Preparation for improving the particle size distribution of a mineral composition having reduced clinker content

Abstract

The present invention relates to a grinding process comprising the step of grinding a mineral composition to be ground in the presence of an adjuvant composition comprising at least one polymer (P) of the following chemical formula: In the above formula, - M represents H+, or a cation of valence (v) selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, and - When M = H, v = 1, and when M is a cation, v represents the valence of the cation M, and - R2, R3, R4, and R5 each independently represent H, CH₃, or -COO(M)1 / v, and - m = 0, 1 or 2 and; p = 0 or 1 and; X is O or N and, - R1 represents -[alkyl-O]z-R6, where each alkyl independently represents a linear or branched C2 to C4 alkylene, R6 represents H, C1 to C20 alkyl, cyclohexyl, or alkylaryl, and z is 40 or more, and The number of units (I) and units (II) in the polymer (P) is defined by a repeating unit (A) comprising one unit (II) and “a” units (I), where a is greater than 0, n is 1.5 to 50, and the molecular weight Mw (A) of the repeating unit (A) is 6500 g / mol or less. The above-mentioned mineral composition to be ground comprises 0% to 80% by weight of clinker based on the total weight of the above-mentioned mineral composition to be ground.

Description

Technology Field

[0001] The present invention relates to a process for grinding a mineral composition in the presence of a specific admixture.

[0002] In addition, the present invention relates to a mineral composition and a hydraulic composition comprising such an admixture.

[0003] In addition, the present invention relates to the use of the admixture for improving the grindability of the mineral composition, particularly the particle size distribution. Background Technology

[0004] Conventional cementitious compositions contain a significant proportion of clinker, even when mineral additives are included. For example, most common cements specified in standard EN 197-1:2011 “Composition, specifications and conformity criteria for common cements” contain at least 65 weight percent of clinker.

[0005] There is a need to reduce the clinker content of cementitious compositions and hydraulic binder compositions in order to reduce carbon influence while maintaining the mechanical and rheological properties of these compositions. New cementitious compositions and hydraulic binders are being developed in which a portion of the clinker is replaced with mineral additives, in particular natural or artificial pozzolan, silica fume, calcined clay, fly ash, and limestone. For example, CEM II / CM described in standard EN 197-5:2021 "Cement - Part 5: Portland-composite cement CEM II / CM and composite cement CEM VI" contains 50% to 64% by weight of clinker.

[0006] Furthermore, grinding is a critical step in the preparation of cementitious compositions because, in addition to being energy-consuming and complex to perform, the fineness and particle size distribution of the resulting cementitious composition affect the performance of hydraulic compositions (e.g., mortar and concrete) containing it, particularly water demand and compressive mechanical strengths. For example, a particle size fraction of less than 32 µm, more specifically between 2 µm and 32 µm, is an important parameter for strength development. In fact, excessively fine particles (< 2 µm) cause setting to proceed too rapidly, leading to a risk of cracking. Additionally, such particles can impair the workability of hydraulic compositions containing the mineral composition. Conversely, excessively coarse particles (> 32 µm) do not hydrate sufficiently quickly and therefore do not contribute significantly to the strength development required for conventional applications.

[0007] In addition, from an environmental perspective, it is also desirable to improve the productivity of the grinding equipment with the lowest possible energy consumption.

[0008] In particular, it is well known that glycols or alkanolamines are used to facilitate the grinding of materials and to shorten grinding time. However, these grinding aids are not satisfactory, especially when grinding mineral compositions with reduced clinker content. Furthermore, grinding control becomes more complex when multiple mineral compounds are co-grinded within the same composition and their hardnesses differ. This applies to the previously mentioned reduced-clinker-content compositions. In practice, when materials with different hardnesses are co-grinded, the relatively lower-hardness material may be over-grinded, while the higher-hardness material may not be sufficiently ground. These conditions can reduce the compressive strength of hydraulic compositions containing minerals, particularly when the mineral composition contains clinker or blast-furnace slag. Furthermore, when the mineral composition reaches a fine particle size, it is necessary to control the water demand that affects the workability of the hydraulic composition containing such minerals. This problem is particularly pronounced when large amounts of calcined clay, limestone, or pozzolan are used. Moreover, friable mineral materials are very difficult to grind properly because the ground particles tend to aggregate or adhere to the surfaces of the grinder, such as the balls of a ball mill, thereby reducing grinding efficiency.

[0009] Therefore, there is a need for a new process to improve the grinding and grindability of mineral compositions with low linker content, particularly when the grinding involves the co-grinding of various different mineral compounds or the grinding of diffusion-type mineral materials.

[0010] In particular, there is a need for a new process that can increase the proportion of 2 to 32 μm particles in the particle size distribution of mineral compositions with low linker content.

[0011] In addition, there is a need for a new mineral composition with low linker content that has high fineness and a high particle fraction of 2 to 32 μm.

[0012] Another object of the present invention is to provide a hydraulic composition based on a mineral composition with a low linker content, said hydraulic composition exhibiting excellent mechanical properties, particularly excellent compressive strength, more specifically excellent compressive strength within a short period (e.g., 1 and 2 days), and having improved workability, especially when said mineral composition contains a high proportion of calcined clay, fly ash, limestone and / or pozzolan.

[0013] For this purpose, the present invention relates to a grinding process comprising the step of grinding a mineral composition to be ground in the presence of an admixture composition comprising at least one polymer (P) of the following chemical formula.

[0014]

[0015] In the above formula,

[0016] - "M" is independently H + , or representing a cation of valence v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, and

[0017] - Here, if "M" represents H, "v" represents 1, and if "M" represents a cation, "v" represents the valence of the corresponding cation M, and

[0018] - "R2" and "R3" are each independently hydrogen, methyl, or -COO(M) having M and v as defined above 1 / vRepresenting a group of the chemical formula, preferably hydrogen or methyl, and

[0019] - "R4" and "R5" are each independently hydrogen, methyl, or -COO(M) having the M and v defined above 1 / v Representing the group of the chemical formula,

[0020] - "m" represents 0, 1, or 2, and

[0021] - "p" represents 0 or 1, and

[0022] - "X" is O or N, and

[0023] - "R1" is -[alkyl-O] z -R6 is represented, wherein "alkyl" of each [alkyl-O] unit independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, "R6" represents H, a C1 to C20 alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is 40 or more, and the number of units (I) and (II) in the polymer (P) is defined by a repeating unit (A) comprising one unit (II) and "a" units (I), and said repeating unit (A) is present "n" times in the polymer (P).

[0024] - "a" represents a non-zero positive number, and

[0025] - "n" is 1.5 to 50, and

[0026] - The molecular weight of the repeating unit (A) is 6500 g / mol or less, and the mineral composition to be ground contains 0 to 80 weight% of clinker based on the total weight of the mineral composition to be ground.

[0027] In other words, the polymer (P) contains n repeating units (A) of the following chemical formula, or is composed of n repeating units:

[0028] ,

[0029] Here, units (I) and (II) are as defined above.

[0030] It should be understood that the repeating units (A) of the polymer (P) may be different from each other, and preferably all are the same.

[0031] In fact, the inventors have surprisingly discovered that using a specific polymer (P) defined as above in the grinding process of a mineral composition with a juckling content can improve the grindability of the composition and, in particular, increase the fraction of 2-32 μm in the particle size distribution of the ground mineral composition. The combination of the length of the side chain (parameter "z"), the number of repeating units (A) (parameter "n"), and the size of the repeating units (A) (molecular weight of the repeating units (A)) can be optionally combined with the number of units (I) (parameter "a") to solve the technical problem mentioned herein.

[0032] In addition, the present invention relates to a mixed pulverized mineral composition, wherein the mixed pulverized mineral composition comprises a mineral composition comprising 0% to 80% by weight of clinker based on the total dry weight of the mineral composition and a polymer (P) as defined above.

[0033] In addition, the present invention relates to a use for improving the grindability of a mineral composition to be ground, comprising 0% by weight to 80% by weight of clinker based on the total weight of the mineral composition to be ground, of the polymer (P) defined above. Preferably, the use is for increasing the proportion of the 2-32 μm fraction in the particle size distribution of the ground mineral composition. Advantageously, the use is for increasing the proportion of the 2-32 μm fraction in the particle size distribution of a ground mineral composition comprising 0% by weight to 80% by weight of clinker based on the total weight of the mineral composition by at least 6% compared to the proportion of the 2-32 μm fraction in the particle size distribution of a ground mineral composition in the absence of the polymer (P). Specific details for implementing the invention

[0034] Grinding process

[0035] The present invention relates to a grinding process comprising the step of grinding a mineral composition to be ground in the presence of an admixture composition comprising at least one polymer (P).

[0036] According to one embodiment, the process comprises the step of preparing a mixture to be ground, which includes the step of mixing a mineral composition to be ground and an admixture composition, and then the step of grinding the mixture to be ground.

[0037] According to another embodiment, the process includes the step of introducing a mineral composition to be crushed into a grinder, and then the step of adding an admixture composition to the grinder during the grinding of the mineral composition to be crushed.

[0038] In a continuous process, various components are introduced at desired ratios using individual feed devices corresponding to each component, and are introduced into the grinder by a belt conveyor or air slide that handles various materials before the main feed to the grinder.

[0039] The admixture composition is added to the material on the conveyor belt before introduction into the grinder using a nozzle, and is also added into the grinder through an injection lance in the first chamber or the second chamber.

[0040] Preferably, the grinding process is carried out in a grinding facility, and the most widely used facilities are as follows:

[0041] - Ball Mill: A first, second, or third-generation separator may or may not be subsequently installed. If a separator is installed, the level of the circulating load is a critical parameter for improving grinding efficiency and yield. Filters and / or cyclones can capture fine particles from the gas flow generated in the separator and grinder, and these captured fine particles are reintroduced into the final product at the separator outlet.

[0042] - Vertical Mill: This is a grinder whose use is gradually expanding due to its low energy consumption. Since the grinding temperature is lower, this grinding process requires stricter conditions regarding the acceptable moisture content of the raw materials. A bag filter enables the separation of the gas flow from the layer of ground solid particles.

[0043] - Mills in series: These can be used to improve productivity; for example, there is a method using a roller press to reduce the particle size of the clinker at the grinder inlet.

[0044] - Other Mills: Mills containing cages filled with grinding agents, such as silica micro beads, are particularly effective in reducing grinding energy and can be used in series with other more traditional mills. This process enables the achievement of very high levels of fineness.

[0045] According to the first alternative, the grinding process is a co-grinding process of at least one first mineral material to be ground and at least one second mineral material to be ground. According to this alternative, the grinding process comprises the step of preparing a mineral composition to be ground, said step comprising mixing at least one first mineral material to be ground and at least one second mineral material to be ground to obtain the mineral composition to be ground.

[0046] The first mineral material to be crushed and the second mineral material to be crushed are as defined in the description of the mineral composition to be crushed below.

[0047] According to the second alternative, the grinding process involves separately grinding the materials of the mineral composition. Accordingly, preferably, the grinding process comprises the steps of: grinding a first mineral material to be ground in the presence of an admixture composition comprising at least one polymer (P) to obtain a first mineral material to be ground; grinding a second mineral material to be ground in the presence of an admixture composition comprising at least one polymer (P) to obtain a second mineral material to be ground; and mixing the first mineral material to be ground and the second mineral material to obtain a ground mineral composition.

[0048] The first mineral material to be crushed and the second mineral material to be crushed are as defined in the description of the mineral composition to be crushed below.

[0049] The above admixture composition may be mixed with the first mineral material to be ground and the second mineral material to be ground before being introduced into the grinder, or it may be mixed during the grinding of the first mineral material to be ground and the second mineral material to be ground.

[0050] Polymer (P)

[0051] The admixture composition used in the above grinding process comprises at least one polymer (P) comprising units of the following chemical formulas (I) and (II).

[0052]

[0053] Here,

[0054] - "M" is independently H + , or represents a cation of valence v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, and

[0055] - If "M" represents H, "v" represents 1, and if "M" represents a cation, "v" represents the valence of the cation M, and

[0056] - "R2" and "R3" are each independently hydrogen, methyl, or -COO(M) having the M and v defined above 1 / v Representing a group of the chemical formula, preferably representing hydrogen or methyl,

[0057] - "R4" and "R5" are each independently hydrogen, methyl, or -COO(M) having the M and v defined above 1 / v Representing the group of the chemical formula,

[0058] - "m" represents 0, 1, or 2, and

[0059] - "p" represents 0 or 1, and

[0060] - "X" is O or N, and

[0061] - "R1" is -[alkyl-O] z-R6 represents, wherein "alkyl" of each [alkyl-O] unit independently represents a linear or branched alkylene containing 2 to 4 carbon atoms, "R6" represents H, a C1 to C20 alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is 40 or more, and the number of units (I) and (II) in the polymer (P) is modeled by a repeating unit (A) comprising one unit (II) and "a" units (I), said repeating unit (A) is present "n" times in the polymer (P), and here,

[0062] - "a" is a non-zero positive number, and

[0063] - "n" is 1.5 to 50, and

[0064] - The molecular weight of the repeating unit (A) is 6500 g / mol or less.

[0065] The above polymer (P) can therefore be represented by the following chemical formula:

[0066]

[0067] Here, "R2", "R3", "M", "v", "R4", "R5", "m", "p", "X", "R1", "a", and "n" are as previously defined or follow any one of the embodiments defined below.

[0068] The repeating unit (A) is understood to be random and does not predetermine the arrangement order of units (I) and (II) within the polymer (P). Units (I) and (II) are preferably distributed randomly within the polymer (P).

[0069] Preferably, the molecular weight of the repeating unit (A) is 1500 to 6500 g / mol, preferably 2000 to 6500 g / mol, preferably 2500 to 6500 g / mol, preferably 3500 to 6000 g / mol, preferably 4500 to 6000 g / mol, preferably 5000 to 6000 g / mol, and more preferably 5200 to 5600 g / mol.

[0070] "z" indicates the number of [alkyl-O] units in the R1 group.

[0071] Preferably, "z" is 50 or more, preferably 70 or more, preferably 80 or more, preferably 85 or more, preferably 90 or more, and preferably 100 or more. "z" is preferably 40 to 230, preferably 50 to 200, preferably 70 to 150, preferably 80 to 120, preferably 90 to 120, and preferably 100 to 120.

[0072] "n" represents the number of repeating units (A) in the polymer (P).

[0073] Preferably, "n" is 4 to 40, preferably 5 to 25, preferably 6 to 20, and preferably 7 to 18.

[0074] Preferably, "a" is 0.2 to 100, preferably 0.5 to 50, preferably 0.8 to 25, preferably 1.0 to 20, preferably 2.0 to 15, preferably 3.0 to 10, preferably 3.9 to 7, and preferably 4.0 to 6.

[0075] Preferably, the polymer (P) has a grafting ratio of more than 5%, preferably 6% or more, preferably 8% or more, preferably 10% or more, preferably 12% or more, preferably 15% or more. In addition, the grafting ratio is preferably 50% or less, preferably 30% or less, preferably 25% or less, preferably 21% or less.

[0076] The graft ratio corresponds to the ratio between the number of units (II) in the polymer (P) and the total number of units (I) and units (II). The graft ratio is determined by the number of moles of the monomers introduced for the synthesis of the polymer (P), assuming that the monomers are completely converted.

[0077] "a" is related to the graft ratio by the following relationship:

[0078] a = (1 - graft ratio) / (graft ratio)

[0079] Molecular weight Mw of the repeating unit (A) (A) can be expressed by the following relationship:

[0080] Mw (A) = Mw (단위 (II)) + a * Mw (단위 (I)) ,

[0081] Here, Mw (단위 (I)) represents the molecular weight of the unit (I) of the polymer (P), and Mw (단위 (II)) represents the molecular weight of the unit (II) of the polymer (P). Mw (A) is the calculated molecular weight, and therefore the weight-average molecular weight of repeating unit (A) is repeating unit (A) ) It is equal to the number average molecular weight.

[0082] n corresponds to the following ratio:

[0083] n = Mw (P) / Mw (A)

[0084] Here, Mw(A) represents the molecular weight of the repeating unit (A) defined above, and M w(P) represents the number average molecular weight of the polymer (P). Mw (P) is determined by steric exclusion chromatography and can be measured, for example, under the following conditions:

[0085] Column: Aquagel guard column, PL aquagel-OH 40, PL aquagel-OH 30, PL aquagel-OH 20

[0086] Mobile phase: Physiological saline eluent (NaNO3 8.5g, NaH2PO4,2H2O 1.4g, Na2HPO4,2H2O 1.9g, NaN30.7g in 1 liter of pure water)

[0087] Flow rate: 1 ml / min

[0088] Detector: Refractive index detector + Light scattering detector + Viscometer

[0089] Column compartment temperature: 30 ℃

[0090] Injection volume: 150 µl

[0091] Sample concentration: Approx. 10 mg / ml

[0092] Standard substance: PEO 45 kDa.

[0093] Preferably, in the polymer (P), m = 0, p = 1 and X = 0.

[0094] The following embodiments may be considered independently of each other, may be combined with each other, and may also be combined with any one of the preferred embodiments described above:

[0095] - v = 1 and M = H + In the case of, and / or

[0096] - If R2 = H, and / or

[0097] - If R3 = CH3, and / or

[0098] - If R4 = H, and / or

[0099] - If R5 = CH3, and / or

[0100] - When m = 0, and / or

[0101] - When p = 1, and / or

[0102] - If X = O, and / or

[0103] - R1 = [alkyl-O] z -R6, where alkyl = CH2-CH2 and / or R6 is a C1 to C20 alkyl group, preferably CH3.

[0104] The polymer (P) is preferably used in a ratio of 0.01% to 1% by weight, particularly 0.05% to 0.5% by weight, preferably 0.05% to 0.3% by weight, and more preferably 0.10% to 0.30% by weight, based on the dry weight of the mineral composition to be ground.

[0105] Accordingly, the admixture composition is preferably used in an amount such that the ratio of the polymer (P) described above can be obtained.

[0106] Admixture composition

[0107] The admixture composition may include additional components. Examples for this include, without limitation, alkanolamines, glycols, glycerols, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or salts thereof (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartaric acid, malonic acid and mixtures thereof), water-reducing and high-water-reducing compounds (including lignosulfonates, hydroxycarboxylic acids, comb-shaped polycarboxylates and mixtures thereof), packset-reducing compounds (including polyacrylic acid), (wherein packset is a relative numerical indicator measured according to the method described in standard ASTM C1565-19, representing the compaction tendency of cement stored or transported in bulk), surfactants, defoamers (tributyl phosphate, triisobutyl phosphate, Examples include dibutyl phthalate, octyl alcohol, alkyl amine, water-insoluble carbonate esters and boric acid esters, and mixtures thereof), air-entraining additives (including wood resin salts, sulfonated lignin salts, and mixtures thereof), set retarders (including sugars, corn syrup, molasses, and mixtures thereof), and mixtures thereof.

[0108] Preferably, the admixture composition further comprises a component selected from alkanolamine, glycol, glycerol, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or salts thereof (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartrate, malonic acid and mixtures thereof).

[0109] The above admixture composition is preferably in the form of a solution, suspension, or powder, and more preferably in the form of a solution.

[0110] Preferably, the content of the polymer (P) in the admixture composition is 0.10% to 60% by weight, preferably 0.10% to 40% by weight, preferably 0.10% to 20% by weight, and preferably 1% to 10% by weight, based on the total weight of the admixture composition.

[0111] The polymer (P), more generally the admixture composition, at the above usage ratio, advantageously enables a larger fraction of 2-32 μm in the particle size distribution of the ground mineral composition.

[0112] This distribution is advantageous in that it promotes excellent compressive strength, particularly short-term compressive strength. Short-term compressive mechanical strength refers to compressive strength at 16 hours, 1 day, and 2 days, preferably compressive strength at 2 days. The said compressive strength is measured according to NF EN 196-1 (September 2016) "Methods of testing cement - Part 1: Determination of strength - Methods of testing cement" or ASTM C109 / C109M-21.

[0113] Mineral composition to be crushed

[0114] The mineral composition to be ground comprises 0% to 80% by weight of clinker based on the total dry weight of the mineral composition to be ground.

[0115] Accordingly, the above-mentioned mineral composition to be ground preferably includes at least one mineral material to be ground other than clinker, and optionally includes clinker.

[0116] With respect to the nature of the mineral composition to be ground, the process according to the present invention and the selection of a specific polymer (P) are particularly advantageous when grinding a pulverizable mineral material, or when co-grinding a hard mineral material such as clinker with a pulverizable mineral material.

[0117] In the present invention, the hard or friable properties of a mineral material are related to its grindability, that is, the ease of grinding. The grindability of a mineral material can be evaluated by grinding the material in a laboratory closed-circuit ball mill without additives. In practice, grindability is related to grinding energy, and, assuming the remaining grinding conditions and grinder conditions are the same, grinding energy is directly related to the grinding time required to obtain the target Blaine fineness. Blaine fineness is measured according to the standard NF EN 196-6. In particular, the particle size of the mineral material before grinding must correspond to passing 100% through a 2.15 mm sieve.

[0118] In the present invention, the mineral material is 1500 to 2500 cm 2 A material is considered diagridigenic if the grinding time required to obtain a Blaine fineness of 1 / g is at least twice as short as the grinding time required for a clinker that meets the requirements of standard NF EN 197-1 to obtain the same Blaine fineness (preferably 2 to 20 times shorter, and more preferably 2 to 10 times shorter). It must be understood that to perform this test, the mineral material under test and the clinker must be ground under the same conditions (conditions excluding grinding time).

[0119] Examples of such pulverizable materials include: calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, pulverized shale, diatomite and any mixture thereof; more specifically, calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash and any mixture thereof; even more specifically, calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof.

[0120] Conversely, mineral materials are 1500 to 2500 cm 2 It is considered hard if the grinding time required to obtain a Blaine fineness of / g corresponds to 0.8 to 10 times the grinding time required to obtain the same Blaine fineness for clinker that meets the requirements of standard NF EN 197-1.

[0121] Examples of hard materials include: clinker, silica fume, granular blast furnace slag, crystallized, expanded, glassy (granular or pellet) blast furnace slag, converter steel slag, carbon steelmaking slag from the electric route, ladle slag, quartz, alumina cement, sulfoalumina clinker, ye'elimite, belitic clinker, recycled glass, zeolite, recycled concrete fines resulting from demolition, and mixtures thereof.

[0122] Preferably, the mineral composition to be ground comprises 20% to 100% by weight of mineral materials other than clinker based on the total dry weight of the mineral composition to be ground, preferably 20% to 99.99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, preferably 45% to 95% by weight, preferably 50% to 95% by weight, and preferably 60% to 90% by weight. If the mineral composition to be ground comprises a plurality of mineral materials other than clinker, the above content corresponds to the total content of mineral materials other than clinker.

[0123] When the mineral composition to be ground includes clinker, the clinker is present in an amount of preferably 0.01 wt% to 80 wt%, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, preferably 10 wt% to 40 wt% based on the total dry weight of the mineral composition to be ground.

[0124] The above clinker is particularly Portland clinker or sulfoalumina clinker, and preferably Portland clinker as defined in Harry FW Taylor, "Cement Chemistry", Edition, 2., Academic Press (1990).

[0125] The mineral material other than the above clinker may be any mineral material that can be included in the composition of the hydraulic binder.

[0126] Examples of mineral materials other than clinker suitable for the present invention include calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale, etc.), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steelmaking slag produced in the electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina cement, zeolite, belite clinker, recycled glass, zeolite, diatomaceous earth, recycled concrete powder generated from demolition work, and mixtures thereof.

[0127] In particular, examples of mineral materials other than clinker suitable for the present invention include calcium sulfate, mineral additives (calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale, etc.), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steel slag produced in the electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina cement, recycled glass, zeolite, diatomite, recycled concrete powder generated from demolition work, and any mixture thereof.

[0128] In particular, mineral materials other than clinker are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof, preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and any mixture thereof.

[0129] In particular, mineral materials other than clinker are selected from calcium sulfate and mineral additives, more specifically from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and blast furnace slag, and furthermore are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and mixtures thereof.

[0130] The expression "mineral additive" refers to granular blast furnace slag defined in Section 5.2.2 of Standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements", pozzolanic materials such as calcined clay defined in Section 5.2.3 of Standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements", fly ash defined in Section 5.2.4 of Standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements", calcined shale defined in Section 5.2.5 of Standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements", and in Section 5.2.6 of Standard NF EN 197-1 (April 2012) It means defined limestone, or silica fume or a mixture thereof as defined in Section 5.2.7 of the standard NF EN 197-1 (April 2012) “Composition, specifications and conformity criteria for common cements”.

[0131] In particular, mineral materials other than clinker are selected from dichotomy mineral materials.

[0132] Preferably, the mineral composition to be crushed comprises a mixture of at least one first mineral material to be crushed and at least one second mineral material to be crushed.

[0133] The first mineral material to be ground and the second mineral material to be ground are each independently selected from one of the lists of "mineral materials other than clinker suitable for the present invention," preferably selected from clinker, calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy blast furnace slag (granular or pellet form), converter steel slag, carbon steelmaking slag produced in the electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina clinker, je-elimite, belite clinker, recycled glass, zeolite, diatomaceous earth, and recycled concrete fine powder generated from demolition work, more preferably selected from clinker, calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof.

[0134] According to a specific embodiment, the first mineral material to be ground is a hard mineral material, and the second mineral material to be ground is a diffusion mineral material. Accordingly, the mineral composition to be ground may include at least one hard mineral material and at least one diffusion mineral material. The hard mineral material and the diffusion mineral material are as defined above.

[0135] According to this embodiment, preferably, the mineral composition to be ground comprises 1% to 99% by weight of a di-grindable mineral material based on the total dry weight of the mineral composition to be ground, preferably 10% to 90% by weight, preferably 20% to 80% by weight, preferably 30% to 70% by weight, and preferably 40% to 60% by weight. If the mineral composition to be ground comprises a plurality of di-grindable mineral materials, their content corresponds to the total content of the di-grindable mineral materials.

[0136] According to this embodiment, preferably, the mineral composition to be ground comprises 1% to 99% by weight of hard mineral materials based on the total dry weight of the mineral composition to be ground, preferably 10% to 90% by weight, preferably 20% to 80% by weight, preferably 30% to 70% by weight, and preferably 40% to 60% by weight. When the mineral composition to be ground comprises a plurality of hard mineral materials, their content corresponds to the total content of the hard mineral materials.

[0137] According to a more specific embodiment, the first mineral material to be crushed is clinker, and the second mineral material to be crushed is a mineral material other than clinker, preferably selected from one of the list of "mineral materials other than clinker suitable for the present invention," preferably selected from calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steelmaking slag produced in an electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoaluminium clinker, zeolite, belite clinker, recycled glass, zeolite, diatomaceous earth, recycled concrete fine powder generated from demolition work, and any mixture thereof. More preferably, the second mineral material to be ground is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof. Even more preferably, the second mineral material to be ground is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and any mixture thereof. Even more preferably, the second mineral material to be ground is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof. The content of the clinker is 0.01% to 80% by weight based on the total dry weight of the mineral composition to be ground, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, and preferably 10% to 40% by weight. In addition, preferably, the content of the second mineral material to be ground is 20% to 99% by weight based on the total dry weight of the mineral composition to be ground.It is 99 weight%, preferably 30 weight% to 99 weight%, preferably 40 weight% to 99 weight%, preferably 45 weight% to 95 weight%, preferably 50 weight% to 95 weight%, preferably 60 weight% to 90 weight%.

[0138] Preferably, according to this embodiment, the second mineral material to be ground is a di-grindable mineral material.

[0139] According to another more specific embodiment, the first mineral material to be ground and the second mineral material to be ground are each mineral materials to be ground other than clinker, preferably each independently selected from one of the list of “mineral materials other than clinker suitable for the present invention,” preferably selected from calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steelmaking slag produced in the electric furnace process, ladle slag, ground shale), quartz, alumina cement, sulfoalumina clinker, jellimite, belite clinker, recycled glass, zeolite, diatomite, recycled concrete fine powder generated in footwork, and any mixture thereof. More preferably, it is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof. Even more preferably, it is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and any mixture thereof. Still more preferably, it is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof.

[0140] Preferably, the mineral composition to be ground is a mixture of clinker and calcium sulfate; or a mixture of clinker and calcined clay; or a mixture of clinker and limestone; or a mixture of clinker and pozzolan (natural or artificially derived); or a mixture of calcium sulfate and calcined clay; or a mixture of calcium sulfate and limestone; or a mixture of calcium sulfate and pozzolan (natural or artificially derived); or a mixture of limestone and calcined clay; or a mixture of limestone and pozzolan (natural or artificially derived); or a mixture of calcined clay and pozzolan (natural or artificially derived).

[0141] or a mixture of clinker, calcium sulfate, and calcined clay; or a mixture of clinker, calcium sulfate, and limestone; or a mixture of clinker, calcium sulfate, and pozzolan (natural or artificial); or a mixture of clinker, calcium sulfate, calcined clay, and limestone; or a mixture of clinker, calcium sulfate, pozzolan (natural or artificial), and limestone; or a mixture of calcined clay, limestone, and pozzolan (natural or artificial). Here, where clinker is present, its content is understood to be 0.01 wt% to 80 wt%, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, preferably 10 wt% to 40 wt% based on the total dry weight of the mineral composition to be ground.

[0142] According to one embodiment, the mineral composition to be ground includes calcium sulfate as an additional component, preferably in an amount of 0.1% to 10% by weight, preferably 1% to 5% by weight, based on the dry weight of the mineral composition to be ground excluding calcium sulfate. In practice, according to this embodiment, the calcium sulfate content is expressed based on the total dry weight of all constituent components of the mineral composition to be ground excluding calcium sulfate. Accordingly, according to this embodiment, the content of the previously described clinker and non-clinker material(s) is also all expressed based on the dry weight of the mineral composition to be ground excluding calcium sulfate.

[0143] According to this embodiment, calcium sulfate is present in addition to a mineral material to be ground other than a clinker and an optional clinker, or is present in addition to a first mineral material to be ground and a second mineral material to be ground. In this embodiment, the mineral material to be ground other than a clinker or the first mineral material to be ground and the second mineral material to be ground are as previously defined, but are different from calcium sulfate (thus, all previously defined embodiments apply, but calcium sulfate is excluded from the list of compounds).

[0144] According to this embodiment, when the content is expressed based on the total dry weight of the mineral composition to be ground (rather than the dry weight of the mineral composition to be ground excluding calcium sulfate), the mineral composition to be ground preferably comprises the following:

[0145] - Clinker: 0 wt% to 80 wt%, preferably 0.01 wt% to 80 wt%, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%;

[0146] - Mineral material other than clinker: 19 wt% to 95 wt%, preferably 19 wt% to 94.99 wt%, preferably 19.9 wt% to 90 wt%, preferably 19.9 wt% to 89.99 wt%, preferably 29 wt% to 94 wt%, preferably 29.9 wt% to 89 wt%, preferably 39 wt% to 94 wt%, preferably 39.9 wt% to 89 wt%, preferably 44.9 wt% to 85 wt%, preferably 44 wt% to 90 wt%, preferably 49 wt% to 90 wt%, preferably 49.9 wt% to 85 wt%, preferably 59 wt% to 85 wt%, preferably 59.9 wt% to 80 wt%; and

[0147] - Calcium sulfate: 0.1% to 10% by weight, preferably 1% to 5% by weight.

[0148] Mixed mineral composition

[0149] The present invention also relates to a mixed mineral composition.

[0150] In this application, the expression "mixed mineral composition" means that the admixture composition is additionally included in the previously defined mineral composition, and "mineral composition" means a mineral composition that does not include an admixture.

[0151] The above-mentioned mixed mineral composition is preferably in a crushed state.

[0152] Preferably, the mixed mineral composition has a central particle size (d 50 ) represents a fineness characterized by being 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, and even more preferably between 1 and 20 μm. The fineness parameter corresponds to a diameter in which half of the particle group has a larger particle diameter and the other half has a smaller particle diameter.

[0153] Preferably, the mixed mineral composition has a central particle size (d 50 When the particle size is 9 μm to 11 μm, preferably about 10 μm, the content of 2 to 32 μm particles based on the total volume of the mixed mineral composition is at least 70 volume%, preferably at least 72 volume%, preferably at least 74 volume%, preferably 70 volume% to 95 volume%.

[0154] The above central particle size (d 50 The content of ) and 2-32 µm particles is calculated from the particle size distribution measured by laser granulometry. For example, it can be measured by the dry method using a MALVERN Mastersizer 3000 instrument, in which case a Mie model of 1.68 + 0.1 i (where i is the imaginary index) is used.

[0155] Preferably, the content of polymer (P) in the mixed mineral composition is 0.01 wt% to 1 wt%, preferably 0.05 wt% to 0.5 wt%, preferably 0.05 wt% to 0.3 wt%, and preferably 0.10 wt% to 0.30 wt% based on the total dry weight of the mineral composition.

[0156] Preferably, the mixed mineral composition comprises 0% to 80% by weight of clinker based on the total dry weight of the mineral composition.

[0157] Accordingly, the mineral composition preferably comprises at least one mineral material other than clinker, and optionally comprises clinker.

[0158] Preferably, the mixed mineral composition comprises 20% to 100% by weight of mineral materials other than clinker based on the total dry weight of the mineral composition, preferably 20% to 99.99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, preferably 45% to 95% by weight, preferably 50% to 95% by weight, and preferably 60% to 90% by weight.

[0159] When the above mixed mineral composition includes clinker, the clinker is present in an amount of preferably 0.01 wt% to 80 wt%, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, and preferably 10 wt% to 40 wt% based on the total dry weight of the mineral composition.

[0160] The mineral material other than the clinker is as previously defined with respect to the mineral composition to be ground. According to one embodiment, the mineral material other than the clinker is a di-grindable mineral material.

[0161] Preferably, the mixed mineral composition comprises a mixture of at least one first mineral material and at least one second mineral material.

[0162] The first mineral material and the second mineral material are each independently selected from clinker, calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steel slag produced in the electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina clinker, jeelimite, belite clinker, recycled glass, zeolite, diatomaceous earth, recycled concrete fine powder generated from demolition work, and any mixture thereof, and more preferably selected from clinker, calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof. According to a specific embodiment, the first mineral material is a hard mineral material and the second mineral material is a diffusion mineral material, preferably present in the mineral composition to be ground in an amount previously defined.

[0163] According to a more specific embodiment, the first mineral material is clinker, and the second mineral material is selected from calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steel slag produced in the electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina clinker, je-elelimite, belite clinker, recycled glass, zeolite, diatomite, recycled concrete powder generated from demolition work, and any mixture thereof. More preferably, the second mineral material is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof. More preferably, the second mineral material is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and any mixture thereof. Even more preferably, the second mineral material is selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof. The clinker content is 0.01 wt% to 80 wt% based on the total dry weight of the mineral composition, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, and preferably 10 wt% to 40 wt%. According to this embodiment, the second mineral material is preferably a bipulverizable mineral material.

[0164] According to another more specific embodiment, the first mineral material and the second mineral material are materials different from clinker, and preferably each are independently selected from calcium sulfate, mineral additives (e.g., calcined clay, limestone, natural or artificial pozzolan, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, glassy (granular or pellet-shaped) blast furnace slag, converter steel slag, carbon steel slag produced in an electric furnace process, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina clinker, jellimite, belite clinker, recycled glass, zeolite, diatomaceous earth, recycled concrete fines generated from demolition work, and any mixture thereof. More preferably, the first mineral material and the second mineral material are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof. Even more preferably, the first mineral material and the second mineral material are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, and any mixture thereof. Even more preferably, the first mineral material and the second mineral material are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, and any mixture thereof.

[0165] In particular, the mixed mineral composition is a mixture of clinker and calcium sulfate; or a mixture of clinker and calcined clay; or a mixture of clinker and limestone; or a mixture of clinker and pozzolan (natural or artificial); or a mixture of calcium sulfate and calcined clay; or a mixture of calcium sulfate and limestone; or a mixture of calcium sulfate and pozzolan (natural or artificial); or a mixture of limestone and calcined clay; or a mixture of limestone and pozzolan (of natural or artificial origin); or a mixture of calcined clay and pozzolan (of natural or artificial origin).

[0166] or a mixture of clinker, calcium sulfate, and calcined clay; or a mixture of clinker, calcium sulfate, and limestone; or a mixture of clinker, calcium sulfate, and pozzolan (natural or artificial); or a mixture of clinker, calcium sulfate, calcined clay, and limestone; or a mixture of clinker, calcium sulfate, pozzolan (of natural or artificial origin), and limestone; or a mixture of calcined clay, limestone, and pozzolan (of natural or artificial origin). Where clinker is present, its content is understood to be 0.01 wt% to 80 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, preferably 10 wt% to 40 wt% based on the total dry weight of the mineral composition.

[0167] According to one embodiment, the mixed mineral composition comprises calcium sulfate as an additional component, preferably in an amount of 0.1% to 10% by weight, preferably 1% to 5% by weight, based on the dry weight of the mineral composition excluding calcium sulfate. In practice, according to this embodiment, the calcium sulfate content is expressed based on the total dry weight of all components of the mineral composition excluding calcium sulfate. Accordingly, according to this embodiment, the content ranges of the clinker and non-clinker material(s) described above are all applicable, but are expressed based on the dry weight of the mineral composition excluding calcium sulfate.

[0168] According to this embodiment, calcium sulfate is present in the mixed mineral composition in addition to a mineral material other than the clinker and an optional clinker, or is present in addition to a first mineral material and a second mineral material. In this embodiment, the mineral material other than the clinker, or the first mineral material and the second mineral material, are as previously defined but are different from calcium sulfate (thus, all previously defined embodiments apply, but calcium sulfate is excluded from the list of mineral compounds).

[0169] According to this embodiment, when the content is expressed based on the total dry weight of the mineral composition (rather than the dry weight of the mineral composition excluding calcium sulfate), the mixed mineral composition preferably comprises the following:

[0170] - Clinker: 0 wt% to 80 wt%, preferably 0.01 wt% to 80 wt%, preferably 1 wt% to 70 wt%, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, preferably 10 wt% to 40 wt%;

[0171] - Mineral material other than clinker: 19 wt% to 95 wt%, preferably 19 wt% to 94.99 wt%, preferably 19.9 wt% to 90 wt%, preferably 19.9 wt% to 89.99 wt%, preferably 29 wt% to 94 wt%, preferably 29.9 wt% to 89 wt%, preferably 39 wt% to 94 wt%, preferably 39.9 wt% to 89 wt%, preferably 44.9 wt% to 85 wt%, preferably 44 wt% to 90 wt%, preferably 49 wt% to 90 wt%, preferably 49.9 wt% to 85 wt%, preferably 59 wt% to 85 wt%, preferably 59.9 wt% to 80 wt%; and

[0172] - Calcium sulfate: 0.1% to 10% by weight, preferably 1% to 5% by weight.

[0173] Preferably, the mixed mineral composition is obtained by a grinding process according to the present invention.

[0174] The above-mentioned mixed mineral composition may include additional components, and these components may be added before grinding, optionally through the addition of the admixture composition of the present application, or after grinding. Examples for this include, without limitation, alkanolamines, glycols, glycerols, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or salts thereof (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartaric acid, malonic acid and mixtures thereof), water reducers and super-water reducer compounds (including lignosulfonates, hydroxycarboxylic acids, comb-shaped polycarboxylates and mixtures thereof), packset reducers (including polyacrylic acids, where packset is a relative numerical indicator measured according to the method described in ASTM C1565-19, representing the compaction tendency of cement stored or transported in bulk), surfactants, and defoamers (tributyl phosphate, triisobutyl phosphate, dibutyl phthalate, octyl alcohol, alkyl amines, water-insoluble carbonate esters and boric acid). Examples include esters, and mixtures thereof), air-entraining additives (including wood resin salts, sulfonated lignin salts, and mixtures thereof), setting retardants (including sugars, corn syrup, molasses, and mixtures thereof), and mixtures thereof.

[0175] Hydraulic composition

[0176] The present invention also relates to a hydraulic composition comprising the following:

[0177] - A mixed mineral composition as defined above,

[0178] - water,

[0179] - Optionally aggregate, and

[0180] - Optional mineral additives.

[0181] The hydraulic composition according to the present invention is preferably a concrete, mortar, or screed composition.

[0182] The hydraulic composition is prepared by a conventional method by mixing the above components.

[0183] "Aggregate" refers to an assembly of mineral particles with an average diameter of 0 mm to 125 mm. Based on their diameter, aggregates are classified into the following six groups according to the standard NF P 18-545 (September 2011) "Aggregates - Elements of definition, conformity and codification": filler, sablón, sand, gravel, chipping, and ballast. The most commonly used aggregates are as follows:

[0184] - Filler: having a diameter of less than 2 mm, at least 85% of the aggregate having a diameter of less than 1.25 mm, and at least 70% having a diameter of less than 0.063 mm.

[0185] - Sand: with a diameter of 0 mm to 4 mm (however, according to the standard NF EN 13242+A1 (March 2008) "Aggregates for hydraulically bound materials and unbound materials for use in civil engineering work and road construction," a diameter of up to 6 mm is permitted).

[0186] - Gravel: Those with a diameter exceeding 6.3 mm.

[0187] - Crushed stone: Those with a diameter of 2 mm to 63 mm.

[0188] Therefore, sand is included in the definition of aggregate in the present invention.

[0189] The above filler may be of particular limestone or dolomitic origin.

[0190] The above hydraulic composition may also include other additives known to a person skilled in the art, for example, mineral additives and / or additives, for example, anti-air-entrainment additives, anti-foam agents, set accelerators or retarders, rheology-modifying agents, additional plasticizers (plasticizers or superplasticizers), in particular superplasticizers. For example, CHRYSO®Fluid Premia 180 or CHRYSO®Fluid Premia 196 superplasticizers may be used.

[0191] Within the scope of the present invention, the setting retardant may be made particularly of a sugar-, molasses-, or vinasse-based setting retardant.

[0192] Preferably, water-reducing and high water-reducing admixtures are selected from the following:

[0193] - Sulfonated salts of naphthalene-formaldehyde condensates, generally referred to as polynaphthalene sulfonates or naphthalene-based high-performance water reducers;

[0194] - Sulfonated salts of melamine-formaldehyde condensates, generally referred to as melamine-based high-performance water reducers;

[0195] - Lignin derivatives such as lignosulfonates;

[0196] - Sodium gluconate and sodium glucoheptoneate;

[0197] - Polyacrylate;

[0198] - Polyaryl ether (PAE);

[0199] - Polycarboxylic acid-based products, particularly polycarboxylate comb copolymer-based products, which are branched polymers in which the main chain has carboxyl groups and the side chains consist of polyether-type chains, particularly polyethylene oxide. Examples include poly[(meth)acrylic acid-graft-polyethylene oxide]. In particular, high-performance superplasticizers from the CHRYSO®Fluid Optima, CHRYSO®Fluid Premia, and CHRYSO®Plast Omega series sold by CHRYSO, and high-performance superplasticizers from ADVA®, MIRA®, ZYLA®, and CONCERA® sold by GCP may be used.

[0200] - Polyalkoxylated polyphosphonate-based products, in particular the product described in patent document EP 0 663 892 (e.g., CHRYSO®Fluid Optima 100).

[0201] The present invention will be described in more detail below through only non-limiting embodiments.

[0202] In all embodiments, unless otherwise specified, the content of the admixture(s) is expressed as weight based on the total dry weight of the non-admixed mineral composition.

[0203] Examples

[0204] The various polymers used are detailed in Table 1 below.

[0205] [Table 1]

[0206]

[0207]

[0208] Example 1: Effect of the properties of the polymer present during the grinding of the mineral composition on the particle size distribution of the ground mineral composition

[0209] A mineral composition comprising 55 wt% clinker, 5 wt% gypsum, and 40 wt% natural pozzolan, based on the weight of the dry mineral composition, was ground alone or in the presence of polymers A, B, C, D, E, and F. The polymers were added in an amount of 0.1 wt% of active material based on the dry weight of the mineral composition. Grinding was performed in a closed-system laboratory ball mill with a capacity of 5 kg.

[0210] If a polymer is present, the polymer was introduced into the grinder along with other materials before the grinding began.

[0211] In each test, the mineral composition is ground to the lowest possible median particle size (d 50 The process was carried out until ) was obtained. The fineness parameter corresponds to a diameter where half of the particle population has a larger diameter and the other half has a smaller diameter, and was calculated from the particle size distribution measured using a MALVERN Mastersizer 3000 instrument with a dry method and a Mie model of 1.68 + 0.1i. In addition, the proportion of particles with a diameter of 2 μm to 32 μm was also calculated from the particle size distribution. The proportion was expressed as a percentage (%).

[0212] The results obtained are shown in Table 2 below.

[0213] [Table 2]

[0214]

[0215] These results show that when a polymer is present during the grinding process, d is compared with a reference system ground without an admixture. 50 It is shown that when α is 10 µm, the proportion of 2-32 µm particles can be increased, and a median particle size smaller than the reference can also be achieved. However, polymers B, C, D, and E according to the present invention d 50When α is 10 µm, the proportion of 2-32 µm particles can be increased even more significantly, that is, showing an increase rate exceeding +6%. The maximization of the proportion of 2-32 µm particles achieved with these specific polymers is related to a combination of the length of the grafted chain (the exponent z of unit II) on the one hand and the molecular weight of the repeating unit (A) on the other.

[0216] Example 2: Effect of the properties of the polymer present during the grinding of the mineral composition on the short-term strength of the hydraulic composition containing the ground mineral composition of Example 1

[0217] Various hydraulic compositions containing the ground mineral composition of Example 1 were prepared according to the protocol in accordance with standard NF EN 196-1 (September 2016) "Methods of testing cement - Part 1: Determination of strength - Methods of testing cement" with a water-to-cementitious-composition ratio of 0.5.

[0218] The 24-hour and 48-hour compressive strength of the final composition was evaluated according to the standard NF EN 196-1 (September 2016) "Methods of testing cement - Part 1: Determination of strength - Methods of testing cement".

[0219] The results obtained are shown in Table 3 below.

[0220] [Table 3]

[0221]

[0222] These results show that polymers B, C, D, and E, which enable a high proportion of 2 to 32 μm particles, can further improve the 24-hour and 48-hour strength of a hydraulic composition based on a pulverized mineral composition in the presence of said polymers.

[0223] Example 3: Influence of properties of mineral composition (calcined clay)

[0224] In this embodiment, a mineral composition comprising 55 wt% clinker, 5 wt% gypsum, and 40 wt% calcined clay, based on the weight of the dry mineral composition, was ground alone or in the presence of polymers A, B, or G defined in Table 1. The polymer was added in an amount of 0.1 wt% of active material, based on the dry weight of the mineral composition. Grinding was performed in a closed-system laboratory ball mill with a grinding capacity of 5 kg. In each test, the mineral composition was ground to the lowest possible median particle size (d). 50 Performed until ) was obtained.

[0225] The obtained results are shown in Table 4 below.

[0226] [Table 4]

[0227]

[0228] In addition, the 24-hour and 48-hour compressive strengths of a hydraulic composition similar to Example 2, comprising the crushed mineral compositions 3-1*, 3-2*, and 3-3 of Example 3, were measured according to the same protocol as Example 2.

[0229] The results obtained are shown in Table 5 below.

[0230] [Table 5]

[0231]

[0232] These results are similar to the results obtained in Example 1, that is, they show that a polymer satisfying the definition according to the present invention enables a higher proportion of 2-32 μm particles than a comparative polymer.

[0233] This shows that the selection of these specific polymers can maximize the proportion of the 2-32 µm particle group for different mineral compositions, and consequently improve short-term compressive strength. These mineral compositions may be ground alone or in the form of a mixture with clinker.

[0234] Example 4: Effect of 2-32 µm particle ratio

[0235] The short-term compressive strength (24 hours) of a hydraulic composition containing mineral compositions 3-5 of Example 3 and a hydraulic composition containing similar mineral compositions but not ground in the presence of polymer G were compared. In the latter case, polymer G was added at the time of mixing, and the amount added was 0.1 wt% of the active material based on the dry weight of the mineral composition.

[0236] The results are shown in Table 6 below.

[0237] [Table 6]

[0238]

[0239] These results show that a ratio of 2-32 μm particles is important to obtain high short-term compressive strength. In this embodiment, the hydration delay at a young age of the hydraulic composition caused by the acidity of the polymer is compensated by an increase in the fineness of the mineral composition.

[0240] Example 5: Comparison with the grinding aid of the prior art

[0241] For the mineral composition of Example 3, the grinding efficiency was compared when 0.1% of polymer B was added and when 0.01% of triethanolamine was added. All added amounts were expressed as a percentage of the active substance based on the weight of the mineral composition. In each test, the grinding of the mineral composition was based on the median particle size (d 50 ) was performed until it reached 7.5 μm.

[0242] The results obtained are shown in Table 7 below.

[0243] [Table 7]

[0244]

[0245] Consistent with the results of Examples 1 and 3, polymer B is given d 50It was possible to obtain a higher proportion of particles with a diameter of 2-32 µm compared to the reference system for (10 µm), and to achieve a higher proportion in the final state. On the other hand, triethanolamine did not improve these characteristics.

[0246] Example 6: Influence of the properties of the mineral composition

[0247] In this example, different mineral compositions were ground in the presence or absence of polymer G defined in Table 1. Polymer G was added in an amount of 0.1 wt% of the active material based on the dry weight of the mineral composition. Grounding was performed in a closed-loop laboratory ball mill with a grinding capacity of 5 kg. In each test, the mineral composition was ground to a predetermined median particle size (d 50 )(hereinafter "Objective d 50 ...performed until reaching "called)"

[0248] The results obtained are shown in Table 8 below.

[0249] [Table 8]

[0250]

[0251] Example 7: Grinding of mineral additives

[0252] Calcined clay and limestone, in the presence of polymer G (Tests 7-2 and 7-4), and in the presence of a conventional grinding aid based on triethanolamine acetate (in the case of calcined clay, Test 7-1 * ), or without any admixture (in the case of limestone, Test 7-3 ** ) crushed.

[0253] The results obtained are shown in Table 9 below.

[0254] [Table 9]

[0255]

[0256] The results for calcined clay show that the use of the polymer (P) enables a higher particle content of 2-32 μm than when using conventional grinding aids, which demonstrates the usefulness of this polymer as a grinding aid for diffusion mineral materials such as calcined clay.

[0257] In addition, the results for limestone also show that the polymer (P) is useful as a grinding aid for pulverizable mineral materials. That is, compared to limestone ground without a grinding aid, the particle content of 2-32 μm increased significantly in the presence of the polymer G.

Claims

Claim 1 A grinding process comprising the step of grinding a mineral composition to be ground in the presence of an admixture composition comprising at least one polymer (P), wherein the polymer (P) comprises n repeating units (A) of the following chemical formula, and In the above formula,- "M" is independently H + , or represents a cation of valence (v) selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, and - Where "M" represents H, "v" represents 1; where "M" represents a cation selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, "v" represents the valence of said cation M, and - "R2" and "R3" are each independently hydrogen, methyl, or -COO(M) having the M and v defined above 1 / v Representing a group of the chemical formula, preferably representing hydrogen or methyl, - "R4" and "R5" are each independently hydrogen, methyl, or -COO(M) having the M and v defined above 1 / v Representing the group of the chemical formula, - "m" represents 0, 1, or 2, and- "p" represents 0 or 1, and - "X" is O or N, and - "R1" is -[alkyl-O] z -R6 represents, wherein "alkyl" of each [alkyl-O] unit independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, "R6" represents H, a C1 to C20 alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is 40 or more, and the number of units (I) and units (II) in the polymer (P) is defined by a repeating unit (A) comprising one unit (II) and "a" units (I), and- "a" is a non-zero positive number, and - "n" is 1.5 to 50, and - A grinding process in which the molecular weight of the repeating unit (A) is 6500 g / mol or less, and the mineral composition to be ground comprises 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker, based on the total weight of the mineral composition to be ground. Claim 2 A grinding process according to claim 1, wherein the molecular weight of the repeating unit (A) of the polymer (P) is 1500 to 6500 g / mol, preferably 2000 to 6500 g / mol, preferably 2500 to 6500 g / mol, preferably 4500 to 6000 g / mol, and more preferably 5200 to 5600 g / mol. Claim 3 A grinding process according to claim 1 or 2, wherein the polymer (P) has “z” of 50 or more, preferably 70 or more, preferably 80 or more, preferably 85 or more, preferably 90 or more, and preferably 100 or more. Claim 4 A grinding process according to any one of claims 1 to 3, wherein the polymer (P) has “a” of 0.2 to 100, preferably 0.5 to 50, preferably 1.0 to 20, preferably 3.0 to 10, preferably 3.9 to 7, and preferably 4.0 to 6. Claim 5 A grinding process according to any one of claims 1 to 4, wherein the polymer (P) has a grafting ratio exceeding 5%, preferably 6% or more, preferably 10% or more, and preferably 12% or more. Claim 6 In any one of claims 1 to 5, the mineral composition to be ground comprises at least one mineral material to be ground other than clinker, optionally comprises clinker in an amount of 0.01 wt% to 80 wt% based on the total dry weight of the mineral composition to be ground, wherein the mineral material other than clinker is selected from calcium sulfate, mineral additives, crystallized blast furnace slag, expanded blast furnace slag, glassy blast furnace slag, converter steel slags, carbon steelmaking slags from the electric route, ladle slag, crushed shale, quartz, alumina cement, sulfoalumina clinker, ye'elimite, belitic clinkers, recycled glass, zeolite, diatomaceous earth, recycled concrete fines resulting from demolition, and any mixture thereof, and preferably the clinker Other mineral materials are selected from calcium sulfate, calcined clay, limestone, natural or artificial pozzolan, fly ash, calcined shale, crushed shale, diatomite, and any mixture thereof, through a crushing process. Claim 7 In any one of claims 1 to 6, the mineral composition to be ground comprises at least one mineral material to be ground other than clinker, optionally comprises clinker in an amount of 0.01 wt% to 80 wt% based on the total dry weight of the mineral composition to be ground, and the mineral material other than clinker is 1500 to 2500 cm 2 A grinding process selected from a friable mineral material, wherein the grinding time required to obtain a Blaine fineness of 1 / g is at least twice as short as the grinding time required for a clinker that meets the requirements of standard NF EN 197-1 to obtain the same Blaine fineness. Claim 8 A grinding process according to any one of claims 1 to 7, wherein the content of the polymer (P) introduced is 0.01% to 1% by weight based on the total dry weight of the mineral composition to be ground, and preferably 0.05% to 0.5% by weight. Claim 9 A grinding process according to any one of claims 1 to 8, wherein the grinding process is a co-grinding process of at least one first mineral material to be ground and at least one second mineral material to be ground, and further comprises a step of preparing the mineral composition to be ground, wherein the preparation step comprises a step of mixing the at least one first mineral material to be ground and the at least one second mineral material to be ground in order to obtain the mineral composition to be ground. Claim 10 A mixed ground mineral composition comprising: a mineral composition comprising 0% to 80% by weight of clinker and 20% to 100% by weight of mineral materials other than clinker, based on the total dry weight of the mineral composition; and a polymer (P) defined in any one of claims 1 to 5. Claim 11 In claim 10, the mixed pulverized mineral composition has a central particle size (d) of 20 μm or less, preferably 15 μm or less, preferably 10 μm or less. 50 A mixed pulverized mineral composition having a fineness characterized by ). Claim 12 A mixed ground mineral composition according to claim 10 or 11, wherein the content of the polymer (P) is 0.01% to 1% by weight based on the total dry weight of the mineral composition, preferably 0.05% to 0.5% by weight. Claim 13 A mixed ground mineral composition according to any one of claims 10 to 12, wherein the content of the clinker is 0.01 wt% to 80 wt% based on the total dry weight of the mineral composition, preferably 1 wt% to 60 wt%, preferably 5 wt% to 55 wt%, preferably 5 wt% to 50 wt%, and preferably 10 wt% to 40 wt%. Claim 14 A mixed crushed mineral composition according to any one of claims 10 to 13, wherein the mixed crushed mineral composition is obtained by a crushing process according to any one of claims 1 to 9. Claim 15 As a hydraulic composition, - A mixed pulverized mineral composition according to any one of claims 10 to 14,- water,- Optionally aggregate, and- A hydraulic composition optionally comprising a mineral additive. Claim 16 A use for improving the grindability of a mineral composition to be ground, of a polymer (P) defined according to any one of claims 1 to 5, wherein the mineral composition to be ground comprises 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker based on the total weight of the mineral composition to be ground, and preferably, for increasing the proportion of a fraction of 2 to 32 μm in the particle size distribution of a ground mineral composition comprising 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker based on the total weight of the mineral composition.

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