15%, by mass of A12O3 relative to the total mass of said composition, and

[0073] - from 25% to 85%, in particular from 30% to 81%, in particular from 34% to 70%, and preferably from 35% to 62%, by mass of limestone relative to the total mass of said composition.

[0074] The present invention also relates to a method for preparing a calcined clay composition, comprising the following steps:

[0075] - a step of preparing a clay-silico-limestone mineral filler according to the process as defined above, and

[0076] - a flash calcination step of the clay-silico-calcareous charge obtained in step previous, said flash calcination step being carried out at a temperature of between 650°C and 820°C.

[0077] The specific heat treatment implemented according to the method for preparing a calcined clay composition according to the invention is a calcination with a very short treatment time, namely a flash calcination. Flash calcination technology is a technology well known to those skilled in the art, which makes it possible to calcine fine particles in hot gases for a very short residence time, more particularly of the order of a second.

[0078] As indicated above, the specificity of the process of the invention is linked to a temperature between 650°C and 820°C. This specific range makes it possible to obtain a calcined clay composition.

[0079] Preferably, the flash calcination step is carried out at a temperature of from 675°C to 790°C, and preferably from 675°C to 740°C.

[0080] The present invention therefore makes it possible to “recycle” products obtained from washing sludge, in particular loaded with clay and limestone, and which were stored in basins, as explained above, to obtain a calcined clay composition.

[0081] By "calcined clay" is meant a clay that has undergone a heat treatment allowing its dehydroxylation so as to give it pozzolanic reactivity. Calcined clays include a set of products with very variable characteristics (metakaolins, meta-illites, meta-palygorskite, mixtures of clay phases, etc.). When calcined between 700°C and 850°C, certain clays have pozzolanic properties sought after for use in concrete, i.e. they have the capacity to form at ordinary temperature, in the presence of water, by combination with lime, stable hydrates with binding properties. According to standard NF EN 197-1, calcined clays are composed essentially of reactive silicon dioxide (SiO2) and aluminum oxide (A12O3). The remaining part contains iron oxide (Fe2O3) and other oxides. The proportion of reactive CaO is negligible for hardening.

[0082] Calcination makes it possible to modify the properties of clays and give them a pozzolanic character. It allows the transition from a stable crystallized state to an unstable and therefore more reactive amorphous state.

[0083] Overall, calcined clays have a very attractive carbon footprint (between 139 and 239 kg eq CO2 / tonne). In fact, clays do not release carbon when heated, unlike limestone, and they are calcined at a much lower temperature compared to the manufacture of clinker, which reduces the amount of fuel required and the resulting emissions. Binders incorporating calcined clays could thus reduce the carbon footprint of Portland cement by around 30% while maintaining its mechanical performance.

[0084] The process of the invention makes it possible to obtain a non-standardized calcined clay, having a reactivity similar to a metakaolin.

[0085] Metakaolin results from the calcination of a clay, kaolinite, associated with different minerals (phyllosilicates, quartz, iron oxides) in variable proportions depending on the deposits. It is obtained either by calcination then grinding or by grinding then calcination, for example in production units with rotary kilns, trays or by so-called "flash" calcination. It is essentially composed of amorphous alumina silicate particles. Due to its pozzolanic power, it can be incorporated into concrete and / or binder formulations.

[0086] Metakaolin consists mainly of amorphous alumina silicate particles having pozzolanic properties, and is composed essentially of silica SiO2 and reactive alumina A12O3. Calcination temperatures are between 600°C and 850°C depending on the degree of order of the kaolinite. A dehydroxylation reaction of the material occurs with a destruction of the initial crystalline structure leading to an amorphous nature of the material.

[0087] Preferably, the calcined clay composition obtained by the above-mentioned method comprises less than 90% by mass of silica and alumina relative to the mass of said composition. According to a preferred embodiment, the mass content of silica and alumina in the calcined clay composition is from 20% to 60%, and preferably from 25% to 50%, relative to the total mass of said composition.

[0088] According to one embodiment, the calcined clay composition obtained comprises from 10% to 40%, preferably from 20% to 35%, in particular from 20% to 25%, and preferentially from 16% to 25% by mass of SiO2 relative to the total mass of said composition.

[0089] Preferably, the calcined clay composition obtained comprises from 5% to 15%, preferably from 8% to 14% by mass of A12O3 relative to the total mass of said composition.

[0090] The contents mentioned above for the calcined clay composition are measured according to the protocols mentioned above. EXAMPLES

[0091] Example 1: Measurement of kaolinite content in washing sludge

[0092] The near infrared spectroscopy technique is based on the vibration of molecules when they are excited by the infrared source. A near-infrared spectrometer is installed on the pipe through which the washing sludge circulates. Light energy passes through the washing sludge and is then analyzed by a detector.

[0093] To determine the kaolinite content, a chemometric model was constructed by associating spectra with reference values. This model makes it possible to determine a mathematical equation associating a factor with each wavelength of the absorption spectrum. Some absorption bands are more specific to certain molecules than others. This is the case for the wavelengths at 7000 cm 1 = 1400 nm and 4500 cm1 = 2200 nm as explained by Maxime Pineau et al. (Estimating kaolinite crystallinity using near-infrared spectroscopy: implications for its geology on Earth and Mars Maxime Pineau, Maximilien Mathian, Fabien Baron, Benjamin Rondeau, Laetitia Le Deit, Thierry Allard, Nicolas Mangold).

[0094] The reference values ​​of kaolinite are determined using X-ray fluorescence analysis and a mathematical model built on X-ray diffraction data according to the equations:

[0095] % kaolinite = (% A12O3 - % illite * 102 * 3 / 796) * 258 / 102

[0096] % illite = % K2O * 796 / 94

[0097] With,

[0098] for illite, M(3(A12O3) 6(SiO2) (K2O) 2(H2O)) = 796 g / mol

[0099] For kaolinite, M((A12O3) 2(SiO2) 2(H2O)) = 258 g / mol

[0100] And M(K20) = 94 g / mol

[0101] M(A12O3) = 102 g / mol

[0102] [Fig. 1] [Fig. 1] represents the continuous monitoring of kaolinite content.

[0103] Table 1 below details the chemical analysis and the mineralogical analysis of the same day over time.

[0104] [Tables 1] PXPB PKPS PN PN 09 / 12 / 2023 09 / 12 / 2023 09 / 12 / 2023 09 / 12 / 2023 09600 10X54 14X02 3:23 p.m. 16.66 18.28 AijOspq 7.18 9.19 6.76 6.42 Fe2O3 (SJ 1.83 1.96 259 2.69 CaO pq 36.94 32.80 34.81 34.97 MgO (%j G.Sü 0 75 1.17 109 MnO (%j C.O4 ■3.04 Na2O{%) 0.05 0.03 <707 0.05 KjO 0.79 1.14 0.85 O.8Ï 0.15 011 0.13 G.14 riOs W 0.37 0.50 0.35 0.33 0.04 0.03 0.08 0.13 52 chemistry 98.30 98.90 59.06 98.70 PAF ■ 3137 33.55 33.-54 on chemical analysis and ÆHryciion of fayœisX; % kaolinite 11.6 13. S 10.1 8.3 % illite / 10 7 / % quartz 7 9 9 TT % eakium carbonate €4 57 59 60 % dotamie 4: .•3 s 5 % goethite 2 z 3 3' .% Rutik + anatsse 0.4 05 G 4 0.3

[0105] Samples taken at different times confirm the good correlation of kaolinite monitoring via the near infrared spectrometer with the quantification of kaolinite by X-ray fluorescence coupled with X-ray diffraction.

[0106] Table 2 below shows examples of correspondence between the measurement by near infrared spectrometer and the laboratory results for the same day.

[0107] [Tables2] % kaolinite Sampling time Near infrared Mineralogy (FX+DX) D9hOÛ 12.2 11.6 10K54 12.9 13.8 MhQ2 12.2 10.1 15h23 9.5 9.3

[0108] These 4 results are examples among the 89 samples which were taken and which allowed the establishment of a calibration line with a good correlation coefficient (R2 of 0.882).

[0109] Example 2: Process for preparing a clay-silico-limestone mineral filler

[0110] Some materials extracted from the quarry need to be washed. This washing of aggregates results in the formation of sludge loaded with fine clay-limestone. An industrial process makes it possible to recover the clean aggregates on one side and the washing sludge on the other. The selection of the washing sludge before the filtration stage is done by near-infrared spectroscopy. Filtration stage

[0111] The filter press used is a device for separating the solid fraction from the water by a filtration process.

[0112] It consists of a series of concave plates covered with filter cloths, a support frame, a network of pipes and channels for transporting the washing sludge from the suspended aggregates, as well as a series of options to optimize its operation (feeding pump and compression membranes, etc.).

[0113] The aqueous composition of wash water is introduced into the filter press with a concentration of the suspension which can vary from 350 g / l to 780 g / l. It fills the chambers and, when the spaces between the plates fill, the liquid passes through the filter cloths retaining the solid particles.

[0114] Once the chambers are filled, the pressure constantly applied to this sludge allows it to filter itself. This pressure can be obtained using centrifugal or pneumatic pumps.

[0115] The liquid that passes through the cloths, also called filtrate, is collected for recycling and ultimate reuse in the aggregate washing process. The solid particles retained by the filter cloths form a cake in the chambers located between the plates.

[0116] Membranes compress the cakes to lower the water content of the cakes.

[0117] The humidity expressed on dry mass of the cake can be between 17% and 24%. Crushing stage

[0118] The filtration step is then followed by a step of breaking up lumps and then drying the filter cake obtained at the end of the filtration step, to obtain a clay-silico-limestone mineral filler.

[0119] The lump breaker is used to fragment the filter cakes into pieces smaller than 40 mm. In a single process, the dryer-deagglomerator allows the deagglomeration and drying of filter cakes until a clay-silico-calcareous powder with a particle size identical to that of the washing sludge is obtained.

[0120] The dryer-deagglomerator used is applied to a product having a humidity expressed on dry mass of the cake of 17% and the product obtained at the end of the process (and therefore after drying) has a humidity of the order of 0.5%.

[0121] Example 3: Process for the preparation of calcined clay

[0122] A clay-silico-calcareous mineral filler obtained in Example 2 is used in this example. It has the following composition: 12% kaolinite, 13% illite, 13% quartz, 48% calcium carbonate - 24.9% SiO2, 10.1% A12O3, 28.7% CaO.

[0123] This charge was first pressed via a filter press (feeding pressure of 6 bars and membrane pressure of 15 bars). Then it was dried in a deagglomerating dryer and finally was flash-calcined at several temperatures to produce a calcined clay.

[0124] The temperature of 700°C made it possible to obtain a pozzolanic material with the following characteristics: • SiO2 = 28.4% • Reactive silica = 18% • A12O3=11.5% • MBf = 4 g / kg • PaF at 1000°C = 23.3% • Free CaO according to NF EN 451-1 = 3.7% • Activity index at 28 days for a 15% substitution = 88%

[0125] Loss on ignition (PaF) is a mass difference that results from the heat treatment of the sample in an oxidizing atmosphere at 1000°C.

[0126] The methylene blue test (NF EN 933-9+Al)(MBf) makes it possible to evaluate the clay fraction contained in the product before and after calcination. The blue test consists of determining the quantity of methylene blue necessary to cover the total surface (external + internal) of the clay particles suspended in water with a monomolecular layer. The blue value represents the quantity of blue in grams adsorbed per kilogram of product when the stain test is positive.

[0127] By "#free lime#" is meant unbound lime in the form of calcium oxide and calcium hydroxide. This content can be measured by different techniques, for example here it is extracted using acetoacetic ester and the extract is titrated with hydrochloric acid, bromophenol blue being used as an indicator.

[0128] According to standard NF EN 197-1, the content of reactive silicon dioxide (SiO2) corresponds to the proportion of soluble silica dioxide after treatment in hydrochloric acid (HCl) and in a boiling solution of potassium hydroxide (KOH). The quantity of reactive silica dioxide is determined by subtracting from the total silica dioxide content (see EN 196-2) the proportion contained in the residue insoluble in hydrochloric acid and in potassium hydroxide (see EN 196-2), both being determined on a dry sample.

[0129] The activity index characterizes the performance of calcined clay when used at x% substitution. It is expressed as the ratio of the compressive strengths of a mortar consisting of 100-x% test cement and x% calcined natural pozzolan, and a mortar prepared with test cement only.

[0130] The temperature of 720°C made it possible to obtain a pozzolanic material with the following characteristics: • SiO2 = 27.8% • Reactive silica = 15% • A12O3=11.5% • MBf = 2 g / kg • PaF at 1000°C = 24.8% • Activity index at 28 days for a 15% substitution = 90% Example 4 (comparative)

[0131] The spectrocolorimetry technique (L*a*b measurements) was also studied on washing water and on washing water after filtration, drying and grinding.

[0132] The spectrophotometer analyzes the light reflected or transmitted by a sample at each wavelength in the visible spectrum between 400 and 700 nm, relative to that of a reference sample. It is equipped with a device, usually a diffraction element, which splits the incident light into individual wavelengths. The spectrophotometer measures the fraction of light reflected / transmitted by the object at each wavelength in the spectrum.

[0133] The notion of color is therefore well associated with the wavelength. Colorimetry can be the technical means of associating numbers with the color of a sample of fine clay-silico-calcareous materials in liquid or solid form.

[0134] The system used was designed to allow a color to be located in a three-dimensional space: the colorimetric space. This space allows the differences between two or more colors to be calculated.

[0135] In this system, each color can be located by its rectangular coordinates. The rectangular coordinates L* a* b* where

[0136] - L* represents the axis of clarity

[0137] - a* represents the Red / Green axis

[0138] - b* represents the Yellow / Blue axis.

[0139] The lightness axis L* is perpendicular to the chromatic plane and passes through the intersection point of the a* and b* axes. The L* value varies from 0 (black) to 100 (white). Between the two, are all the gray values. The L*, a* and b* values ​​are used to quantify the color.

[0140] Whatever the parameters evaluated, no correlation between the values ​​of L, a*, b* and the values ​​of %A12O3, %SiO2 and %kaolinite could be demonstrated. Indeed, the best correlation is given by monitoring L as a function of %kaolinite (correlation coefficient R2 of 0.34), a value much lower than the R2 obtained with the near infrared spectrometer.

[0141] In conclusion, too much good goes bad and the R2 coefficient of 0.34 was significantly worse than that given by the near infrared spectrometer.

[0142] This technique therefore does not provide satisfactory results.

Claims

Claims

1. Process for preparing a clay-silico-calcareous mineral filler, comprising the following steps: - a step of measuring the kaolinite content in an aqueous composition of wash water from processes for washing mineral materials, in particular from processes for washing calcareous materials, said step being characterized in that it is carried out by near infrared spectrometry; - a step of filtering said aqueous composition, if the content measured in the previous step is greater than or equal to 8%, preferably greater than or equal to 10%, by mass relative to the total mass of said aqueous composition, to obtain a filter cake; and - a step of lumping and then drying the filter cake obtained at the end of the filtration step, to obtain a clay-silico-calcareous mineral filler.

2. The preparation method according to claim 1, wherein the measuring step is carried out continuously.

3. Preparation process according to claim 1 or 2, wherein the aqueous wash water composition has a solids concentration of from 100 gL 1 to 800 gL *, preferably from 110 gL 1 to 780 g.L'.

4. A process for preparing a calcined clay composition, comprising the following steps: - a step of preparing a clay-silico-calcareous mineral filler according to the process as defined in any one of claims 1 to 3, and - a step of flash calcination of the clay-silico-calcareous filler obtained in the preceding step, said flash calcination step being carried out at a temperature of from 650°C to 820°C, in particular from 675°C to 790°C, and preferably from 675°C to 740°C.

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