USOO9624 129B2
(12) United States Patent (10) Patent No.: US 9,624,129 B2 Hoang et al. (45) Date of Patent: *Apr. 18, 2017
(54) INERTING PROCESS FOR IMPURITIES (56) References Cited (75) Inventors: Lé-Chien Hoang, Ruy-Montceau (FR); U.S. PATENT DOCUMENTS Serge Ghilardi, Mery (FR) 5,366,550 A * 11/1994 Schad ...... C04B 28.02 106,691
(73) Assignee: LAFARGE, Paris (FR) 5,731,259 A * 3/1998 Palumbo et al. 502.404 8,257.490 B2 * 9/2012 Alain et al...... 106,802 (*) Notice: Subject to any disclaimer, the term of this 8.425,680 B2 * 4/2013 Jacquet et al...... 106,802 patent is extended or adjusted under 35 8,466.224 B2 * 6/2013 Georges et al. ... 524,445 8,834,626 B2 * 9/2014 Jacquet et al...... 106,802 U.S.C. 154(b) by 1129 days. 2013.0035417 A1* 2, 2013 Villard et al. .. 523,401 This patent is Subject to a terminal dis claimer. FOREIGN PATENT DOCUMENTS Appl. No.: 13/501.774 EP O 471597 B1 2, 1992 (21) EP 2 090 620 A1 8, 2008 FR 2875 496 A1 3, 2006 (22) PCT Fed: Oct. 12, 2010 GB 508 929. A 7, 1939 JP 2006-045010 2, 2006 (86) PCT No.: PCT/FR2O10/0521.60 WO WO 2006/032785 3, 2006 WO WO 2006/032786 A2 3, 2006 S 371 (c)(1), WO WO 2009/052362 A2 4/2009 (2), (4) Date: May 21, 2012 WO WO 2010.005117 1, 2010 WO WO 2010/040915 A2 4/2010 (87) PCT Pub. No.: WO2O11AO4S528 PCT Pub. Date: Apr. 21, 2011 OTHER PUBLICATIONS (65) Prior Publication Data “What do we Mean by Building Technology?” Habitat International vol. 15, No. 1/2 pp. 3-26 (1991), Ranko Bon.* US 2012/0216723 A1 Aug. 30, 2012 International Search Report for PCT/FR2010/052160. (30) Foreign Application Priority Data * cited by examiner Oct. 14, 2009 (FR) ...... O9 O4923 Primary Examiner — Paul Marcantoni (74) Attorney, Agent, or Firm — Pillsbury Winthrop Shaw (51) Int. C. C04B I6/04 (2006.01) Pittman LLP C04B I6/08 (2006.01) (57) ABSTRACT C04B 20/02 (2006.01) C04B 24/26 (2006.01) An inerting process for impurities in aggregates intended for C04B 24/38 (2006.01) preparation of hydraulic or hydrocarbon compositions, C04B 28/02 (2006.01) includes adding to the composition or to one of its constitu (52) U.S. C. ents a cationic polymer corresponding to at least one deriva CPC ...... C04B 20/023 (2013.01); C04B 24/2652 tive of a natural polymer or a polymer of natural origin (2013.01); C04B 24/38 (2013.01); C04B 28/02 selected from the group including dextrin (in particular (2013.01) yellow dextrin and white dextrin), chitosan, chitin, alginates, (58) Field of Classification Search hemicellulose, pectin, polyols or proteins. CPC ...... C04B 16/04: CO4B 16/08 See application file for complete search history. 22 Claims, No Drawings US 9,624,129 B2 1. 2 INERTING PROCESS FOR IMPURITIES one of its constituents a cationic polymer corresponding to at least one derivative of a natural polymer or a polymer of CROSS REFERENCE TO RELATED natural origin selected from the group comprising dextrin (in APPLICATIONS particular, yellow dextrin and white dextrin), chitosan, chi tin, alginates, hemicellulose, pectin, polyols or proteins. This application is the U.S. National Stage of PCT/ Advantageously, at least certain cationic polymers FR2010/052160, filed Oct. 12, 2010, which in turn claims according to the invention may be obtained from products priority to French Patent Application No. 09/04923, filed widely available in nature. Oct. 14, 2009, the entire contents of all applications are The invention offers another advantage in that the cationic incorporated herein by reference in their entireties. 10 polymer, according to the invention, is soluble in water, The present invention relates to an inerting process for which facilitates its use. harmful impurities such as clays of aggregates in cement The invention offers another advantage in that the inerting hydraulic compositions or bituminous hydrocarbon compo efficiency of the cationic polymer, according to the inven sitions. tion, is not very sensitive to the nature of the clay. It is sometimes difficult to control in a constant manner 15 Another advantage of the present invention is that the the rheological properties of cement hydraulic compositions cationic polymer according to the invention does not induce or adhesion properties between a hydrocarbon binder and an increase of the viscosity of the hydraulic or hydrocarbon the aggregates of hydrocarbon compositions. The quality of composition. the raw materials is often responsible for these variations. In Another advantage of the present invention is that the particular, it has been found that sands or more particularly dosage of the cationic polymer according to the invention in the impurities contained in Sands, for example clays, can the hydraulic or hydrocarbon composition is reduced. generate fluctuations of the rheological properties of hydrau Finally, the invention has the advantage of being able to lic compositions or the adhesion properties between a hydro be used in the construction industry, the chemical industry carbon binder and the aggregates of hydrocarbon composi (admixture Suppliers), the cement industry, in construction tions. 25 markets (buildings, civil engineering, roads or pre-cast For hydraulic compositions, these fluctuations may be due plants) or in concrete mixing plants. to a decrease of the efficiency of superplasticizers of the Other advantages and characteristics of the invention will anionic polymer type having a comb structure, for example clearly appear after reading the following description and the polyoxyalkylene polycarboxylate (PCP). examples provided purely for illustrative and non-limiting During the production of aggregates, in particular sands, 30 purposes. a known means of eliminating clays and other impurities of In the present description, the term (3) 35 (A) R1 -- -(CH2) -car-ti-ji, Z o NaOH R3 OH X (4) 40 R1 -- -(CH3).--N-(CHR)-CH-CH, Z The first step is preferably carried out in a basic medium. R3 O Advantageously, it is carried out at ambient temperature in 45 a neutral atmosphere. Depending on the type of the amine compound, the wherein p is an integer from 2 to 10 and n, R. R. R. R. process of production of the cationic polymer may comprise X and Z are as previously defined. a second step corresponding to activation of the amine Preferably, R, R, R and Rare each hydrogen. When one compound by formation of an epoxide according to the of these groups is an organic radical, R, R, R and Rare 50 following reaction (B): each advantageously an alkyl, hydroxyalkyl, alkenyl or aryl group. Sizeable organic groups increase the molecular weight of the product, therefore Smaller groups are pre (B) ferred. Preferably, R. R. Rand Rare each hydrogen oran alkyl, hydroxyalkyl, alkenyl or aryl group comprising up to 55 NaOH -- 10 carbon atoms. Advantageously, the organic group is methyl or hydroxymethyl. arr- -- According to an example of an embodiment, the quater nary amine compound is selected from the group compris v- + NaCl 1ng: 60 2,3-epoxypropyl-N,N.N-trimethylammonium chloride O c. (commercialised by Degussa A.G. in the form of an aqueous solution at 70% under the name QUAB 151 or Advantageously, the second step is carried out at ambient commercialised by Fluka in the form of a solid com temperature in a neutral atmosphere. pound under the product code 50045); 65 The process of production of the cationic polymer may 3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium comprise a third step corresponding to the following etheri chloride (commercialised by Degussa A.G. in the form fication reaction (C): US 9,624,129 B2 10 According to an example of an embodiment of a grafting (C) operation by esterification, the process of production of a cationic polysaccharide comprises an esterification reaction according to the following reaction (D): (D) OH w O 10 o O -- --- 1 -- HO Y N C OH O ROHC 15 o O RO wherein OR - The third step may be carried out by adding in several O additions, at ambient temperature and in a neutral atmo wherein Y = OH, O, or ClandR = Hor -uk sphere, the epoxide compound obtained in step (B) to the n activated polysaccharide obtained in step (A). The tempera Cl ture may then be increased to promote the reaction (C). The third step may be followed by a fourth step of Reaction (D) may be catalyzed by a chemical or enzy neutralisation which comprises the addition of a (mineral or matic catalyst. organic) acid to the mixture from reaction (C). Preferably, 25 According to another example of a process of production the acid is acetic acid. of the cationic polymer, when the natural polymer or poly The fourth step may be followed by a fifth step of mer of natural origin initially comprises amine groups, a purification which may comprise precipitation of the cat quaternisation reaction may be carried out directly of all the ionic polymer in an alcohol medium, ultra filtration, dialysis amine groups of the natural polymer or polymer of natural or electro dialysis of the neutralised solution. 30 origin. When the natural polymer or polymer of natural According to an example of an embodiment of the inven origin is a polysaccharide, this type of reaction may in tion, in the case where the grafting operation of the quater particular be used when the polysaccharide is chitosan. nary amine groups on the natural polymer or polymer of According to an example of an embodiment of a grafting natural origin comprises esterification reactions, the quater operation of a polysaccharide by quaternisation, the process nary amine groups may be derived from a quaternary amine 35 of production of the cationic polysaccharide comprises a compound according to formula (5): quaternisation reaction according to the following reaction (E): (5) 40 RI -- (E) HO Y--Ichi-- Z O R3 O MeI, NaI He 45 HO On NaOH, NMP wherein Y is a halogen, in particular fluorine, chlorine, NH2 bromine or iodine, preferably chlorine, OH, or O: HO n, Z. R. R. Rare as previously defined, R* may be hydrogen, an organic radical or a group O according to formula (6): 50 HO On e Nt (6) RI -- 55 This reaction may be carried out by putting polyglu -(CH2) cosamine (or a protein) in the presence of methyl iodide (Mel), sodium iodide (NaI) and sodium hydroxide in a R3 O solution of N-methylpyrrolidone (NMP). According to another example of the process of produc wherein p, R, R', R. R. Y and Z are as previously 60 tion of the cationic polymer, re-dox reactions and amination defined. reduction reactions are carried out on the natural polymer or According to an example of an embodiment, the quater polymer of natural origin. According to an example of an nary amine compound is selected from the group compris embodiment of an operation of transformation of a polysac 1ng: charide by re-dox reactions and amination-reduction reac betaine (trimethylglycine); 65 tions, the process of production of the cationic polysaccha betainyl chloride; or ride comprises an initial re-dox reaction corresponding to betaine chloride. the following reaction (F): US 9,624,129 B2 11 12 It does not disturb the mechanical strengths of the hydrau (F) lic composition in the short term or in the long term; It does not have a setting-retarding effect; OH It is stable over time and is resistant to heat and freezing; HO It involves the introduction of a reduced quantity of a O halogen, for example chlorine, in the hydraulic com O Her O position. HO O CH| HC The cationic polymer according to the invention is par OH pi O ticularly useful to neutralise the harmful effects of impurities O 10 contained in hydrocarbon compositions. It furthermore has at least one of the following advantages: It makes it possible to obtain a hydrocarbon composition The process of production of the cationic polymer may having improved behaviour in water, that is to say that comprise a second step corresponding to the following hydrocarbon binder/aggregates adhesion of a hydrocar amination-reduction reaction (G): 15 bon composition according to the invention after immersion in water or exposure to humidity is better than the one of a hydrocarbon composition not com (G) prising the cationic polymer according to the invention; It makes it possible to upgrade non-conforming aggre OH OH gates relative to the Standards pertaining to aggregates for hydrocarbon compositions (in particular see the XP O O P 18545 Standard chapters 7 and 8, and the NF EN O He- O 13043 Standard) and that it is consequently not possible i" y to use. The process according to the invention makes it O " NH2 possible for example to use aggregates having a high methylene blue value, which is to say greater than 2 g, O pi NH2 pi 2.5 g or 3 g of methylene blue per kilogramme of aggregates depending on the target application; The process of production of the cationic polymer may It has no negative influence on the usage properties of comprise a third step corresponding to the following quater 30 hydrocarbon compositions; nisation reaction (H): It avoids over-consumption of water compared to the washing operation of aggregates typically used. The cationic polymers may be used according to the (H) envisaged application, in the Solid form (granule, beads), 35 liquid or emulsion forms. OH OH The described process is useful for impurities, in particu lar clays present in certain constituents of the given com O O positions. These impurities may affect the properties of the O O -- compositions. 40 The treatment of materials containing clays is particularly +N(CH3)3 easy and rapid. The cationic polymer according to the invention has considerable affinity with the clays. Therefore, pi it suffices to put the cationic polymer in contact with the material to inert the clays contained in the materials. A few In the case where the cationic polymer according to the 45 seconds of contact is generally sufficient. invention is associated with a halide ion, in particular the Advantageously, the cationic polymer is contacted with chloride ion, the examples of the process of production of the material by spraying an aqueous solution of the cationic the cationic polymer previously described may comprise an polymer. additional step of exchange of anions which consists of In the case of a particulate material, the material is mixed exchanging at least part of the chloride ions by less corrosive 50 during or after treatment of the material with the cationic ions. By way of exchange, the cationic polymer according to polymer in order to ensure good distribution of the cationic the invention may, after ion-exchange treatment, be associ polymer and obtain a homogenously treated material. ated with at least 0.1% of halide ions. Clays are a frequent source of impurities in sands. There Advantageously, the hydraulic composition for which the fore, according to an embodiment of the invention, the sand 55 is treated with the cationic polymer. cationic polymer is used is a concrete or a mortar. Preferably, the sand is contacted with the cationic polymer The cationic polymer according to the invention is par by spraying the product in aqueous solution on the sand. ticularly useful to neutralise the harmful effects of impurities Preferably the sand is treated dry. Therefore the sand contained in hydraulic compositions, in particular clays preferably has a humidity value less than 10% by weight. found in certain sands. It furthermore presents at least one of 60 The treatment of the sand is preferably carried out at the the following advantages: quarry. It makes it possible to reduce the quantity of water or In order to ensure good distribution of the cationic poly fluidizer (plasticizer or Super plasticizer) required to mer and obtain a homogenously treated sand, the sand is obtain a given fluidity; preferably mixed. It is efficient for different clays: 65 The spraying may be carried out in a container, for It does not disturb the characteristics of the mortar in example in a baffle box at the output of a conveyor belt. This cases of over dosage; embodiment furthermore ensures little loss of the product. US 9,624,129 B2 13 14 As a variant, it may be envisaged spraying a solution of the Finally, the process does not require installation of par cationic polymer in a mixer placed at the output of the ticular equipment. conveyor belt. It may also be envisaged to prepare a pre-mix The result is that the described process may be efficient of a small quantity of sand with the product, then adding this for a broad range of conditions, for different types of pre-mix to the sand. hydraulic compositions and clays. The cationic polymer is preferably applied on the sand in The invention will be described in more detail in the a suitable quantity to ensure that the clays present in the sand following examples provided for non-limiting purposes. are completely inerted and to avoid an over dosage of Superplasticizer. EXAMPLES Nevertheless, partial treatment may be envisaged and the 10 application of a greater quantity does not deteriorate the The present invention is illustrated by the following target properties of the hydraulic composition. Therefore, it non-limiting examples. The materials used in the examples is not necessary to measure the quantity of clay in the sand are available from the following suppliers: beforehand to determine the necessary quantity of cationic polymer. 15 The quantity of cationic polymer required for inerting (1) Cement Lafarge France, Le Havre. (2) ISO sand Nouvelle de Littoral, France depends mainly on the content of clays in the sand. It may (3) Siliceous Fulchiron PE2 LS Fulchiron, France also vary according to the nature of the clays in the sand. For sand (4) Erbray Filler MEAC, France information purposes, treatment of sand is generally satis (5) Glenium 27 Superplasticizer Chryso, France factory with a dosage of 2 to 20%, preferably from 5 to 10% (6) FL-2250 cationic polymer SNF, France by weight of dry extract of cationic polymer relative to the (7) C*Plus 08011 yellow dextrin Cargill weight of dry clay in the sand. or TACKIDEX (R) C172Y white Roquette Company Preferably, the treatment of sand is generally satisfactory dextrin (8) QUAT188 Dow Chemical Company with a dosage of 300 ppm to 10,000 ppm, preferably 1,000 (9) Chitosan 652 France Chitine ppm to 3,000 ppm by dry mass of cationic polymer relative 25 (10) Hydroxyethyl cellulose Hercules to the mass of sand. (Natrosol 250 LR) The cationic polymer may be added to one or more of the (11) GTMAC Aldrich constituents containing the harmful impurities. It may also be added at the time of the preparation of the hydraulic Determination of the Degree of Substitution of a Polymer composition, for example in the mixing water. 30 which was Obtained with a Base of Dextrin by a Measure The cationic polymer may therefore be added at the ment of Total Nitrogen quarry as well as at the concrete mixing plant. Determination of the degree of substitution, DS of a Direct treatment of the constituents, for example at a sand polymer by quaternary amine groups is carried out by quarry, is generally more efficient and therefore is preferred. determining the polymer’s percentage of nitrogen by mea The constituents thus treated may also be used in the 35 Surement of total nitrogen. typical manner, in particular for preparation of hydraulic The measurement of nitrogen is carried out with a titrator setting compositions. They are useful for preparation of of total organic carbon (TOC) with a nitrogen module (TON hydraulic compositions having constant properties. “Total Organic nitrogen). It is possible to measure the In particular, sands thus treated are useful for the prepa totality of the nitrogen contained in a sample. After complete ration of hydraulic compositions, in which clays could 40 oxidation at 1050° C., the nitrogenized compounds release disturb the efficiency of the superplasticizers. They may be nitric oxide in Stoichiometric quantities. This is transformed, used in the typical manner for preparation of hydraulic by contact with oZone (generated by the apparatus) into setting compositions. nitrogen dioxide, an unstable compound, according to the The hydraulic compositions comprising sands with a following reaction (I): content of clay treated with the cationic polymer according 45 to the invention have comparable rheological properties to those prepared with clay-free sands or those prepared with The return to a stable state of the nitrogen dioxide takes the cationic polymers described in patent application place with the emission of photons (close to infrared), the WO2006032785, without an over dosage of superplasticizer emissions of light proportional to the concentration of nitric and, therefore at a lower cost. 50 oxide according to the following reaction (J): This process therefore makes it possible to reduce the quantity of water or fluidizer required to obtain a desired The light emitted by chemiluminescence is then measured fluidity. by a photomultiplier, then a signal is obtained which can be Furthermore, advantageously the described process does observed in the form of a peak. not disturb the characteristics of the compositions, even in 55 After having quantified the nitrogen contained in the cases of over dosages. In particular, no air-entraining or sample, it is possible to determine the degree of Substitution, retarded setting effects are observed. Furthermore, the use of DS, by considering that when a group from a compound the described process does not affect the other characteristics according to formula (1) is grafted to a repetition unit of a of hydraulic compositions, for example workability and its homopolymer, the mass of the obtained final product cor slump retention over time, short and long-term mechanical 60 strengths or the setting time. responds to the sum of masses of the repetition unit and the The described process makes it possible to even treat very compound minus the mass of the Z element and of the mass polluted constituents. The described cationic polymer is of a hydrogen atom. This therefore gives the following indeed efficient at a low dosage, and therefore makes an relation (K): industrial scale inerting treatment economically viable. Fur 65 Mcationic Polysaccharide MUNIT+DSX (MoUAT-Mitz) (K) thermore, the cationic polymer is stable over time and resists wherein M is is the molar mass of the heat and freezing cationic polysaccharide, M is the molar mass of the US 9,624,129 B2 15 16 repetition unit of the polymer, Moz is the molar mass of TABLE 1. the amine compound from which the amine group is obtained, M is the molar mass of the HZ compound. Mortar Formulation Furthermore, by calling, My the total mass of the nitrogen Component Mass (g) (14 g/mol) and C the mass concentration (in 96) of nitrogen Cement 480.4 in the total quantity of the cationic polysaccharide, one ISO sand 1350 obtains: Siliceous sand 2001 Limestone filler 3S4.1 Clays 30 My xDS (L) 10 Glenium 27 Superplasticizer O.81 CN = H Total water, including 326.7 Mcationic Polysaccharide mixing water 226.7 sand wetting water 1OO Finally one obtains: 15 The Water/Cement ratio was 0.68. The cement was a Portland cement of the CEMI 52.5 N type. MUNIT X Cw (M) The ISO sand was a certified CEN EN 196-1 sand. This DS = - - - - - is a natural siliceous sand, with round grains, a content of MN - Cw (MoUAT - MHz) silica at least equal to 98%. Its particle size composition was within the boundaries given in Table 2. In the case where the amine compound is QUAT 188, that the Z is chlorine and that the polymer is dextrin, the relation TABLE 2 (M) becomes: Particle size composition of the ISO Sand 25 Dimensions of the Cumulated oversize DS 162Cy (N) Square meshes (mm) on the sieve (%) T 14-152, 5x Cy 2.OO O 1.60 7 S 1.OO 33 S Determination of the Degree of Substitution of a Cationic 30 OSO 67 S O16 87 S Polymer which was Obtained with a Base of Chitosan by O.08 99 1 Measurement of the Chlorine The content of chlorine of the cationic polymers is The clay comprised one third of kaolinite, one third of determined by potentiometric measurements. The chlorides, 35 illite and one third of montmorillonite. The quantity of clays present in Solution, are precipitated by the addition of a corresponded to 1.95% by weight relative to the weight of solution of silver nitrate of a known volume, then the the sands. quantity of silver nitrate introduced in excess is measured by Method to Measure the Spread of a Hydraulic Composi HCl (hydrochloric acid). The content of measured chlorine tion also makes it possible to determine the degree of Substitu 40 The principle of the spread measurement consists in tion. filling a truncated spread measurement cone with the Method of Preparation of a Mortar hydraulic composition to be tested, then releasing the said composition from the said truncated spread measurement The mortar is made using a mixer of the Perrier type. The cone in order to determine the surface of the obtained disk entire operation is carried out at 20° C. The method of 45 when the hydraulic composition has finished spreading. The preparation comprises the following steps: truncated spread measurement cone corresponds to a repro Introduce the sands, with or without clay, in a mixing duction at the scale /2 of the cone as defined by the NFP bowl; 18-451 Standard, 1981. The truncated spread measurement At T=0 second: begin mixing at low speed (140 rpm) and cone has the following dimensions: 50 top diameter: 50+/-0.5 mm; simultaneously add the wetting water in 30 seconds, bottom diameter: 100+/-0.5 mm; and then continue to mix at low speed (140 rpm) until 60 height: 150+/-0.5 mm. seconds; The entire operation is carried out at 20° C. The spread At T=1 minute: stop the mixing and leave to rest for 4 measurement is carried out in the following manner: minutes; 55 Fill the reference cone in one single operation with the hydraulic composition to be tested; At T=5 minutes (TO for the measurement method of the If necessary, tap the hydraulic composition to homog setting time): add the hydraulic binder; enously distribute it in the truncated cone; At T-6 minutes: mix at low speed (140 rpm) for 1 minute: Level the top surface of the cone; At T-7 minutes: add the mixing water in 30 seconds 60 Lift the truncated cone vertically; and (whilst mixing at low speed (140 rpm)); and Measure the spread according to four diameters at 45° with a calliper square. The result of the spread mea At T-7 minutes and 30 seconds: mix at high speed (280 Surement is the average of the four values, +/-1 mm. rpm) for 2 minutes. Method to Measure the Viscosity of a Hydraulic Compo Mortar Formulation 65 sition The following mortar formulation was used to carry out The Viscosity measurement consists in measuring the flow the tests. time through a truncated Viscosity measurement cone of a US 9,624,129 B2 17 18 hydraulic composition to be tested. The truncated viscosity TABLE 3 measurement cone has the following dimensions: larger diameter: 150 mm; and Measurement of the Spread of mortar Smaller diameter: 17 mm. Inerting agent Spread (nn The truncated viscosity measurement cone further com- 5 prises first and second marks which may be parallel marks Mortar (%) 5 mins 15 mins 30 mins 60 mins 90 mins provided on the sides of the truncated cone and defining M1 O 100 1OO 100 1OO 100 planes perpendicular to the axis of the truncated cone. The M2 O 325 3OO 287 270 first mark is closer to the base of the larger diameter than the MREF 10 3OO 297 290 270 225 second mark. The distance between the two marks is 60 mm, 10 the first mark being at 12 mm from the base with the larger diameter. The entire operation is carried out at 20°C. The viscosity TABLE 4 measurement of a hydraulic composition is carried out in the Viscosity following manner: 15 Orient the axis of the truncated cone vertically, the smaller Inerting Viscosity Viscosity Viscosity diameter being oriented downwards and being obtu Mortar agent (%) 5 mins. 30 mins. 60 mins. rated by a plug; M1 O Fill the truncated cone with the hydraulic composition up M2 O 17 30 50 to above the first mark; 2O MREF 10 17 29 44 Tap the hydraulic composition with a spatula in order to ensure the absence of big air bubbles; Remove the plug; TABLE 5 Start the stopwatch when the level of hydraulic compo sition passes the first mark; 25 Setting Time Stop the stop watch when the level of hydraulic compo Mortar Inerting agent (%) Setting time (h/mins) sition passes the second mark; and Record the time, which is representative of the viscosity M1 O 2 h 20 mins M2 O 4h 40 mins of the hydraulic composition. MREF 10 4h 40 mins Method to Measure the Setting Start Time of a Mortar 30 The concrete mortar (150 g) is introduced in a plastic container placed in a semi-adiabatic enclosure. A tempera The spread of the M1 mortar containing clays and not ture probe is then introduced into the concrete mortar to containing an inerting agent was Smaller than the spread of measure the evolution of the temperature. The curve of the the M2 mortar not containing clay. The viscosity of the M1 evolution of the temperature measured as a function of the 35 mortar was too significant and could not be measured. The time is stored for 24 hours. This curve successively com setting time of the M1 mortar was shorter than the setting prises an initial portion where the temperature changes, a time of the M2 mortar. second portion where the temperature increases, generally in The spread, viscosity and setting time of the reference a more or less linear manner and a third portion where the MREF mortar containing the inerting agent were substan temperature drops. The beginning of the setting time corre- 40 tially of the same order as those of the M2 mortar not sponds to the moment at which there is an inflexion of the containing clay. evolution curve between the initial and second portions. The quantity of cationic polymer according to the inven Examples 1 to 6 tion introduced in the following examples is given in per centages by weight of polymer relative to the weight of the 45 For Examples 1 to 6, the cationic polymers, Dext1 to clays contained in the mortar. DextG, were prepared from yellow dextrin C*Plus 08011 as follows. REFERENCE EXAMPLE Yellow dextrin (33.8 g at 96% of dry extract, i.e. 0.2 mole of AGU) and a quantity Q of water were introduced A mortar M1 was prepared having the formulation pre- 50 into a 1-liter double jacket reactor, at ambient temperature viously described. and mechanically stirred. When the dextrin was perfectly A mortar M2 was prepared having the formulation pre dissolved, an initial quantity of sodium hydroxide at 50% viously described the difference being that the M2 mortar (48 g, i.e. 0.6 mole) was added, then the mix was mechani did not comprise clays. cally stirred for one hour in a nitrogen atmosphere. Then, a The product commercialised by SNF under the name of 55 quantity Qouriss of QUAT188 was gradually added, fol FL-2250 was used as the REF polymer. It is a polyamine lowed by the addition of a second quantity Q of sodium coming from the condensation of epichlorohydrin and dim hydroxide at 50%, the addition being carried out in two ethylamine. additions every 20 minutes. Once this addition of sodium The REF polymer has a cationicity of 7.27 meq/g and hydroxide was complete, the reaction mixture was heated to 26% content of chlorine. 60 70° and left in a nitrogen atmosphere for two hours, then AMREF mortar was then prepared as previously indi cooled before being neutralized with adipic acid. cated by adding, with the pre-wetting water, 10% by weight For Examples 1 to 4, the obtained product was ultra of the REF polymer relative to the weight of the clays. filtered on a 5 kDa membrane of polyethersulfone for The spread, viscosity and setting time were measured purification. Only the molecules with a molar mass greater after preparing the M1, M2 and MREF mortars as previously 65 than 5 kDa were kept. described. The results are grouped together in Tables 3, 4 For each cationic polymer Dext1 to DextA, the quantities and 5 below. of Quazer, Qolariss and Qvor, the mass yield, the degree US 9,624,129 B2 19 20 of substitution (DS) of the obtained cationic groups by Example 2 measurement of the nitrogen are given in Table 6 below: A MDext2 mortar was prepared as previously described, TABLE 6 but adding the Dext2 polymer (DS of 0.35) after the pre Cationic Dextrins at Different DS wetting water, in the quantities given in Tables 9, 10 and 11 below. Reference Dext1 Dext2 Dext3 DextA The spread, viscosity and setting time were measured QWATER (g) 187 235 224 235 after preparation of the MDext2 and MREF mortars as 62.67 125.3 188 250.7 QoUA T1ss (g) 10 QNaOH (g) 16 32 48 642 previously described. The results are gathered together in Mass yield of cationic 78 78 89 84 Tables 9, 10 and 11 below. dextrin (%) Total content of 1.9 2.3 3.5 4.3 TABLE 9 nitrogen (%) DS 0.27 O.35 O.65 Content of chlorine (%) 2.3 3.6 7.0 9.8 15 Measurement of the spread of mortar The polymer DextS was obtained using the same process Spread (mm) as the one previously described for the polymer DextA (DS: 0.92) the difference being that the purification step was Dosage 60 90 120 carried out using a 10 kDa membrane of polyethersulfone. Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins Only the molecules with a molar mass Substantially greater than 10 kDa were kept. MDext2 10 190 18O 170 The polymer DextG was obtained using the same process 15 190 210 200 195 - as the one previously described for the polymer DextA (DS: 25 2O 300 340 350 340 33O 310 0.92) the difference being that the purification step was 30 410 410 40S 39S carried out in two steps. In an initial step, a 10 kDa MREF 10 300 297 290 27O 225 membrane of polyethersulfone was used. Only the mol ecules with a molar mass substantially lower than 10 kDa 30 were kept. In a second step, a 5 kDa membrane of polyether TABLE 10 sulfone was used. Only the molecules with a molar mass substantially greater than 5 kDa were kept. At the end of the Viscosity two steps, only the molecules with a molar mass Substan Dosage Viscosity Viscosity Viscosity Viscosity tially between 5 kDa and 10 kDa were kept. 35 Mortar (% of clay) 5 mins 15 mins 30 mins 60 mins MDext2 10 >50 >50 >50 >50 Example 1 15 >50 >50 >50 >50 2O 29 31 45 30 A mortar MDext1 was prepared as previously described, 40 MREF 10 17 29 44 but adding the Dext1 polymer (DS of 0.27) after the pre wetting water in the quantities given in Tables 7 and 8 below. The spread and the setting time were measured after TABLE 11 preparation of the MDext1 and MREF mortars as previously described. The results are given in Tables 7 and 8 below. 45 Setting Time Mortar Dosage (% of clay) Setting time (h/mins) TABLE 7 MDext2 10 5h 15 mins 2O 38 Measurement of the Spread of mortar MREF 10 4h 40 mins 50 Spread (nn Dosage 60 90 120 A 20% dosage of cationic polymer, calculated by weight Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins of dry polymer relative to the weight of clay, made it MDext1 10 185 170 16S 170 170 115 possible to reach a bigger spread than the spread of the 2O 185 210 215 205 205 195 55 reference MREF mortar. MREF 10 3OO 297 290 270 225 Example 3 TABLE 8 60 A MDext3 mortar was prepared as previously described, Setting Time but adding the Dext3 polymer (DS of 0.65) after the pre Dosage (% of clay) Setting time (h/mins) wetting water in the quantities given in Tables 12, 13 and 14 hereinafter. MDext1 10 7 h MREF 10 4h 40 mins 65 The spread, viscosity and setting time were measured after preparation of the mortars as previously described. The results are gathered together in Tables 12, 13 and 14 below. US 9,624,129 B2 21 22 TABLE 12 TABLE 16 Measurement of the spread of mortar Viscosity Dosage Viscosity Viscosity Viscosity Viscosity Spread (mm) Mortar (% of clay) 5 mins 15 mins 30 mins 60 mins Dosage 60 90 120 MDextA 8 24 46 9 16 23 48 Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins 10 18 26 S4 MREF 10 17 29 44 MDext3 10 250 255 240 220 190 18O 10 12 320 335 325 3OO 280 2SS 15 400 410 40S 400 385 - MREF 10 3OO 297 290 27O 225 TABLE 17 Setting Time 15 Mortar Dosage (% of clay) Setting time (h/mins) TABLE 13 MDextA 8 Sh Viscosity 10 5h 20 mins MREF 10 4h 40 mins Dosage Viscosity Viscosity Viscosity Viscosity Mortar (% of clay) 5 mins 15 mins 30 mins 60 mins A 9% dosage of cationic polymer, calculated by weight of MDext3 10 37 12 2O 46 dry polymer relative to the weight of clay, made it possible 15 19 27 to reach a bigger spread than the spread of the reference MREF 10 17 29 44 MREF mortar. 25 Examples 1 to 4 show that the lower the degree of substitution of the polymer with a base of dextrin, the greater TABLE 1.4 the quantity of polymer to be introduced in the mortar to obtain a similar spread to the spread of the reference MREF Setting Time 30 mortar. Dosage (% of clay) Setting time (h/mins) Example 5 MDext3 10 6 h 10 mins 12 7 h 30 mins 15 11 h 08 mins A MDext5 mortar was then prepared as previously MREF 10 4h 40 mins 35 described, but adding the Dext5 polymer (DS of 0.92 and molecular mass greater than 10 kDa) after the pre-wetting water in the quantities given in Tables 18, 19 and 20 A 12% dosage of cationic polymer, calculated by weight hereinafter. of dry polymer relative to the weight of clay, made it The spread, viscosity and setting time were measured possible to reach a bigger spread than the spread of the 40 after preparation of the MDext5 and MREF mortars as reference MREF mortar. previously described. The results are gathered together in Tables 18, 19 and 20 below. Example 4 TABLE 1.8 45 AMDextA mortar was prepared as previously described, Measurement of the Spread of mortar but adding the Dext4 polymer (DS of 0.92) after the pre wetting water in the quantities given in Tables 15, 16 and 17 Spread (nn hereinafter. Dosage 60 90 120 The spread, viscosity and setting time were measured 50 Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins after preparation of the MDext4 and MREF mortars as MDexts 8 275 26S 250 230 220 18S 10 390 392 380 350 320 285 previously described. The results are gathered together in MREF 10 300 297 290 27O 225 Tables 15, 16 and 17 below. 55 TABLE 1.5 TABLE 19 Measurement of the spread of mortar Viscosity Spread (nn 60 Viscosity Dosage 60 90 120 Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins Dosage Viscosity Viscosity Viscosity Viscosity Mortar (% of clay) 5 mins 30 mins 60 mins 90 mins MDextA 8 28O 26S 255 220 200 175 9 320 315 305 275 255 220 MDexts 8 27 58 10 350 355 340 3OO 280 240 10 17 22 36 MREF 10 3OO 297 290 27O 225 65 MREF 10 17 29 44 US 9,624,129 B2 23 24 TABLE 20 mechanically stirred for one hour in a nitrogen atmosphere. The obtained product was ultra-filtered on a 0.5 kDa mem Setting Time brane of polyethersulfone for purification. Only the mol Mortar Dosage (% of clay) Setting time (h/mins) ecules with a molar mass greater than 5 kDa were kept. For each of the cationic polymers, Chitl to Chit3, the MDexts 10 7 h 30 mins quantities Qcurr, QuarER, QoUATss and Qvor, the mass MREF 10 4h 40 mins yield, the degree of substitution (DS) of the cationic groups obtained by measurement of the chlorine are given in Table At low dosages of the cationic polymer, 8% or 10%, 24 below: calculated by weight of dry polymer relative to the weight of 10 clay, a spread close to the spread of the reference MREF TABLE 24 mortar can be obtained. Chit1 Chit? Chit3 Example 6 QCHIT (g) 30 10 15 15 QWATER (g) 25 235 150 A MDexté mortar was then prepared as previously QoUAT188 (g) 43.9 40.2 O QoUAT151 (g) O O 50 described, but adding the Dexté polymer (DS of 0.92 and QNaOH (g) 12 22.6 O molecular mass of from 5 kDa to 10 kDa) after the pre DS O.65 O.S9 1.35 wetting water in the quantities given in Tables 21, 22 and 23 Mass yield (%) 50 50 52 hereinafter. The spread, viscosity and setting time were measured after preparation of the MDexté and MREF mortars as previously described. The results are gathered together in Example 7 Tables 21, 22 and 23 below. 25 A MChit 1 mortar was prepared as previously described, TABLE 21 but adding the Chitl (DS of 0.65) polymer in the pre-wetting water in the quantities given in Tables 25, 26 and 27 Measurement of the spread of mortar hereinafter. Spread (nn The spread, viscosity and setting time were measured 30 after preparation of the MChitl and MREF mortars as Dosage 60 90 120 previously described. The results are gathered together in Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins Tables 25, 26 and 27 below. MDexté 10 315 330 315 305 285 255 MREF 10 3OO 297 290 270 225 TABLE 25 35 Measurement of the spread of mortar TABLE 22 Spread (Inn Viscosity Dosage 60 90 120 40 Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins Viscosity MChit1 6 315 275 250 200 Dosage Viscosity Viscosity Viscosity Viscosity 8 330 305 290 250 225 175 Mortar (% of clay) 5 mins 30 mins 60 mins 90 mins 10 340 315 295 260 235 18S MREF 10 300 297 290 27O 225 MDexté 10 19 26 40 45 MREF 10 17 29 44 TABLE 26 TABLE 23 Viscosity 50 Setting Time Mortar Dosage (% of clay) Viscosity 5 min Mortar Dosage (% of clay) Setting time (h/mins) MChit1 6 33 8 30 MDexté 10 6 h 15 mins 10 34 MREF 10 17 MREF 10 4h 40 mins 55 Examples 7 to 9 TABLE 27 For Examples 7 to 9, the Chitl to Chit3 cationic polymers 60 Setting Time were prepared as follows from chitosan. Mortar Inerting agent (%) Setting time (h/mins) A quantity QCruz of chitosan, a quantity Quarter of Water MChit1 6 4h and a quantity Qriss at 65% of QUAT188 were intro 8 4h duced into a 1-liter double-jacket reactor, at ambient tem 10 4h 30 mins perature and mechanically stirred. When the chitosan was 65 MREF 10 4h 40 mins perfectly dispersed, a quantity Q of sodium hydroxide at 50% (12 g i.e. 0.15 mole) was added, then the mix was US 9,624,129 B2 25 26 Example 8 TABLE 32 Viscosity A MChit? mortar was prepared as previously described, but adding the Chit? polymer (DS of 0.59) in the pre-wetting Dosage Viscosity Viscosity water in the quantities given in Tables 28, 29 and 30 Mortar (% of clay) 5 mins 30 mins hereinafter. MChit 10 30 56 The spread, viscosity and setting time were measured MREF 10 17 29 after preparation of the MChit? and MREF mortars as previously described. The results are gathered together in 10 Tables 28, 29 and 30 below. TABLE 33 TABLE 28 Setting Time Mortar Inerting agent (%) Setting time (h/mins) Measurement of the spread of mortar 15 MChit 10 4h 30 mins Dosage Spread (mm) MREF 10 4h 40 mins Mortar (% of clay) 5 mins 15 mins 30 mins 60 mins 90 mins Example 10 MChit? 10 360 335 325 3OO 260 MREF 10 3OO 297 290 270 225 A cationic polymer, called Dext7, was prepared from dextrin as follows. To a solution of yellow dextrin, C*Plus 08011 (17 g i.e. 106 mmol), solubilised in an aqueous solution, 0.8 MNaOH (132.5 mL), in a nitrogen atmosphere TABLE 29 25 at 45° C. for 30 minutes, a solution of GTMAC (Glycidyl TriMethylAmmonium Chloride) (71.1 mL i.e. 371 mmol), Viscosity solubilised beforehand in 18 mL of distilled water was added. The reaction was stirred for a total of 20 hours at 45° Viscosity C. in a nitrogen atmosphere. The solution, after having been Dosage Viscosity Viscosity 30 brought back to ambient temperature, was neutralised with Mortar (% of clay) 5 mins 30 mins a solution of HCl, then diluted with an aqueous solution 0.5 MNaCl until reaching a total volume of one liter. It was then MChit? 10 32 48 ultra-filtered by tangential ultra filtration using a MILLI MREF 10 17 29 PORE membrane (cut-off threshold 1000 g/mol), commer cialised by Millipore, of polyethersulfone. The ultra filtra 35 tion was stopped when the conductivity of the filtrate was TABLE 30 stable and reached a value less than 10 LS. The solution was then lyophilized. Setting Time The yield of this reaction was 45%. The degree of Substitution of the cationic groups by potentiometric mea Mortar Inerting agent (%) Setting time (h/mins) 40 surement was 0.85. MChit? 10 4h 30 mins MREF 10 4h 40 mins Example 11 A cationic polymer, called Chit4 was prepared from 45 chitosan as follows. To a solution of chitosan (15g, i.e. 87.2 Example 9 mmol), dispersed in distilled water (150 mL) for one night at ambient temperature, GTMAC (GlycidylTriMethylAm monium Chloride) was added drop by drop under stirring A Mchit3 mortar was then prepared as previously (165.5 mL i.e. 863 mmol being given that it is an aqueous described, but adding the Chit3 polymer (DS of 1.35) in the solution at approximately 30%) in three additions with pre-wetting water in the quantities given in Tables 31, 32 and 50 2-hour intervals between each addition (58, 58 and 49.5 33 hereinafter. mL). The reaction was stirred for a total of 10 hours at 85° The spread, viscosity and setting time were measured C. After cooling to ambient temperature, the reaction after preparation of the MREF and MChit3 mortars as medium was diluted with water until reaching a total volume previously described. The results are gathered together in 55 of one liter. It was then ultra-filtered by tangential ultra filtration using a MILLIPORE membrane (cut-off threshold Tables 31, 32 and 33 below. 1000 g/mol) of polyethersulfone. The ultra filtration was stopped when the conductivity of the filtrate was stable and TABLE 31 reached a value less than 10 LS. The solution was then Measurement of the spread of mortar lyophilized. The compound (20.25 g i.e. 45.4 mmol) was 60 thus isolated. The yield of this reaction was 52.1%. The Dosage Spread (Inn degree of Substitution of the cationic groups by potentio Mortar (% of clay) 5 mins 15 mins 30 mins 60 mins 90 mins metric measurement was 1.35. MChit 10 330 335 295 255 225 Example 12 for Comparison MREF 10 3OO 297 290 270 225 65 A cationic polymer, called Hec 1, was prepared from hydroxyethyl cellulose as follows. To a solution of hydroxy US 9,624,129 B2 27 28 ethyl cellulose (17 g i.e. 31 mmol), solubilised in an aqueous solution was then heated at 70° C. with magnetic stirring for solution, 0.8 MNaOH (132.5 mL) in a nitrogen atmosphere 5 days. The Solution was then concentrated under vacuum at 45° C. for 30 minutes, a solution of GTMAC (Glycidyl and the pH was brought to 12 with a solution of NaOH (1 TriMethylAmmonium Chloride) 5.1 mL i.e. 21.8 mmol), M). At this pH, a gel formed. It was then filtered on a frit 3 solubilised beforehand in 18 mL of distilled water, was 5 and copiously washed in distilled water. The dimethyl added. The reaction was stirred for a total of 20 hours at 45° chitosan (DMC) was then solubilised in water with a pH C. in a nitrogen atmosphere. The Solution, after having been equal to 4 (adjusted with a solution of HCl at 1 M), filtered brought back to ambient temperature, was neutralised with on a frit, then purified by ultra filtration (Pall Minimate TFF a solution of HCl then diluted with an aqueous solution, 0.5 system with an Omega membrane 5000 Dalton). The prod 10 uct was finally lyophilised. The DMC was then quaternised M NaCl, until reaching a total volume of one liter. It was with methyl iodide. To avoid O-methylation, the reaction then ultra-filtered by tangential ultra filtration using a MIL was carried out in a mix of HO/DMF. More particularly, 20 LIPORE membrane (cut-off threshold 1000 g/mol) of g of DMC was placed in a 2-liter Erlenmeyer flask, then 500 polyethersulfone. The ultra filtration was stopped when the mL of a mix of HO/DMF (50/50) was added. The assembly conductivity of the filtrate was stable and reached a value 15 was magnetically stirred. A solution of NaOH (4 M) was less than 10 LS. The solution was then lyophilized. then added until the formation of a gel, then 12 mL of CHI The yield of this reaction was 46%. The degree of was added. The reaction medium was then vigorously stirred Substitution of the cationic groups by potentiometric mea for 48 hours at ambient temperature. At the end of the Surement was 1.1. reaction, it was concentrated under vacuum and the trim A MHec1 mortar was prepared as previously described, ethyl chitosan (TMC) was precipitated by three volumes of but adding 10% by mass dry extract of the Hec1 polymer cold ethanol, then filtered on a frit. Solubilised in water it after the pre-wetting water. was precipitated a second time with ethanol. The obtained The spread, viscosity and setting time were measured product was then solubilised in a solution of NaCl at 5% to after preparation of the MREF and MHec1 mortars as carry out the ion exchange, then it was precipitated again previously described. The results are gathered together in 25 with 3 volumes of ethanol. The TMC was finally purified by Tables 34, 35 and 36 below. ultra filtration (Pall Minimate TFF system with an Omega membrane 5000 Dalton), then lyophilised. The NMR'H TABLE 34 analysis gave a quaternisation percentage of 22%. Measurement of the Spread of mortar 30 Example 14 Spread (nn A cationic polymer was prepared according to a process Dosage 60 90 120 using re-doX and amination-reduction reactions. Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins 15 g of cellulose (92.5 mol) was dissolved in 750 mL of MHec1 10 340 3OO 275 235 200 - 35 distilled water. 39.59 g of sodium periodate (185 mmol) was MREF 10 3OO 297 290 27O 225 added in 300 mL of distilled water and 50 mL of propanol. Mixing was carried out by magnetic stirring for 100 hours sheltered from light. It was then filtered on a Bichner funnel, TABLE 35 the residue was washed with distilled water. The last wash H 40 ing was carried out with ethanol to facilitate the drying of the Viscosity cellulose, after filtration, the cellulose was dried in a drying oven. 12 g of oxidised cellulose was obtained. Mortar Dosage (% of clay) Viscosity 5 min 10 g of oxidised cellulose was put into Suspension in MHec1 10 45 water. An excess of sodium borohydride was added and the MREF 10 17 45 reaction was left to continue for 48 hours at ambient temperature. The reduced cellulose being soluble in water, it was purified by dialysis and evaporated to dryness. 8.15g of TABLE 36 reduced cellulose was obtained, i.e. 80% yield. 20g of carboxymethyl cellulose (CMC) was dissolved in Setting Time 50 700 mL of distilled water. 200 mL of an aqueous solution containing 30.06 g of sodium periodate (140 mmol) and 50 Dosage (% of clay) Setting time (h/mins) mL of propanol were added. It was then magnetically stirred MHec1 10 4h 10 mins for 25 hours. At the end of the reaction the solution was MREF 10 4h 40 mins concentrated and filtered under vacuum. The residue was left 55 to dry at ambient temperature. 15 g of oxidised CMC was The use of the Hec1 cationic polymer resulted in high obtained. initial viscosities. Furthermore, the spread at 90 minutes was 10 g of oxidised CMC was dissolved in 400 mL of insufficient. distilled water by magnetic stirring. Then an aqueous solu tion containing 5.04 g of Sodium cyanoborohydride and 3.6 Example 13 60 mL of methylamine was added. The mix was magnetically stirred for 24 hours. It was concentrated and filtered under A cationic polymer was prepared according to a process vacuum. It was washed with dimethyl acetamide and filtered using a quaternisation reaction. 40 g of chitosan were placed again. The yield of this reaction was 67.4%. in a 2-liter Erlenmeyer flask and 120 mL of formic acid then 10 g of aminated CMC (4 mmol) was dissolved in a mix 160 mL of an aqueous solution of formaldehyde at 30% and 65 of 300 mL of DMSO (DiMethyl Sulfoxide) and 300 mL of finally 720 mL of distilled water were added, bringing the water. Six methyl iodide equivalents (24 mmol) were added total volume of the reaction medium to one liter. The and magnetically stirred for 4 days. After the reaction US 9,624,129 B2 29 30 finished, it was filtered on a Bichner funnel, washed with A solution of cationic starch was prepared from the Aml ethanol and dried. 8 g of the product was obtained, that is to cationic polymer and water. The measured dry extract was say, a yield of 80%. A quaternary ammonium group of the 9%. aminated CMC was formed. A MAm1 mortar was prepared as previously described, but adding 10% by mass of dry extract of the cationic starch Example 15 in Solution with the pre-wetting water. The spread, viscosity and setting time were measured A Dext8 cationic polymer was prepared from TACKI after preparation of the MREF and MAm1 mortars as DEX(R) C172Y yellow dextrin as follows. Yellow dextrin previously described. The results are gathered together in (50.3 g at 96% of dry extract, i.e. 0.3 mole of AGU) and a Tables 40 and 41 below. quantity of sodium hydroxide at 15% (79.5 g. i.e. 0.3 moles) 10 were introduced into a 1-liter double jacket reactor at TABLE 40 ambient temperature and mechanically stirred for 15 hours. The medium was heated to 45° C. A quantity Qouriss of Measurement of the spread of mortar QUAT188 was then gradually added followed by the gradual addition of sodium hydroxide at 15%, the addition carried 15 Spread (Inn out in 5 hours. Once this addition was finished, the reaction Dosage 60 90 120 mixture was cooled before being neutralised with hydro Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins chloric acid at 37%. The obtained product was then ultra filtered on a 5 kDa MAm1 10 100 membrane of polyethersulfone for purification. Only the MREF 10 300 297 290 27O 225 molecules with a molar mass greater than 5 kDa were kept. The yield of this reaction was 75%. The degree of substi tution of the cationic groups by measurement of the content TABLE 41 of nitrogen was 0.8. AMDext8 mortar was prepared as previously described, 25 Setting Time but adding 10% by mass of dry extract of the Dext8 polymer after the pre-wetting water. The spread, Viscosity and setting Dosage (% of clay) Setting time (h/mins) time were measured after preparation of the MREF and MAm1 10 3 h 30 mins MDext8 mortars as previously described. The results are MREF 10 4h 40 mins gathered together in Tables 34, 35 and 36 below. 30 The use of the Am1 cationic starch resulted in a spread TABLE 37 which was too small to be handled. This cationic polymer has a very high molecular weight (higher than 1,000,000 Measurement of the spread of mortar g/mol) and is not soluble in water at the temperature of the Spread (nn 35 mortar. The invention claimed is: Dosage 60 90 120 1. A process for preparation of an inerted hydraulic or Mortar (% of clay) 5 mins 15 mins 30 mins mins mins mins hydrocarbon composition, comprising: a) providing aggregates comprising impurities and a MDext8 10 350 350 350 325 305 2.65 hydraulic or hydrocarbon binder to prepare a hydraulic MREF 10 3OO 297 290 27O 225 40 or hydrocarbon composition, and b) adding a cationic polymer to the composition or to one of its constituents, the cationic polymer corresponding TABLE 38 to at least one derivative of dextrin, chitosan or chitin. 2. The process according to claim 1, wherein the cationic Viscosity 45 polymer is cationic dextrin. Mortar Dosage (% of clay) Viscosity 5 mins 3. The process according to claim 2, wherein the cationic polymer is yellow cationic dextrin. MDext8 10 16 4. The process according to claim 1, wherein the cationic MREF 10 17 polymer is Substituted by quaternary amine groups. 50 5. The process according to claim 4, wherein the quater nary amine groups are derived from a quaternary amine TABLE 39 compound according to formulae (1) or (2): Setting Time Dosage (% of clay) Setting time (h/mins) 55 (1) R1 -- MDext8 10 5 h 15 mins MREF 10 4h 40 mins ti-in-chi-- Z X OH R3 The use of the Dext8 cationic polymer resulted in low 60 initial viscosities and a high spread until 120 minutes. (2) RI -- Example 16 CH-CH-(CHR)-N-R Z N/ Starch was used as a cationic polymer, commercialised 65 O R3 under the name of Hi Cat 985 580T624 by the Roquette company. US 9,624,129 B2 31 32 wherein n is an integer from 1 to 16: 11. The process according to claim 1, wherein the hydrau X is a halogen; lic composition is a concrete or a mortar. Z is an inorganic or organic anion; 12. The process according to claim 1, wherein the cationic R. R. R. and R, which may be identical or different, are polymer is added to a sand of the aggregates. each hydrogen or an organic radical, R furthermore 5 13. The process according to claim 1, wherein the cationic capable of being a group according to formulae (3) or polymer is added to a mixing water when preparing the (4): hydraulic composition. 14. The process according to claim 1, wherein the impu (3) rities are clays. 10 15. A process for preparation of an inerted hydraulic or RI -- hydrocarbon composition, comprising: a) providing sand comprising impurities; -(CH3), -car-ti-ji, Z b) adding a cationic polymer to the sand of step a), the R3 OH X cationic polymer corresponding to at least one deriva (4) 15 tive of dextrin, chitosan or chitin, and R1 -- c) mixing the inerted sand obtained after step b) and a hydraulic or hydrocarbon binder to prepare the inerted -(CH2).--N-(CHR), -CH-CH Z. hydraulic or hydrocarbon composition. N/ 16. The process according to claim 15, wherein the sand is contacted with the cationic polymer by spraying the wherein p is an integer from 2 to 10 and n, R, R', R. R. cationic polymer in aqueous solution on the sand. X and Z are as previously defined. 17. The process according to claim 15, wherein the sand 6. The process according to claim 5, wherein R, R', R has a humidity value less than 10% by weight. and Rare each hydrogen or an alkyl, hydroxyalkyl, alkenyl 25 18. The process according to claim 15, wherein the sand or aryl group comprising up to 10 carbon atoms. is treated with a dosage of 300 ppm to 10000 ppm by dry 7. The process according to claim 5, wherein R, R', R mass of cationic polymer relative to a mass of sand. and R are each hydrogen. 19. The process according to claim 15, wherein the 8. The process according to claim 6, wherein the quater impurities are clays. nary amine compound is selected from the group consisting 30 20. A process for preparation of an inerted hydraulic of: composition, comprising: 2,3-epoxypropyl-N,N.N-trimethylammonium chloride; a) providing aggregate comprising impurities; 3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium b) providing a hydraulic binder; chloride; c) adding a cationic polymer to mixing water, the cationic 3-chloro-2-hydroxypropyl-N,N-dimethylethanolammo 35 polymer corresponding to at least one derivative of nium chloride; and dextrin, chitosan or chitin, and 1,3-bis-(3-chloro-2-hydroxypropyl-N,N-dimethylammo d) mixing the aggregates, hydraulic binder and mixing nium)N-propane dichlorohydrin. water to prepare the inerted hydraulic composition. 9. The process according to claim 5, wherein the quater 21. The process according to claim 1, wherein the poly nary amine compound is selected from the group consisting 40 mer is added at a quarry or at a concrete mixing plant. of betaine, betainyl chloride and betaine chloride. 22. The process according to claim 12, wherein the 10. The process according to claim 1, wherein the cationic cationic polymer is added by spraying an aqueous solution. polymer has a degree of substitution of from 0.2 to 2.5. k k k k k