WO2016012662A1 - Calcium-cellulose organo-mineral complex, preparation process and applications - Google Patents
Calcium-cellulose organo-mineral complex, preparation process and applications Download PDFInfo
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- WO2016012662A1 WO2016012662A1 PCT/FR2014/051929 FR2014051929W WO2016012662A1 WO 2016012662 A1 WO2016012662 A1 WO 2016012662A1 FR 2014051929 W FR2014051929 W FR 2014051929W WO 2016012662 A1 WO2016012662 A1 WO 2016012662A1
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- cellulose
- complex
- paste
- calcium
- quicklime
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- 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
- C04B28/10—Lime cements or magnesium oxide cements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the invention relates to an organo-mineral complex obtainable by chemical degradation of cellulose, a process for producing such a complex and the applications thereof, in particular in construction.
- Cellulose the most abundant organic polymer in the biosphere, is a polysaccharide made up of glucose units connected by ⁇ (1-4) bonds, the number of which can reach several thousand. It is a linear polymer whose linking gives it a secondary structure which can be assimilated to a helix consisting of dimeric units of cellulobiosis at each step of the helix, and whose tertiary structure is a bundle of polysaccharide chains arranged. parallel to each other and in the same direction from the non-reducing end to the reducing end, forming microfibrils. In this structure come into play a considerable number of intramolecular and intermolecular hydrogen bonds, at the origin of the remarkable mechanical strength of cellulose.
- FR2700163A1 discloses a process for the manufacture of a building material which is obtained by a reaction mixture comprising a suspension of cellulosic fibers from waste paper and cardboard, lime and a mono- or trivalent sulfate of metal salts like aluminum, in stoichiometric quantities.
- a reaction mixture comprising a suspension of cellulosic fibers from waste paper and cardboard, lime and a mono- or trivalent sulfate of metal salts like aluminum, in stoichiometric quantities.
- Such conditions lead to the formation of a calcium ligno-sulphoaluminate in the form of a paste which is pressed and then dried, or molded, and is then used to manufacture a structural element having mechanical and sound and thermal insulation properties.
- the Applicant has developed a method of chemical degradation of cellulose using quicklime, not hydrated lime, resulting in an organo-mineral complex different from those known.
- This complex possesses exceptional mechanical and physicochemical properties which
- the material of the invention makes it possible to obtain more efficient construction elements, as some of the properties of such elements, listed below:
- the invention relates to a calcio-cellulosic organo-mineral complex that can be obtained by reaction of quicklime on cellulose, in aqueous suspension.
- quicklime reacts with cellulose at a much higher rate than the hydration of quicklime in the aqueous medium, but the two reactions, having different kinetics, co-exist.
- a complex is formed, that of the invention, which consists of polysaccharide chains resulting from a rupture of the intermolecular hydrogen bonds of cellulose and a decarboxylation of the CH 2 OH group (carbon 6) carried by the carbon 5 of the units.
- glucose of cellulose associated with calcite CaCO 3 . This is formed by the reaction of the carbon dioxide released by said decarboxylation on Ca (OH) 2 from the hydration of quicklime in the reaction medium.
- the intermolecular hydrogen bond breaking and decarboxylation of the CH 2 OH group carried by the carbon 5 of glucose units may be concomitant.
- At least 50% of the non-reducing ends of the cellulose are decarboxylated according to the decarboxylation described above, preferably at least 75%, or even at least 90%, or even all.
- at least 50% of the intermolecular hydrogen bonds of the cellulose are broken, preferably at least 75%, or even at least 90%, or even all.
- Decarboxylation of the CH 2 OH group carried by the carbon of the glucose units requires the rupture of the intramolecular hydrogen bond between the hydrogen atom of the C6 hydroxyl group of the glucose unit concerned by the decarboxylation, and the atom of oxygen from the pyranic ring of the next glucose unit. During complex formation, other intramolecular hydrogen bonds can also be broken, without subsequent decarboxylation.
- the invention also relates to a process for the preparation of a calcio-cellulosic complex, in which aqueous lime is reacted in aqueous suspension on cellulose and the complex is obtained in the form of a paste.
- the cellulose to be treated can be in any form, pretreated or not, and come from any source. It is preferably in the form of cellulose fibers, it can come from all papermaking waste and cardboard, such as cellulosic waste from recycling, landfills, waste paper, cardboard, newspapers, magazines or other cellulosic waste. It can also come from paper sludge or waste paper.
- the implementation of the process is simple, and the complex is obtained regardless of the order of addition of the ingredients, namely, water, quicklime and cellulose. Their addition may be concomitant.
- quicklime is poured into water and the cellulose is then introduced.
- the weight ratio of CaO to cellulose is preferably between 30/70 and 70/30.
- it is 50/50, the amount of quicklime reacted being the same as that of the cellulose to be treated.
- various ingredients may be added, depending on the desired applications, such as a salt of a metal chosen from aluminum, potassium, magnesium and calcium, the salt being preferably chosen from sulphates, phosphates, carbonates, oxalates and silicates, or calcium stearate, alumina, cellulose powder, sawdust and / or calcium silicate.
- a salt of a metal chosen from aluminum, potassium, magnesium and calcium the salt being preferably chosen from sulphates, phosphates, carbonates, oxalates and silicates, or calcium stearate, alumina, cellulose powder, sawdust and / or calcium silicate.
- the complex of the invention has applications in many other industrial fields, such as in furniture, for example in the manufacture of furniture, objects or decorative panels, such as in the civil engineering and public works sector, for example as filling mortar, laying and jointing mortar, as a material for the manufacture of road panels, for the manufacture of pavers and curbs.
- objects or decorative panels such as in the civil engineering and public works sector, for example as filling mortar, laying and jointing mortar, as a material for the manufacture of road panels, for the manufacture of pavers and curbs.
- Figures 1-5 show the infrared spectra of a control cellulose, a complex of the invention and the superposition of these spectra with others of chemical entities likely to be found in one or both samples
- Figures 6 and 7 show the X-ray diffraction spectra of the cellulose control and a complex of the invention.
- Example 1 Process for the Preparation of an Organo-mineral Complex of the Invention
- the complex is prepared from cellulosic waste from recycling, landfills, waste paper, cardboard, newspapers, magazines or other cellulosic waste. It could just as easily be made from paper sludge or waste paper.
- Infrared spectroscopy in total reflection attenuated on diamond crystal was performed on a sample of paste obtained according to the invention in Example 1 and a starting cellulose sample obtained by dispersing the starting waste in water, said cellulose control, for comparison.
- the IR spectra are shown in FIG. 1 for the cellulose control, and 2 for the paste of example 1.
- FIG. 3 is superimposed on the spectrum of FIG. 1 (cellulose control), the spectra of cellulose, calcite (calcium carbonate) and kaolinite (hydrated aluminum silicate, of formula AI 2 Si 2 0 5 (OH) 4 ) from the spectral libraries of the analysis laboratory.
- FIG. 4 the same spectra of calcite and kaolinite are superimposed on the spectrum of FIG. 2 (invention) as in FIG.
- FIG. 5 the spectra of FIGS. 1 and 2 are superimposed.
- FIGS. 1 and 3 show the following characteristic bands:
- FIGS. 2 and 4 show the following characteristic strips:
- the analyzes were performed on a 40-300 kV X-ray beam dosimeter apparatus, at a wavelength of 1.5406 nm.
- FIG. 6 shows the X-ray diffraction spectrum of the cellulose control.
- FIG. 7 shows the X-ray diffraction spectrum of the calcio-cellulosic complex of the invention of Example 1.
- This calcite is formed by a reaction of the carbon dioxide released during the exothermic reaction of quicklime on cellulose, the pyranic cycle on Ca (OH) 2 from the hydration of quicklime in the reaction medium.
- Example 1 The calcio-cellulosic complex obtained in Example 1 in paste form has many applications, some of which are hereinafter illustrated.
- compositions based on a paste of the invention and cement is prepared in proportions to be determined according to the desired result, and then calcium or zinc stearate is added in a proportion 0.1 to 0.5% (w / w) as a water repellent.
- the composition thus prepared can be projected.
- the paste of the invention is dried to obtain a powder, which is then mixed with cement, in proportions to be determined according to the desired result.
- a powder In the form of a powder, it can be added as an adjuvant for the preparation of a cement or a plaster to be tempered, which can in particular be used for the manufacture of a building element or panel having a high power of thermal and sound insulation.
Abstract
The invention relates to a calcium-cellulose organo-mineral complex capable of being obtained by reaction of quicklime over cellulose, in aqueous suspension, to the method of obtaining same and to the applications thereof.
Description
COMPLEXE ORGANO-MINERAL CALCIO-CELLULOSIQUE, PROCEDE DE PREPARATION CALCIO-CELLULOSIC ORGANO-MINERAL COMPLEX, PROCESS FOR PREPARATION
ET APPLICATIONS AND APPLICATIONS
L'invention concerne un complexe organo-minéral susceptible d'être obtenu par dégradation chimique de la cellulose, un procédé de production d'un tel complexe et les applications de celui-ci, en particulier dans la construction. The invention relates to an organo-mineral complex obtainable by chemical degradation of cellulose, a process for producing such a complex and the applications thereof, in particular in construction.
La cellulose, le polymère organique le plus abondant de la biosphère, est un polysaccharide constitué d'unités de glucose reliées par des liaisons β(1-4) et dont le nombre peut atteindre plusieurs milliers. C'est un polymère linéaire dont l'enchaînement lui confère une structure secondaire qui peut s'assimiler à une hélice constituée d'unités dimériques de cellulobiose à chaque pas de l'hélice, et dont la structure tertaire est un faisceau de chaînes polysaccharidiques disposées parallèlement les unes aux autres et dans la même sens de l'extrémité non réductrice vers l'extrémité réductrice, formant des microfibrilles. Dans cette structure, entrent en jeu un nombre considérable de liaisons hydrogène intramoléculaires et intermoléculaires, à l'origine de la résistance mécanique remarquable de la cellulose. Cellulose, the most abundant organic polymer in the biosphere, is a polysaccharide made up of glucose units connected by β (1-4) bonds, the number of which can reach several thousand. It is a linear polymer whose linking gives it a secondary structure which can be assimilated to a helix consisting of dimeric units of cellulobiosis at each step of the helix, and whose tertiary structure is a bundle of polysaccharide chains arranged. parallel to each other and in the same direction from the non-reducing end to the reducing end, forming microfibrils. In this structure come into play a considerable number of intramolecular and intermolecular hydrogen bonds, at the origin of the remarkable mechanical strength of cellulose.
Compte tenu de son abondance naturelle, la cellulose est depuis très longtemps exploitée dans différents domaines industriels, ainsi que ses produits de dégradation, à différents stades. Given its natural abundance, cellulose has long been exploited in various industrial fields, as well as its degradation products, at different stages.
A titre d'exemple, on connaît, selon le document US5538553A, un procédé pour la fabrication d'un matériau pour le bâtiment, comprenant le mélange d'une suspension aqueuse de cellulose, d'une suspension aqueuse de chaux et d'une solution aqueuse d'un sulfate, de préférence d'un sulfate de fer. La chaux mise en réaction est à l'état hydraté et, en présence d'un sulfate, sa réaction avec la cellulose conduit à la formation d'une pâte qui est utilisée en l'état, associée à des cendres volcaniques et un liant hydraulique comme le ciment, pour obtenir un matériau possédant de bonnes propriétés mécaniques. By way of example, according to the document US5538553A, there is known a process for the manufacture of a material for the building, comprising mixing an aqueous suspension of cellulose, an aqueous suspension of lime and a solution aqueous sulfate, preferably iron sulfate. The lime reacted is in the hydrated state and, in the presence of a sulphate, its reaction with cellulose leads to the formation of a paste which is used in the state, associated with volcanic ash and a hydraulic binder like cement, to obtain a material with good mechanical properties.
Le document FR2700163A1 décrit un procédé pour la fabrication d'un matériau de construction qui est obtenu par un mélange réactionnel comprenant une suspension de fibres cellulosiques provenant de déchets de papier et de carton, de la chaux et un sulfate mono- ou trivalent de sels métalliques comme l'aluminium, en quantités stoechiométriques. De telles conditions conduisent à la formation d'un ligno-sulfo-aluminate de calcium sous forme de pâte qui est pressée puis séchée, ou moulée, puis est utilisée pour fabriquer un élément de construction présentant des propriétés mécaniques et d'isolation phonique et thermique intéressantes.
Le demandeur a mis au point un procédé de dégradation chimique de la cellulose mettant en œuvre de la chaux vive, et non de la chaux hydratée, conduisant à un complexe organo-minéral différent de ceux connus. Le demandeur a au surplus constaté que ce complexe possède des propriétés mécaniques et physico-chimiques exceptionnelles qui en font un matériau de base de choix notamment pour la construction, mais aussi pour d'autres domaines. FR2700163A1 discloses a process for the manufacture of a building material which is obtained by a reaction mixture comprising a suspension of cellulosic fibers from waste paper and cardboard, lime and a mono- or trivalent sulfate of metal salts like aluminum, in stoichiometric quantities. Such conditions lead to the formation of a calcium ligno-sulphoaluminate in the form of a paste which is pressed and then dried, or molded, and is then used to manufacture a structural element having mechanical and sound and thermal insulation properties. interesting. The Applicant has developed a method of chemical degradation of cellulose using quicklime, not hydrated lime, resulting in an organo-mineral complex different from those known. The applicant has moreover noted that this complex possesses exceptional mechanical and physicochemical properties which make it a basic material of choice, particularly for construction, but also for other areas.
En particulier, par rapport aux matériaux de l'art antérieur précité, le matériau de l'invention permet d'obtenir des éléments de construction plus performants comme le supportent quelques unes des propriétés de tels éléments, listées ci-dessous : In particular, with respect to the materials of the aforementioned prior art, the material of the invention makes it possible to obtain more efficient construction elements, as some of the properties of such elements, listed below:
- Résistance mécanique élevée, - High mechanical resistance,
- Forts pouvoirs isolants thermique, avec une conductivité thermique lambda de l'ordre de 0,1 à 0,7 W/m°C selon l'épaisseur de l'élément, et phonique, avec une atténuation acoustique de l'ordre de 30 à 80 dBa selon l'épaisseur de l'élément, - Strong thermal insulating powers, with a lambda thermal conductivity of the order of 0.1 to 0.7 W / m ° C depending on the thickness of the element, and phonic, with an acoustic attenuation of the order of 30 at 80 dBa depending on the thickness of the element,
- Rigidité élevée, avec un module d'élasticité variant de 0,9 à 4,3 Mpa selon l'épaisseur de l'élément. - High rigidity, with a modulus of elasticity ranging from 0.9 to 4.3 MPa depending on the thickness of the element.
C'est en outre un matériau très léger, en particulier plus léger que le bois ou l'aggloméré, il peut absorber son propre poids en eau sans se déformer, il peut aussi être teinté dans la masse et il est imputrescible. It is also a very light material, especially lighter than wood or agglomerate, it can absorb its own weight in water without deformation, it can also be tinted in the mass and it is rotproof.
Du point de vue environnemental, il est obtenu à partir d'une matière naturelle inépuisable, il est totalement recyclable, son procédé de fabrication ne génère aucun produit toxique et les déchets de fabrication peuvent être réintroduits dans le processus industriel de fabrication. From the environmental point of view, it is obtained from an inexhaustible natural material, it is completely recyclable, its manufacturing process generates no toxic products and the manufacturing waste can be reintroduced in the industrial process of manufacture.
Ainsi, l'invention concerne un complexe organo-minéral calcio- cellulosique susceptible d'être obtenu par réaction de la chaux vive sur de la cellulose, en suspension aqueuse. Thus, the invention relates to a calcio-cellulosic organo-mineral complex that can be obtained by reaction of quicklime on cellulose, in aqueous suspension.
Selon l'invention, la chaux vive réagit avec la cellulose, à une vitesse bien plus élevée que celle de l'hydratation de la chaux vive dans le milieu aqueux, mais les deux réactions, ayant des cinétiques différentes, co-existent. According to the invention, quicklime reacts with cellulose at a much higher rate than the hydration of quicklime in the aqueous medium, but the two reactions, having different kinetics, co-exist.
Il se forme un complexe, celui de l'invention, qui est constitué de chaînes polysaccharidiques résultant d'une rupture des liaisons hydrogène intermoléculaires de cellulose et d'une décarboxylation du groupe CH2OH (carbone 6) porté par le carbone 5 des unités glucose de la cellulose, associées à de la calcite CaC03. Celle-ci est formée par la réaction du gaz carbonique libéré par ladite décarboxylation sur le Ca(OH)2 provenant de l'hydratation de la chaux vive dans le milieu réactionnel. La
rupture des liaisons hydrogène intermoléculaires et la décarboxylation du groupe CH2OH porté par le carbone 5 des unités glucose peuvent être concomitantes. A complex is formed, that of the invention, which consists of polysaccharide chains resulting from a rupture of the intermolecular hydrogen bonds of cellulose and a decarboxylation of the CH 2 OH group (carbon 6) carried by the carbon 5 of the units. glucose of cellulose, associated with calcite CaCO 3 . This is formed by the reaction of the carbon dioxide released by said decarboxylation on Ca (OH) 2 from the hydration of quicklime in the reaction medium. The intermolecular hydrogen bond breaking and decarboxylation of the CH 2 OH group carried by the carbon 5 of glucose units may be concomitant.
Avantageusement, dans ce complexe, au moins 50% des extrémités non réductrices de la cellulose sont décarboxylés selon la décarboxylation décrite ci- dessus, de préférence au moins 75%, voire au moins 90%, ou même la totalité. Avantageusement, et en combinaison ou non avec la caractéristique précédente, au moins 50% des liaisons hydrogène intermoléculaires de la cellulose sont rompues, de préférence au moins 75%, voire au moins 90%, ou même la totalité. Advantageously, in this complex, at least 50% of the non-reducing ends of the cellulose are decarboxylated according to the decarboxylation described above, preferably at least 75%, or even at least 90%, or even all. Advantageously, and in combination or not with the preceding characteristic, at least 50% of the intermolecular hydrogen bonds of the cellulose are broken, preferably at least 75%, or even at least 90%, or even all.
La décarboxylation du groupe CH2OH porté par le carbone 5 des unités glucose nécessite la rupture de la liaison hydrogène intramoléculaire entre l'atome d'hydrogène du groupe hydroxyle en C6 de l'unité glucose concernée par la décarboxylation, et l'atome d'oxygène du cycle pyranique de l'unité glucose suivante. Au cours de la formation du complexe, d'autres liaisons hydrogène intramoléculaires peuvent aussi être rompues, sans décarboxylation subséquente. Decarboxylation of the CH 2 OH group carried by the carbon of the glucose units requires the rupture of the intramolecular hydrogen bond between the hydrogen atom of the C6 hydroxyl group of the glucose unit concerned by the decarboxylation, and the atom of oxygen from the pyranic ring of the next glucose unit. During complex formation, other intramolecular hydrogen bonds can also be broken, without subsequent decarboxylation.
La structure du complexe de l'invention est supportée par les analyses effectuées dont certaines sont illustrées à l'exemple 2. The structure of the complex of the invention is supported by the analyzes carried out, some of which are illustrated in Example 2.
L'invention concerne aussi un procédé de préparation d'un complexe calcio-cellulosique, selon lequel on fait réagir, en suspension aqueuse, de la chaux vive sur de la cellulose et on obtient le complexe sous forme d'une pâte. The invention also relates to a process for the preparation of a calcio-cellulosic complex, in which aqueous lime is reacted in aqueous suspension on cellulose and the complex is obtained in the form of a paste.
La cellulose à traiter peut être sous toute forme, prétraitée ou non, et provenir de toute source. Elle est de préférence sous forme de fibres de cellulose, elle peut provenir de tous déchets papetiers et de cartons, tels que déchets cellulosiques provenant du recyclage, en déchetteries, de vieux papiers, cartons, journaux, revues ou autres déchets cellulosiques. Elle peut aussi provenir de boues papetières ou déchets de papèteries. The cellulose to be treated can be in any form, pretreated or not, and come from any source. It is preferably in the form of cellulose fibers, it can come from all papermaking waste and cardboard, such as cellulosic waste from recycling, landfills, waste paper, cardboard, newspapers, magazines or other cellulosic waste. It can also come from paper sludge or waste paper.
La mise en œuvre du procédé est simple, et le complexe est obtenu quel que soit l'ordre d'ajout des ingrédients, à savoir, eau, chaux vive et cellulose. Leur ajout peut être concomitant. Selon une variante avantageuse d'un procédé de l'invention, on verse de la chaux vive dans de l'eau, puis on introduit la cellulose. Le rapport massique de CaO à la cellulose est de préférence compris entre 30/70 et 70/30. Avantageusement, il est de 50/50, la quantité de chaux vive mise en réaction étant la même que celle de la cellulose à traiter. The implementation of the process is simple, and the complex is obtained regardless of the order of addition of the ingredients, namely, water, quicklime and cellulose. Their addition may be concomitant. According to an advantageous variant of a process of the invention, quicklime is poured into water and the cellulose is then introduced. The weight ratio of CaO to cellulose is preferably between 30/70 and 70/30. Advantageously, it is 50/50, the amount of quicklime reacted being the same as that of the cellulose to be treated.
A la pâte obtenue selon ce procédé, divers ingrédients peuvent être ajoutés, en fonction des applications recherchées, comme un sel d'un métal choisi parmi l'aluminium, le potassium, le magnésium et le calcium, le sel étant de préférence choisi parmi les sulfates, les phosphates, les carbonates, les oxalates et les
silicates, ou bien comme du stéarate de calcium, de l'alumine, de la poudre de cellulose, de la sciure de bois et/ou du silicate de calcium. In the paste obtained according to this process, various ingredients may be added, depending on the desired applications, such as a salt of a metal chosen from aluminum, potassium, magnesium and calcium, the salt being preferably chosen from sulphates, phosphates, carbonates, oxalates and silicates, or calcium stearate, alumina, cellulose powder, sawdust and / or calcium silicate.
Du fait de ses remarquables propriétés, en plus du secteur de la construction, le complexe de l'invention trouve des applications dans beaucoup d'autres domaines industriels, comme dans l'ameublement, par exemple dans la fabrication de meubles, d'objets ou de panneaux décoratifs, comme dans le secteur du génie civil et des travaux publics, par exemple comme mortier de remplissage, mortier de pose et de jointement, comme matériau de fabrication de panneaux de voirie, pour la fabrication de pavés et bordures de trottoir. Ces applications ne sont bien entendu pas limitatives. Because of its remarkable properties, in addition to the construction sector, the complex of the invention has applications in many other industrial fields, such as in furniture, for example in the manufacture of furniture, objects or decorative panels, such as in the civil engineering and public works sector, for example as filling mortar, laying and jointing mortar, as a material for the manufacture of road panels, for the manufacture of pavers and curbs. These applications are of course not limiting.
D'autres caractéristiques et avantages du complexe de l'invention, sont illustrés dans les exemples qui suivent et à l'appui des figures 1-7 où : Other characteristics and advantages of the complex of the invention are illustrated in the examples which follow and in support of FIGS. 1-7 where:
les figures 1-5 représentent les spectres en infrarouge d'une cellulose témoin, d'un complexe de l'invention et la superposition de ces spectres avec d'autres d'entités chimiques susceptibles d'être retrouvées dans l'un ou les deux échantillons, Figures 1-5 show the infrared spectra of a control cellulose, a complex of the invention and the superposition of these spectra with others of chemical entities likely to be found in one or both samples
les figures 6 et 7 représentent les spectres de diffraction aux rayons X du témoin cellulose et d'un complexe de l'invention. Exemple 1 : Procédé de préparation d'un complexe organo-minéral de l'invention Figures 6 and 7 show the X-ray diffraction spectra of the cellulose control and a complex of the invention. Example 1 Process for the Preparation of an Organo-mineral Complex of the Invention
Dans cet exemple, le complexe est préparé à partir de déchets cellulosiques provenant du recyclage, en déchetteries, de vieux papiers, cartons, journaux, revues ou autres déchets cellulosiques. Il pourrait tout aussi bien être fabriqué à partir de boues papetières ou déchets de papèteries. In this example, the complex is prepared from cellulosic waste from recycling, landfills, waste paper, cardboard, newspapers, magazines or other cellulosic waste. It could just as easily be made from paper sludge or waste paper.
Dans un mélangeur ou un malaxeur ou tout autre appareil de mélange de 1 à 5 m3, on introduit successivement : In a mixer or a kneader or any other mixing apparatus of 1 to 5 m 3 , one successively introduces:
- 1000 litres d'eau, - 1000 liters of water,
puis sous agitation légère, 180 kilogrammes d'oxyde de calcium, sous forme poudreuse et d'une pureté supérieure à 95% 180 kilograms of calcium oxide in powder form and with a purity of more than 95%
(exprimée en CaO) ; le temps d'ajout doit être inférieur à 5 minutes, (expressed in CaO); the addition time must be less than 5 minutes,
180 kilogrammes de déchets cellulosiques définis tel que précédemment, tout en maintenant l'agitation, éventuellement plus forte, pendant 20 minutes après l'ajout des déchets. 180 kilograms of cellulosic waste defined as above, while maintaining agitation, possibly stronger, for 20 minutes after the addition of waste.
FEU I LLE RECTI FI ÉE (RÈG LE 91) ISA/ EP
Au cours de cette dernière phase, la température du milieu réactionnel s'élève à 75-80°C ; il s'agit effectivement d'une réaction exothermique. FIRE I LLE RECTI FIED (RULE 91) ISA / EP During this last phase, the temperature of the reaction medium is 75-80 ° C .; it is indeed an exothermic reaction.
On obtient 1400 kg d'une pâte de l'invention. Exemple 2 : Caractérisation du complexe organo-minéral de l'invention 1400 kg of a paste of the invention are obtained. Example 2 Characterization of the Organomineral Complex of the Invention
Analyse par spectroscopie infrarouge : Infrared spectroscopy analysis:
Une spectroscopie infrarouge en réflexion totale atténuée sur cristal de diamant a été réalisée sur un échantillon de pâte obtenue selon l'invention à l'exemple 1 et un échantillon de cellulose de départ obtenue par dispersion des déchets de départ dans de l'eau, dit témoin cellulose, à titre de comparaison. Infrared spectroscopy in total reflection attenuated on diamond crystal was performed on a sample of paste obtained according to the invention in Example 1 and a starting cellulose sample obtained by dispersing the starting waste in water, said cellulose control, for comparison.
Les spectres IR sont reportés aux figures 1 pour le témoin cellulose, et 2 pour la pâte de l'exemple 1. The IR spectra are shown in FIG. 1 for the cellulose control, and 2 for the paste of example 1.
Sur la figure 3, sont superposés sur le spectre de la figure 1 (témoin cellulose), les spectres de la cellulose, de la calcite (carbonate de calcium) et de la kaolinite (silicate d'aluminium hydraté, de formule AI2Si205(OH)4) issus des bibliothèques spectrales du laboratoire d'analyse. FIG. 3 is superimposed on the spectrum of FIG. 1 (cellulose control), the spectra of cellulose, calcite (calcium carbonate) and kaolinite (hydrated aluminum silicate, of formula AI 2 Si 2 0 5 (OH) 4 ) from the spectral libraries of the analysis laboratory.
Sur la figure 4, sont superposés sur le spectre de la figure 2 (invention), les mêmes spectres de la calcite et de la kaolinite que sur la figure 3. In FIG. 4, the same spectra of calcite and kaolinite are superimposed on the spectrum of FIG. 2 (invention) as in FIG.
Sur la figure 5, sont superposés les spectres des figures 1 et 2. Concernant l'échantillon de témoin cellulose, on observe sur les figures 1 et 3, les bandes caractéristiques suivantes : In FIG. 5, the spectra of FIGS. 1 and 2 are superimposed. For the cellulose control sample, FIGS. 1 and 3 show the following characteristic bands:
Bandes caractéristiques de la présence d'un sucre de type cellulose à 3345, 2895, 1057 et 1032 cm"1 ; Bands characteristic of the presence of a cellulose type sugar at 3345, 2895, 1057 and 1032 cm -1 ;
Bandes caractéristiques de la présence d'un carbonate de calcium à 1429 et 874 cm"1 ; Strips characteristic of the presence of a calcium carbonate at 1429 and 874 cm -1 ;
Bandes caractéristique de la présence d'un silicate de type kaolinite à 3692, 3619, 1107, 541 et 470 cm"1. Tapes characteristic of the presence of kaolinite silicate at 3692, 3619, 1107, 541 and 470 cm- 1 .
Concernant l'échantillon de pâte de l'invention, on observe sur les figures 2 et 4, les bandes caractéristiques suivantes : With regard to the dough sample of the invention, FIGS. 2 and 4 show the following characteristic strips:
- Bandes caractéristiques de la présence de fonctions hydroxyle à - Characteristic bands of the presence of hydroxyl functions at
3413 cm"1 ; 3413 cm -1 ;
Bandes caractéristiques de la présence d'un carbonate de calcium à 1431 et 874 cm"1 ; Characteristic bands of the presence of calcium carbonate at 1431 and 874 cm -1 ;
Bandes caractéristique de la présence d'un silicate à 3629, 1112, 541 et 470 cm"1.
On n'observe pas les bandes caractéristiques de la cellulose, alors que subsistent les bandes caractéristiques de la fonction hydroxyle. De plus, un carbonate de calcium différent s'est formé dans la pâte de l'invention. Tapes characteristic of the presence of a silicate at 3629, 1112, 541 and 470 cm -1 . The characteristic bands of cellulose are not observed, while the bands characteristic of the hydroxyl function remain. In addition, a different calcium carbonate was formed in the paste of the invention.
Il convient de préciser que la présence d'entités est observée sans lien directe avec l'invention. Elles proviennent ou sont des résidus des déchets de cellulose de départ. A titre d'exemple, les silicates sont présents dans la pâte à papier. It should be noted that the presence of entities is observed without any direct link with the invention. They come from or are residues of the starting cellulose waste. For example, silicates are present in the pulp.
La figure 5 confirme les observations ci-dessus. Figure 5 confirms the observations above.
Analyse par diffraction aux rayons X : X-ray diffraction analysis:
Les analyses ont été effectuées sur un appareil 40-300 kV X-ray beam dosimeter, à une longueur d'ondes de 1,5406 nm. The analyzes were performed on a 40-300 kV X-ray beam dosimeter apparatus, at a wavelength of 1.5406 nm.
Sur la figure 6, est reporté le spectre de diffraction aux rayons X du témoin cellulose. FIG. 6 shows the X-ray diffraction spectrum of the cellulose control.
Sur la figure 7, est reporté le spectre de diffraction aux rayons X du complexe calcio-cellulosique de l'invention de l'exemple 1. FIG. 7 shows the X-ray diffraction spectrum of the calcio-cellulosic complex of the invention of Example 1.
Par comparaison des deux spectres, on observe sur celui du complexe de l'invention, une bande importante entre 21 et 25 pour l'angle 2Θ, caractéristique de la présence de calcite différente de celle contenue dans le témoin cellulose. By comparison of the two spectra, there is observed on that of the complex of the invention, a significant band between 21 and 25 for the angle 2Θ, characteristic of the presence of calcite different from that contained in the control cellulose.
Cette calcite est formée par une réaction du gaz carbonique libéré lors de la réaction exothermique de la chaux vive sur la cellulose, du cycle pyranique sur le Ca(OH)2 provenant de l'hydratation de la chaux vive dans le milieu réactionnel. This calcite is formed by a reaction of the carbon dioxide released during the exothermic reaction of quicklime on cellulose, the pyranic cycle on Ca (OH) 2 from the hydration of quicklime in the reaction medium.
Exemple 3 : Application du complexe organo-minéral de l'invention à la fabrication d'un matériau de construction Example 3 Application of the organomineral complex of the invention to the manufacture of a building material
Dans un mélangeur ou un malaxeur ou tout autre appareil de mélange on introduit successivement : In a mixer or a kneader or any other mixing device, one successively introduces:
De l'eau, Some water,
250 kilogrammes de déchets cellulosiques définis tel que précédemment, 250 kilograms of cellulosic waste defined as above,
puis sous agitation légère, 300 kilogrammes d'oxyde de calcium, sous forme poudreuse et d'une pureté supérieure à 95% 300 kilograms of calcium oxide in powder form and with a purity of more than 95%
(exprimée en CaO), (expressed in CaO),
- du sulfate d'aluminium (AI2(S04)3, 14H20). aluminum sulphate (Al 2 (SO 4 ) 3 , 14H 2 O).
Après filtration, on obtient une pâte de l'invention. After filtration, a paste of the invention is obtained.
Cette pâte est compactée puis moulée pour réaliser un élément de construction.
Exemple 4 : Autres applications du complexe organo-minéral de l'invention This paste is compacted and then molded to make a construction element. Example 4 Other Applications of the Organomineral Complex of the Invention
Le complexe calcio-cellulosique obtenu à l'exemple 1 sous forme de pâte trouve de multiples applications, dont certaines sont ci-après illustrées. The calcio-cellulosic complex obtained in Example 1 in paste form has many applications, some of which are hereinafter illustrated.
II peut être utilisé en enduit extérieur : on prépare une composition à base d'une pâte de l'invention et de ciment, dans des proportions à déterminer en fonction du résultat recherché, puis on ajoute du stéarate de calcium ou de zinc dans une proportion de 0,1 à 0,5% (m/m) en tant qu'agent hydrofuge. La composition ainsi préparée peut être projetée. It may be used as an external coating: a composition based on a paste of the invention and cement is prepared in proportions to be determined according to the desired result, and then calcium or zinc stearate is added in a proportion 0.1 to 0.5% (w / w) as a water repellent. The composition thus prepared can be projected.
II peut aussi être utilisé sous forme de poudre : la pâte de l'invention est séchée pour obtenir une poudre, qui est ensuite mélangée à du ciment, dans des proportions à déterminer en fonction du résultat recherché. It can also be used in powder form: the paste of the invention is dried to obtain a powder, which is then mixed with cement, in proportions to be determined according to the desired result.
Sous forme de poudre, il peut être ajouté comme adjuvant pour la préparation d'un ciment ou d'un plâtre à gâcher, qui peut notamment être utilisé pour la fabrication d'un élément de construction ou d'un panneau présentant un pouvoir élevé d'isolation thermique et phonique. In the form of a powder, it can be added as an adjuvant for the preparation of a cement or a plaster to be tempered, which can in particular be used for the manufacture of a building element or panel having a high power of thermal and sound insulation.
Ainsi d'autres objets de l'invention sont les suivants : Thus other objects of the invention are the following:
- un procédé de fabrication d'un matériau composite, selon lequel on prépare une pâte d'un complexe calcio-cellulosique tel que défini précédemment, on met en forme ladite pâte et on sèche le matériau ainsi obtenu ; a method of manufacturing a composite material, according to which a paste of a calcio-cellulosic complex as defined above is prepared, said paste is shaped and the material thus obtained is dried;
- les utilisations d'un matériau tel qu'obtenu selon le procédé, pour la réalisation de plaques, parpaings, planches, briques, crépis de façade ; the uses of a material as obtained according to the process, for the production of plates, blocks, planks, bricks, plaster of facade;
- les utilisations d'un matériau tel qu'obtenu selon le procédé ci-dessus, dans le domaine du bâtiment, des travaux publics, du génie civil, de l'ameublement et de la décoration ; - uses of a material as obtained by the above process, in the field of building, public works, civil engineering, furniture and decoration;
- un élément de construction ou de décoration fabriqué par moulage d'une pâte telle qu'obtenue selon l'invention.
- A construction element or decoration manufactured by molding a paste as obtained according to the invention.
Claims
1. Complexe organo-minéral calcio-cellulosique susceptible d'être obtenu par réaction de la chaux vive sur de la cellulose, en suspension aqueuse. 1. calcio-cellulosic organo-mineral complex obtainable by reaction of quicklime on cellulose, in aqueous suspension.
2. Complexe selon la revendication 1, caractérisé en ce qu'il est constitué de chaînes polysaccharidiques résultant d'une rupture des liaisons hydrogène intermoléculaires de cellulose et d'une décarboxylation du groupe CH2OH porté par le carbone 5 des unités glucose de la cellulose, associées à de la calcite CaC03. 2. Complex according to claim 1, characterized in that it consists of polysaccharide chains resulting from a rupture of the intermolecular hydrogen bonding of cellulose and a decarboxylation of the CH 2 OH group carried by the carbon 5 glucose units of the cellulose, associated with calcite CaCO 3 .
3. Complexe selon la revendication 2, caractérisé en ce que la calcite est formée par la réaction du gaz carbonique libéré par ladite décarboxylation sur le Ca(OH)2 provenant de l'hydratation de la chaux vive dans le milieu réactionnel. 3. Complex according to claim 2, characterized in that the calcite is formed by the reaction of the carbon dioxide released by said decarboxylation on Ca (OH) 2 from the hydration of quicklime in the reaction medium.
4. Procédé de préparation d'un complexe calcio-cellulosique, caractérisé en ce qu'on ajoute de la chaux vive dans de l'eau, puis on ajoute de la cellulose et on obtient le complexe sous forme d'une pâte. 4. Process for preparing a calcio-cellulosic complex, characterized in that quicklime is added in water, then cellulose is added and the complex is obtained in the form of a paste.
5. Procédé selon la revendication 4, caractérisé en ce que la cellulose est sous forme de fibres de cellulose, provenant notamment de déchets papetiers. 5. Method according to claim 4, characterized in that the cellulose is in the form of cellulose fibers, especially from paper waste.
6. Procédé selon la revendication 4 ou 5, caractérisé en ce que rapport massique de CaO à la cellulose est compris entre 30/70 et 70/30. 6. Method according to claim 4 or 5, characterized in that mass ratio of CaO to cellulose is between 30/70 and 70/30.
7. Procédé selon l'une quelconque des revendications 4 à 6, caractérisé en ce qu'on ajoute à la pâte au moins un sel d'un métal choisi parmi l'aluminium, le potassium, le magnésium et le calcium. 7. Process according to any one of Claims 4 to 6, characterized in that at least one salt of a metal chosen from aluminum, potassium, magnesium and calcium is added to the pulp.
8. Procédé selon la revendication 7, caractérisé en ce que le sel est choisi parmi les sulfates, les phosphates, les carbonates, les oxalates et les silicates. 8. Process according to claim 7, characterized in that the salt is chosen from sulphates, phosphates, carbonates, oxalates and silicates.
9. Procédé selon l'une quelconque des revendications 4 à 8, caractérisé en ce qu'on ajoute à la pâte du stéarate de calcium, de l'alumine, de la poudre de cellulose, de la sciure de bois et/ou du silicate de calcium. 9. Process according to any one of claims 4 to 8, characterized in that calcium stearate, alumina, cellulose powder, sawdust and / or silicate are added to the paste. of calcium.
10. Procédé de fabrication d'un matériau composite caractérisé en ce qu'on prépare une pâte d'un complexe calcio-cellulosique selon l'une quelconque des revendications 4 à 9, on met en forme ladite pâte et on sèche le matériau ainsi obtenu. 10. A method of manufacturing a composite material characterized in that a paste of a calcio-cellulosic complex according to any one of claims 4 to 9 is prepared, said paste is shaped and the material thus obtained is dried .
11. Utilisation d'un matériau tel qu'obtenu selon la revendication 10, pour la réalisation de plaques, parpaings, planches, briques, crépis de façade. 11. Use of a material as obtained according to claim 10 for the production of plates, blocks, planks, bricks, plaster facade.
12. Utilisation d'un matériau tel qu'obtenu selon la revendication 10, dans le domaine du bâtiment, des travaux publics, du génie civil, de l'ameublement et de la décoration. 12. Use of a material as obtained according to claim 10, in the field of building, public works, civil engineering, furniture and decoration.
13. Elément de construction ou de décoration fabriqué par moulage d'une pâte telle qu'obtenue selon la revendication 4.
13. Element of construction or decoration manufactured by molding a paste as obtained according to claim 4.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2014/051929 WO2016012662A1 (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
| EP14750776.8A EP3172179A1 (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
| CN201480080895.2A CN106660880A (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2014/051929 WO2016012662A1 (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016012662A1 true WO2016012662A1 (en) | 2016-01-28 |
Family
ID=51352717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2014/051929 WO2016012662A1 (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3172179A1 (en) |
| CN (1) | CN106660880A (en) |
| WO (1) | WO2016012662A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102464540B1 (en) * | 2021-12-28 | 2022-11-09 | 김준형 | pH-responsive Cement Admixture Capable of Self-recovery of Cement Composite |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB638501A (en) * | 1946-10-25 | 1950-06-07 | John Frederick Barrow | Improvements in or relating to building material |
| GB907043A (en) * | 1960-06-03 | 1962-10-03 | Karoly Szepesi | Improvements in and relating to building blocks |
| AU540536B2 (en) * | 1979-04-17 | 1984-11-22 | Robert Gordon Leigh Bohm | Building panel material |
| EP0262031A1 (en) * | 1986-09-18 | 1988-03-30 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | High porosity silicocalcareous mass for gas storage, and production process |
| US5118219A (en) * | 1991-03-21 | 1992-06-02 | Chemstar Lime Company | Method of capping tailings ponds |
| DE4110829A1 (en) * | 1991-04-04 | 1992-10-08 | Hiendl Heribert | Moulded constructional part esp. board - made from mixt. of waste paper and mineral binder |
| FR2700163A1 (en) * | 1993-01-05 | 1994-07-08 | Decros Raymond Rene Jean | Method for manufacturing a building material. |
| US5538553A (en) * | 1995-12-18 | 1996-07-23 | Burgand; Yves | Organomineral paste and method of use as construction material |
-
2014
- 2014-07-24 CN CN201480080895.2A patent/CN106660880A/en active Pending
- 2014-07-24 EP EP14750776.8A patent/EP3172179A1/en not_active Withdrawn
- 2014-07-24 WO PCT/FR2014/051929 patent/WO2016012662A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB638501A (en) * | 1946-10-25 | 1950-06-07 | John Frederick Barrow | Improvements in or relating to building material |
| GB907043A (en) * | 1960-06-03 | 1962-10-03 | Karoly Szepesi | Improvements in and relating to building blocks |
| AU540536B2 (en) * | 1979-04-17 | 1984-11-22 | Robert Gordon Leigh Bohm | Building panel material |
| EP0262031A1 (en) * | 1986-09-18 | 1988-03-30 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | High porosity silicocalcareous mass for gas storage, and production process |
| US5118219A (en) * | 1991-03-21 | 1992-06-02 | Chemstar Lime Company | Method of capping tailings ponds |
| DE4110829A1 (en) * | 1991-04-04 | 1992-10-08 | Hiendl Heribert | Moulded constructional part esp. board - made from mixt. of waste paper and mineral binder |
| FR2700163A1 (en) * | 1993-01-05 | 1994-07-08 | Decros Raymond Rene Jean | Method for manufacturing a building material. |
| US5538553A (en) * | 1995-12-18 | 1996-07-23 | Burgand; Yves | Organomineral paste and method of use as construction material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102464540B1 (en) * | 2021-12-28 | 2022-11-09 | 김준형 | pH-responsive Cement Admixture Capable of Self-recovery of Cement Composite |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3172179A1 (en) | 2017-05-31 |
| CN106660880A (en) | 2017-05-10 |
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