Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B7/00—Hydraulic cements
  • C04B7/36—Manufacture of hydraulic cements in general
  • C04B7/48—Clinker treatment
  • C04B7/52—Grinding ; After-treatment of ground cement
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/122—Hydroxy amines
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/50—Defoamers, air detrainers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/52—Grinding aids; Additives added during grinding

Definitions

• the present invention relates to the stabilization of alkanolamines used in the grinding processes, in particular in the grinding processes of hydraulic binder, in particular clinker.
• alkanolamines when grinding the clinker. Alkanolamines are also known to improve the mechanical strengths of cement-based hydraulic compositions.
• alkanolamines in particular triisopropanolamine (TIPA), used during grinding, will be degraded by temperature and will therefore no longer be available to participate in obtaining good mechanical strengths during the preparation of the hydraulic binder compositions.
• TIPA triisopropanolamine
• the increase in the alkanolamine concentration in certain mills results in too high a grinding efficiency and the overfluidification of the cement powder leads to an emptying of the mill, which is not desired.
• An object of the present invention is therefore to provide a process for stabilizing the alkanolamines used in a mill.
• Another objective of the invention is to provide such a method making it possible, at the same time, to retain an impact on the improvement of the mechanical strengths, in particular at 28 days, of the hydraulic binder compositions.
• Yet another objective of the present invention is to provide a means making it possible to control the performances of grinding agent of the alkanolamines while retaining the properties for improving the mechanical strengths, in particular at 28 days during the preparation of the hydraulic binder compositions .
• the object of the present invention is particularly advantageous in all situations where the required grinding performance is low (nature of the clinker, co-grinding of the clinker with soft materials - for example limestone filler, natural pozzolans -, inefficient mills, open mills without separation system, closed grinding systems with, for example, constant air flow separators, process with cement transfer by inclined conveyor belt, open bucket elevators, dust filters not very efficient or close to saturation (high differential pressure , worn bag filters)).
• the object of the present invention is particularly advantageous during the co-grinding of clinker and limestone for the manufacture of OEM ll / A or OEM ll / B LL, which require for the improvement of the mechanical strengths at 28 days high dosages of amine (for example 120 g of triisopropanolamine (TIPA) per ton of cement).
• TIPA triisopropanolamine
• the salt form preferably an inorganic acid salt, of the alkanolamine
• the method further preferably includes grinding said hydraulic binder.
• the present invention relates to a process for using secondary or tertiary alkanolamine for the grinding of at least one hydraulic binder comprising:
• the method further preferably includes grinding said hydraulic binder.
• the alkanolamine is an alkanolamine of formula (I) N (R 1 OH) (R 2 ) (R 3 ) (I) in which the R 1 , identical or different, represent a linear or branched alkyl group comprising 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, R 2 represents H or a group R 1 -OH, R 3 represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms, of preferably from 1 to 5 carbon atoms, a group R 4 -OH in which R 4 represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, or an (alkyl) group ) -N (alkyl-OH) 2 , the alkyl being linear or branched and comprising from 1 to 5 carbon atoms, preferably (OH2-OH2) -N (OH2-OH 2 -OH) 2, at least the one of
• the alkanolamine is an alkanolamine of formula (I) N (R 1 OH) (R 1 OH) (R 3 ) (I) in which the R 1 , identical or different, represent a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, R 3 represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, a group R 4 -OH in which R 4 represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms.
• the process of the present invention does not cover the use of salts of acetic acid.
• the process of the present invention does not cover the use of AMP (2-amino-2-methyl-propanol).
• the present invention also relates to a process for improving the mechanical strengths of a hydraulic binder composition
• a process for improving the mechanical strengths of a hydraulic binder composition comprising the use of an alkanolamine salt, preferably an inorganic alkanolamine salt, preferably of alkanolamine of formula ( I), during the grinding of the hydraulic binder.
• the method allows the mechanical strengths of the hydraulic binder composition to be improved without affecting the performance of the grinding of hydraulic binder, in particular clinker.
• the mechanical resistances when reference is made to the mechanical resistances, it is preferably the mechanical resistances at 28 days.
• the inorganic alkanolamine salts of formula (I) are chosen from acid halide salts, sulfuric acid salts, phosphoric acid, phosphonic acid, or hydrogen sulfates.
• the alkanolamine salt is a salt of sulfuric acid, phosphoric acid or phosphonic acid, preferably sulfuric acid.
• the alkanolamine salt is an acid halide salt.
• a hydrochloric acid salt is particularly preferred.
• the process of the present invention can be applied to any type of alkanolamine, preferably secondary or tertiary, preferably of formula (I), in particular to any type of secondary or tertiary alkanolamine of formula (I) used in grinders, especially in clinker and hydraulic binder crushers. More particularly, triisopropanolamine (TIPA), diisopropanolamine (DIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine (THEED) may be mentioned and methyldiethanolamine (MDEA).
• TIPA triisopropanolamine
• DIPA diisopropanolamine
• DEIPA diethanolisopropanolamine
• EDIPA ethanoldiisopropanolamine
• the alkanolamine is chosen from triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA) and ethanoldiisopropanolamine (EDIPA).
• TIPA triisopropanolamine
• DEIPA diethanolisopropanolamine
• EDIPA ethanoldiisopropanolamine
• TIPA triisopropanolamine
• the preparation of the alkanolamine salt is preferably carried out by stoichiometric mixing between the alkanolamine and the acid.
• the reaction can be exothermic it may be necessary to cool the medium during the reaction.
• the synthesis of the alkanolamine salt is preferably carried out in a glass container immersed in a cold water bath and the temperature as well as the pH are measured continuously.
• the present invention also relates to a method of reducing the fluidity of the hydraulic binder in a mill comprising the use of an inorganic salt of a secondary or tertiary alkanolamine, preferably of formula (I), during the grinding of the hydraulic binder .
• any type of grinder can be used.
• the invention relates to the implementation in vertical mills, ball mills, cylinder mills, open without separation system, closed grinding systems with separators with constant or non-constant air flow, process with transfer of cement by inclined conveyor belt, open bucket elevators, dust filters which are ineffective or close to saturation (high differential pressure, worn bag filters).
• the mill is a ball mill, or a vertical mill.
• the object of the present invention is particularly advantageous during co-grinding of clinker and mineral additions for the manufacture of OEM ll / A or OEM ll / B or OEM III, which require for the improvement of mechanical strengths to 28 days , high dosages of amine (for example 120 g of TIPA per ton of cement). When such dosages are used in certain factories, rapid emptying of the mill is observed, critical dust phenomena at the outlet of the mill and at the elevator.
• the present invention deals with the grinding of any type of hydraulic binder and in particular of clinker and / or mineral additions.
• hydraulic binder is understood to mean any compound having the property of hydrating in the presence of water and the hydration of which makes it possible to obtain a solid having mechanical characteristics, in particular a cement such as Portland cement, aluminous cement, pozzolanic cement or even anhydrous or semi-hydrated calcium sulphate.
• the hydraulic binder can be a cement according to standard EN197-1 (2001) and in particular a Portland cement, mineral additions, in particular dairy additives, or a cement comprising mineral additions.
• cement means a cement according to standard EN 197-1 (2001) and in particular a cement of type OEM I, OEM II, OEM III, OEM IV or OEM V according to standard Cement NF EN 197-1 (2012) . Cement may include mineral additions.
• the inventors have shown that the salt form of the alkanolamine according to the invention makes it possible to reduce its vapor pressure and therefore to protect it from degradation, in particular due to the temperature, in the mill. .
• the inventors have shown that, against all expectations, despite this salt form, the alkanolamine retains its properties for improving the mechanical properties of a hydraulic binder composition, in particular its properties for improving the mechanical strengths, especially the strengths mechanical at 28 days.
• the inventors have shown that the placing in the form of inorganic acid salts, unlike the known examples of the literature with organic acid salts, allows better grinding and results in a decrease in the fluidity hydraulic binder.
• the present invention makes it particularly advantageous to add the alkanolamine at the time of grinding without it degrading and while improving the grinding and retaining its properties for improving the mechanical properties of the hydraulic binder compositions.
• the alkanolamine salt is used during grinding in a content of 0.003 to 0.025% by weight of the hydraulic binder, preferably from 0.005 to 0.015%.
• the alkanolamine salt used during grinding can be used in combination with other additives generally used in hydraulic compositions or during grinding of the hydraulic binder, mention may in particular be made of alkanolamines other than those of formula (I), the salts such as sodium chloride, calcium chloride, sodium thiocyanate, calcium thiocyanate, sodium nitrate and calcium nitrate and their mixtures, glycols, glycerols, adjuvants water reducers and high water reducers, surfactants, carboxylic acids such as acetic, adipic, gluconic, formic, oxalic, citric, maleic, lactic, tartaric, malonic acids and mixtures thereof.
• the alkanolamine salt can also be used in combination with setting retarders.
• setting retarders based on sugar, molasses or vinasse.
• the water reducing and high water reducing additives are chosen from:
• melamine-based superplasticizers The sulfonated salts of polycondensed melamine and formaldehyde, commonly called melamine-based superplasticizers;
• polycarboxylic acids in particular polycarboxylate comb copolymers, which are branched polymers in which the main chain carries carboxylic groups and in which the side chains are composed of polyether type blocks, in particular polyethylene oxide, such as for example poly [(meth) acrylic acid - grafted - polyethylene oxide].
• polyether type blocks in particular polyethylene oxide, such as for example poly [(meth) acrylic acid - grafted - polyethylene oxide].
• the superplasticizers of the CHRYSO ® Fluid Optima, CHRYSO ® Fluid Premia and CHRYSO ® Plast Omega ranges sold by CHRYSO can in particular be used;
• the alkanolamine salt used during grinding can be used in combination with one or more defoamers, in particular chosen from ethoxylated fatty amines.
• the inventors have in particular shown that the salt form of the alkanolamine makes it possible to obtain a pH zone allowing the solubilization of ethoxylated fatty amines while retaining their effectiveness in applications in particular concrete which are in pH zones where they become active.
• the present invention also relates to a composition
• a composition comprising:
• composition can also comprise at least one additive as described above.
• the present invention also relates to a hydraulic composition
• a hydraulic composition comprising:
• the hydraulic composition can also comprise at least one additive as described above.
• aggregates is meant a set of mineral grains with an average diameter of between 0 and 125 mm. According to their diameter, the aggregates are classified into one of the following six families: fillers, sand, sand, gravel, gravel and ballast (standard XP P 18-545). The most used aggregates are:
• the fillers can in particular be of limestone or dolomitic origin.
• the hydraulic composition can also comprise other additives known to a person skilled in the art, for example a mineral addition and / or additives, for example an anti-air entraining additive, an anti-foaming agent, a setting accelerator or retarder. , a rheology modifying agent, another fluidifier (plasticizer or superplasticizer), in particular a superplasticizer, for example a superplasticizer CHRYSO®Fluid Premia 180 or CHRYSO®Fluid Premia 196.
• additives known to a person skilled in the art, for example a mineral addition and / or additives, for example an anti-air entraining additive, an anti-foaming agent, a setting accelerator or retarder.
• a rheology modifying agent such as a rheology modifying agent, another fluidifier (plasticizer or superplasticizer), in particular a superplasticizer, for example a superplasticizer CHRYSO®Fluid Premia 180 or CHRYSO®Fluid Premia 196.
• Figure 1 is a top view of the inclined plane for the rolling bottle test of Example 2.
• Figure 2 is a side view of the inclined plane for the rolling bottle test in Example 2.
• a hydrochloric acid salt of triisopropanolamine is used.
• This salt is obtained according to the following process: a mass of 1 13 g of triisopropanolamine (TIPA) at a mass concentration of 63% in water was kept stirring with a magnetic stirrer and 35 g of hydrochloric acid at 37% mass were added in 30 minutes to obtain approximately 150 g of solution.
• the stoichiometric ratio between TIPA and HCl is 1: 1. During the formulation, the temperature did not exceed 40 ° C. The solution obtained is clear.
• DEIPA + HCI protonated amine can be confirmed by reverse acid-base titration.
• the compound DEIPA + HCI clearly exhibits a jump in pH characteristic of the acid-base compound DEIPA / DEIPA + HCI when adding sodium hydroxide, which indicates a pKa close to 8.
• TIPA and DEIPA are amines with very similar acid constants, with a pKa around 8.
• unprotonated DEIPA does not show a jump in pH when adding sodium hydroxide.
• TIPA triisopropanolamine sulfuric acid
• a dosage of 90 ppm of TIPA makes it possible to increase the throughput of the cement crusher 1 1%.
• a dosage of 120 ppm of TIPA creates harmful effects by overfluidifying the cement powder which becomes very volatile.
• TIPA + HCI does not give a negative impact on the grinding of the cement (no overfluidification) and leads to improved mechanical strengths.
• the table below shows that the clinker ground in the presence of TIPA does not promote the fluidity of the clinker powder. This effect is explained by a particle size distribution which negatively impacts the flow of clinker powder contained in the bottle, which indicates an over-efficiency of TIPA which is not favorable for grinding.
• the distance traveled by the bottle is greater, showing that TIPA + HCI avoids the effect of overfluidification known for TIPA and reduces the clinker sample to a behavior favorable to the flow of powder on an industrial scale.
• the Blaine specific surface target at the outlet of the mill is 5100 cm 2 / g.
• a dosage of 150 g / t of grinding agent (composition 1) which provides 41 g / t of TIPA generates harmful effects by overfluidifying the cement powder which becomes very volatile.
• the ball mill must be stopped because the dust filters are saturated. This saturation is followed by the measurement of the pressure at the inlet of the filter - mill outlet, which increases significantly with composition 1 comprising TIPA.
• composition 2 Used at a dosage close to TIPA of 36 g / t in the milling agent (composition 2), TIPA + HCI has no negative impact on the grinding of the cement (no overfluidification).
• the protonated amine maintains a rejection of the separator and a dust rate of the filter equivalent to the reference.
• the dosage of composition 2 containing this amine salt from 36 to 84 g / t TIPA
• the Blaine surface of the slag increases thanks to the effect of the milling agent.
• the fine particles do not saturate the filter, maintaining a separator rejection and a dusting rate of the filters equivalent to that of the reference.
• the TIPA salt makes it possible to promote the grinding of the slag, while maintaining the particles in an agglomerated state and therefore without the risk of dusting and overfluidification.
• TIPA salt form overcomes these drawbacks.
• the inlet flow rate of the mill can be kept constant while promoting the grinding of the slag and without the risk of overfluidification.
• a CEM ll / A LL 42.5 N cement containing 10% by mass of limestone is ground with a double-chamber ball mill (so-called open circuit configuration without coupling to a separator) to obtain a Blaine specific surface target of 3300 cm 2 / g.
• the use of an adjuvant containing TIPA. HCl (composition 4) makes it possible to reduce even more than with an adjuvant containing TIPA (composition 3) the rejection 45 and 25 ⁇ m at the outlet of the ball mill compared to the reference.
• the salt form of TIPA therefore makes it possible to more effectively reduce the particle sizes of the cement and thus to have a gain in resistance to compression compared to the control higher at 2 days.
• replacing TIPA with a TIPA salt maintains a marked long-term activating effect, with resistance to compression at 28 days significantly higher than that of the reference.
• CEM I In a double-chamber ball mill combined with 2 first generation separators installed in parallel, 108 tonnes per hour of type cement are introduced CEM I in the presence of an activator comprising TIPA (composition 5) to obtain a Blaine specific surface of approximately 360 m 2 / kg.
• CEM I 42.5 N cement is composed of 90.5% m clinker, 4.5% m limestone and 5.0% m gypsum.
• the use of an activator containing TIPA + HCI (composition 6) in place of TIPA (composition 5) with iso-dosage in amine makes it possible to improve the grinding efficiency.
• the specific surface of the cement is higher and the rejection 45 ⁇ m lower in the presence of chlorinated salt of TIPA than of TIPA.
• the additive based on TIPA + HCI remains a very effective milling agent since it maintains a high Blaine surface.
• the TIPA acetate used in a grinding agent (composition 6) makes it possible to obtain a specific surface of the ground cement equivalent to that of the TIPA.
• TIPA acetate leads to fouling of the grinder filter detectable by increasing the filter cleaning time and the number of purges per hour.
• TIPA + HCI makes it possible to form less dust during grinding and therefore to reduce the purging time of the filters.
• the compressive strengths are higher in the presence of TIPA + HCI because the cement is ground more finely than in the presence of TIPA or TIPA acetate.
• the compressive strengths at 28 days are equivalent for all adjuvants.
• TIPA SUBSTITUTE SHEET (RULE 26) TIPA, by limiting the clogging of the filters and therefore the time spent cleaning them.
• TIPA + HCI instead of TIPA allows a slight gain in resistance to compression at 2 days and a maintenance of resistance to compression at 28 days.
• Triisopropanolamine is known to entrain air in mortars and concretes, which can lead to a decrease in compressive strengths.
• Diethanolisopropanolamine (DEIPA) has an effect similar to TIPA on air entrainment.
• the adjuvants containing the protonated amines TIPA + HCI or even DEIPA + HCI promote the entrainment of air in cements. It is therefore interesting to combine TIPA + HCI and DEIPA + HCI with anti-foaming agents.
• defoamers are by their very nature chemical species poorly soluble in water, which makes their use complicated in the formulation of grinding agents or activators. They tend not to dissolve in solutions predominantly consisting of water.
• Formulations have been made by combining TIPA + HCI and DEIPA + HCI with an ethoxylated fatty amine defoamer (ADMA® 10 AMINE and ADMA® 12 AMINE from ALBEMARLE) at different dosages.
• the formulas obtained are stable, the ethoxylated fatty amine dissolving in the protonated amine solutions according to the invention having a pH of less than 7.5.
• composition 9 makes it possible to have a direct impact on the efficiency of grinding by generating a cement with improved fineness (drop in parameters d50 and d90) without impact on process parameters.
• the salt form of TIPA therefore makes it possible to more effectively reduce the particle sizes of the cement.
• This grinding efficiency can also translate into productivity gains for the crusher (tonnes per hour) while adjusting the process parameters and keeping the crusher vertical in an optimized operating zone to guarantee the targeted fineness of the cement.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Disintegrating Or Milling (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Steroid Compounds (AREA)

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