(12) United States Patent (10) Patent No.: US 9,624,129 B2 Hoang Et Al
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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 <polymers> is to be the aggregates is by washing in water. The dirty water is then understood as a compound comprising more than two iden treated by a flocculation agent which makes it possible to tical or different, linear and/or branched monomeric units accelerate the liquid-solid separation and hence recover presenting a particular or not particular order. clean water. This water is then recycled to wash sand again. 35 The term <cationicity> is to be understood as denoting However, this solution is expensive in terms of equipment the density of positive charges carried by a compound. and requires a considerable Supply of water. The expression <degree of substitution (DS)> is to be Another solution consists of not separating the clays from understood according to the invention as the average number the sands but inerting the clays in the sands. Patent Appli of moles of the quaternary group carrying one or more cation WO2006032785 provides the use of absorption 40 cationic functions (for example quaternary nitrogen) linked agents modifying the activity of the clay, for example by to a unit of for example, glucose and/or of glucosamine. The reducing its absorption capacity or by carrying out a pre value of the DS may vary from 0 to 3. absorption process. This document WO2006032785 The expression <degree of polymerisation (DP)> is to describes in particular the use of cationic polymers com be understood according to the invention as the number of prising groups of quaternary amines. Nevertheless, the use 45 constitutive units (repetition units) of the polymer. Gener of products used in the described examples in this document ally, a polymer comprises several macromolecules which can lead to the addition of a significant amount of chlorine can have different degrees of polymerisation. The expression into the hydraulic composition. This is not desirable inas <average degree of polymerisation (ADP)> is to be much as standards generally impose a maximum quantity of understood according to the invention as the ratio between chlorine in the hydraulic compositions (the NF EN 206-1 50 the total number of constitutive units (repetition units) and Standard specifies a maximum quantity of 1% of chloride the total number of macromolecules. ions Cl relative to the cement for non-reinforced concretes The term <hydraulic composition> is to be understood and a maximum quantity of 0.1% of chloride ions Cl as any composition capable of hydraulic setting, and most relative to the cement for metal-reinforced concretes) or particularly the mortars and concretes intended for all the hydrocarbon compositions due to the corrosive property of 55 construction markets (buildings, civil engineering or pre chlorine. cast plants). The aim of the present invention is therefore to provide a The expression <hydraulic binderd is to be understood process for the preparation of hydraulic or hydrocarbon according to the present invention as a pulverulent material compositions which are useful to reduce the undesirable which, mixed with water, forms a paste which sets and effects related to the presence of such harmful impurities as 60 hardens as a result of hydration reactions, and which, after clays and which makes it possible to reduce the introduction hardening, retains its strength and its stability, even under of chlorine into the hydraulic or hydrocarbon composition. Water. This aim is reached by using specific cationic polymers. The term <concreted, is to be understood as a mix of Therefore, the invention relates to an inerting process for hydraulic binders (for example cement), aggregates, water, impurities, for example clays, in aggregates intended for the 65 optionally additives, and optionally mineral additions, for preparation of hydraulic or hydrocarbon compositions, com example high performance concrete, very high performance prising a step consisting of adding to the composition or to concrete, self-placing concrete, self-levelling concrete, self US 9,624,129 B2 3 4 compacting concrete, fibre concrete, ready-mix concrete or hydraulic or hydrocarbon compositions.