WO2013079732A1 - Procédé de durcissage à l'air pour obtenir des pièces préfabriquées à matrices liantes, matrices et pièces préfabriquées ainsi obtenues, et leur utilisation - Google Patents

Procédé de durcissage à l'air pour obtenir des pièces préfabriquées à matrices liantes, matrices et pièces préfabriquées ainsi obtenues, et leur utilisation Download PDF

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Publication number
WO2013079732A1
WO2013079732A1 PCT/ES2011/070826 ES2011070826W WO2013079732A1 WO 2013079732 A1 WO2013079732 A1 WO 2013079732A1 ES 2011070826 W ES2011070826 W ES 2011070826W WO 2013079732 A1 WO2013079732 A1 WO 2013079732A1
Authority
WO
WIPO (PCT)
Prior art keywords
prefabricated
carbonation
prefabricated parts
matrices
matrix according
Prior art date
Application number
PCT/ES2011/070826
Other languages
English (en)
Spanish (es)
Inventor
Miguel Bermejo Sotillo
Carlos Rodriguez Navarro
Encarnación RUIZ AGUDO
Kerstin Elert
Original Assignee
Geosilex Trenza Metal, S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Geosilex Trenza Metal, S.L. filed Critical Geosilex Trenza Metal, S.L.
Priority to PCT/ES2011/070826 priority Critical patent/WO2013079732A1/fr
Publication of WO2013079732A1 publication Critical patent/WO2013079732A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • C04B28/12—Hydraulic lime
    • 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 present invention relates to an air setting procedure for obtaining prefabricated pieces with cementitious matrices, the matrices used in this procedure and the prefabricated parts obtained by the application of the procedure, for use, among other fields, in construction , public works or street furniture.
  • the process of the invention consists of an air setting procedure, accelerated by forced carbonation in autoclave, of prefabricated pieces with cementitious matrices that include calcium idroxide, from artificial hydraulic limes and / or aerial, preferably carbide limes, where the setting speed is increased to a high degree compared to the setting processes known for the addition of carbonic anhydrase as the catalytic accelerator of carbonation.
  • the pieces, demoulded after having been sufficiently endured are placed in an autoclave where the air is removed by vacuum and replaced by CO 2 and water vapor until carbonation.
  • the present procedure in addition to an ultra-fast air setting, allows to obtain prefabricated parts with high mechanical performance at an early age.
  • this refers to matrices for cementitious mixtures based on carbide limes, that is hydrated calcium limes derived from the manufacture of acetylene from calcium carbide, in particular paste nanocals obtained from the residues which are generated in the manufacture of acetylene, also comprising water, pozzolans, aggregates and CO 2 matrices, all of them obtained from industrial waste, obtained from the process of the present invention.
  • the invention relates, according to a third aspect, to prefabricated parts produced from the process of the invention, in any form geometric possible, as well as its use in construction, public works and street furniture.
  • high strength and stability materials are obtained by the transformation of calcium hydroxide, in contact with CO2 and in the presence of certain humidity, in calcium carbonate, of high cementing power.
  • vacuum treated concrete made under vacuum conditions called "vacuum treated concrete", where the concrete is subjected to suction (accompanied or not by a compaction process) immediately after being put in a mold. In this process part of the moisture is extracted leaving a drier concrete that, after a while, will reach a much greater hardness than that of common concrete. This causes a vacuum process to be used in the manufacture of concrete slabs and similar products made with hydraulic presses.
  • US Patent 2046867 “Method of and apparatus for treating concrete” refers to a method for treating concrete that consists of treating the concrete with an excess of water to ensure plasticity and then apply a suction to imitate excess water from the breast of the same and then apply a large compaction pressure.
  • US 4362679 “Method of casting concrete” describes a method for producing carbonated cement-based elements in an accelerated manner. This method consists in vacuum extraction of moisture and gases from an already molded paste based on cement, with different types of aggregates and additives, achieving its compaction. After that, the cement paste is subjected to forced carbonation under an atmosphere of pCO2 of up to 1.5 atm. The forced carbonation of cement-based building elements is also described in US 5,650,562 and US 5,744,078. However, the use of lime as the main binder or of any carbonation accelerator is not contemplated in the cited patents.
  • US Patent 3,149,986 indicates that it is possible to obtain prefabricated elements (artificial stone) made from calcified hydrated lime and dolomitic aggregate with a high tensile strength of 4.27 MPa after subjecting them to forced carbonation during 48 h; while patent GB774.432 indicates that, using similar materials, products with compressive strength of up to 48 MPa are obtained after a forced carbonation period of three weeks.
  • a low shrinkage cement composition proposes the addition of carbamates that release CO2 in an alkaline environment, which could on the one hand accelerate carbonation and on the other reduce the shrinkage of cement elements.
  • European patent EP 0650940 A1 "Inorganic hardening composition” proposes the addition of a compound based on organic carbonic acid (olefinic carbonate, soluble carbonates of amines, carbamic acid or even urea) to prepare inorganic prefabricated products. However, such parts need at least 28 days to achieve an adequate mechanical strength value.
  • the results obtained in the indicated inventions are not satisfactory, especially in regard to the very slow carbonation rate, of days or weeks, since one of the aspects not considered to date is that the slowest reaction that controls the overall kinetics of the carbonation process of Ca (OH) 2 is the dissolution of atmospheric CO2 in the water or in the pores of the lime-based element to be carbonated.
  • this refers to a process that allows to favor carbonation and make it progress more rapidly.
  • the method of accelerated aerial setting by forced carbonation in the autoclave of the invention includes a step of adding a carbonation accelerator and this, in addition, is favored by extracting the air from the mixture to replace it with CO2 and water vapor. dosed in specific concentrations.
  • Said carbonation reaction can be accelerated as proposed in this invention, without having to significantly increase the hardening temperature of the prefabricated parts and pressures of CO2 is relatively lower than those used in the prior art methods, adding carbonic anhydrase to the fresh paste in appropriate proportions.
  • carbonic anhydrase catalyzes the first part of the following reaction, in which carbon dioxide (CO2) in the presence of water (H 2 O) is converted to carbonic acid (H2CO3), which at its Once it dissociates forming bicarbonate and carbonate ions depending on the pH:
  • Carbonic anhydrase increases the dissolution rate of CO2 in water by several orders of magnitude. Each molecule of carbonic anhydrase can catalyze r 1, 4 x 10 6 CO2 molecules per second (Yadavy col. 201 1, CurrentScience, 100, 520-524). Given its high effectiveness, carbon dioxide has found applications in CO2 sequestration in both solution and solid phase (Bond et al. 2001, Energy & Fuels, 15, 309-316; Mirjafariy col., 2007, Industrial EngineeringChemistryResearch 46, 921 -926; Fabre et al., 2009, Journal of Molecular Catalysis B: Enzymatic, 60, 163-170).
  • the cement matrices based on carbide nanocals said matrices also comprising water, pozzolans, aggregates and CO2, all of them obtained from industrial waste, obtained from the process of the present invention and the third aspect thereof, the prefabricated parts produced from the process of the invention, in any possible geometric form, as well as its use in construction, public works and urban furniture, the advantages of the materials obtained are due to the fact that they allow the use of recycled components with a very low carbon footprint, especially nanocals, mineralize dirty CO2 recovered from industrial process emissions, obtain high resistance at an early age never before reached in agglomerates with calcium hydroxide, avoid efflorescence by leaching or dispersion of calcium hydroxides, admit light and dry recycled aggregates duo pozzolanic and reduce thermal density and conductivity, which makes these products obtained with the process of the invention a paradigm of waste utilization and positive environmental action in the construction materials industry.
  • the accelerated air setting process of the invention allows the use of hydraulic and / or air limes, preferably carbide limes, as the only binding reagent in cementitious matrices for prefabricated parts, obtaining results comparable to or superior to cement prefabricated at similar setting times.
  • the process of the invention includes the following steps: one .
  • the carbonic anhydrase of the first stage is added in concentrations ranging between 0.0001 and 0.1% by weight with respect to the total of the mixture, with particular preference between 0.001 and 0.01% by weight with respect to the total weight of the mixture.
  • the cementitious matrix that includes calcium hydroxide is that obtained as a residue in the Acetylene production, called in particular carbide lime in particular that purified and optimized as described in PCT / ES201 0/070294, of the same applicant.
  • the relative humidity considered in step 2 does not exceed 85%; in particular it is 25% to 85% and particularly preferably it is maintained between 50% and 75%.
  • the process temperature ranges between 10 and 50 ° C, in particular between 20 and 40 ° C.
  • the CO2 mentioned in step 5 of the present process is that recovered directly from the combustion gases of industrial processes, for example the coal thermoelectric, either the so-called “dirty CO2” or “CO2 clean "suitable for food use (purity> 95%).
  • the time necessary for the prefabricated parts to reach the total carbonation in the autoclave is a function of thickness, gas permeability, humidity, CO2 concentration and composition of the mixture of the pieces in addition to the characteristic properties of the lime used, where appropriate, of the other cementing compounds, pozzolanic materials, aggregates and additives.
  • the free calcium hydroxide thereof will also be carbonated contributing to the concrete reaching greater initial strengths.
  • the invention also provides various cementitious matrices that, regardless of whether they incorporate cement or not, comprise different materials dispersed in a lime matrix.
  • aluminosilicate phases hydrated calcium silicate phases and hydrated calcium aluminates
  • Aerial nanocals due to their high reactivity, also develop hydraulic reactions in the presence of pozzolans.
  • the invention shows as preferred examples a nanocal matrix commercially named GeoSilex obtained by purifying and optimizing the residues from carbide lime used in the Acetylene manufacturing, as described in patent application PCT / ES2010 / 070294.
  • This matrix incorporates recycling pockets such as residual metacaolin from various industries, or residual fly ash from the thermoelectric industry.
  • the preferred matrix object of the invention also includes recycling aggregates such as recycled glass powder, whether it is simply crushed or expanded in the form of hollow spheres.
  • the matrix of the invention incorporates glass powder of a particle size between 10 and 50 ⁇ , preferably recycled
  • the matrix of the invention incorporates hollow glass spheres of a granulometry between 200 ⁇ and 8 mm.
  • the process of the invention may also include the use of aerating additives and other additives typical of cryogenic concretes or cellular cements and concrete (cellular concrete) .
  • the cementitious matrix of the invention and the parts obtained therefrom and applying the method of this invention may also include the usual additives in the cement industry, such as plasticizers, water repellent, accelerators or setting retardants, as well as any of the heavy or light aggregates, the loads and the fibers or reinforcement materials usual in the concrete industry.
  • the prefabricated material with the cementitious matrix and that prepared according to the process of the invention is characterized by the following properties:
  • cementitious matrix of the invention is obtained by applying the present process and from the following elements, the percentages expressed as percentages by weight:
  • Binder reagent 20% GeoSilex (50% solid), 100% recycled nanocal
  • Carbonation accelerator carbonic anhydrase (0.001%)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Le procédé décrit dans cette invention est un procédé de durcissage à l'air accéléré, au moyen de la carbonatation forcée dans un autoclave, de pièces préfabriquées à matrices liantes qui contiennent un hydroxyde de calcium, à partir de chaux hydrauliques et/ou aérées, de préférence, nanochaux de carbure, la vitesse de durcissage augmentant en comparaison aux processus connus par ajout d'anhydrase carbonique comme accélérateur catalytique de carbonatation. Pour améliorer la carbonatation ultrarapide, les pièces, après un durcissage suffisant et le démoulage, sont introduites dans un autoclave d'où on extrait l'air par le vide et on le substitue par CO 2 et de la vapeur d'eau jusqu'à sa carbonatation. Le procédé de cette invention, en plus d'un séchage à l'air ultrarapide, permet d'obtenir industriellement des pièces préfabriquées dont les performances mécaniques sont très rapidement élevées.
PCT/ES2011/070826 2011-11-29 2011-11-29 Procédé de durcissage à l'air pour obtenir des pièces préfabriquées à matrices liantes, matrices et pièces préfabriquées ainsi obtenues, et leur utilisation WO2013079732A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2011/070826 WO2013079732A1 (fr) 2011-11-29 2011-11-29 Procédé de durcissage à l'air pour obtenir des pièces préfabriquées à matrices liantes, matrices et pièces préfabriquées ainsi obtenues, et leur utilisation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2011/070826 WO2013079732A1 (fr) 2011-11-29 2011-11-29 Procédé de durcissage à l'air pour obtenir des pièces préfabriquées à matrices liantes, matrices et pièces préfabriquées ainsi obtenues, et leur utilisation

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WO2013079732A1 true WO2013079732A1 (fr) 2013-06-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446620A (zh) * 2014-11-14 2015-03-25 安徽中龙建材科技有限公司 钢纤维蒸压加气混凝土(alc)板及其制备方法
CN104446618A (zh) * 2014-11-14 2015-03-25 安徽中龙建材科技有限公司 玻璃纤维蒸压加气混凝土(alc)板及其制备方法
CN110461556A (zh) * 2017-03-29 2019-11-15 楠石灰株式会社 使用水硬性石灰的成型体及其制造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2046867A (en) 1935-10-05 1936-07-07 Vacuum Concrete Corp Method of and apparatus for treating concrete
GB774432A (en) 1954-01-04 1957-05-08 Nissan Zelmanoff Artificial stone and building elements and process for their manufacture
US3149986A (en) 1961-03-13 1964-09-22 Zelmanoff Nissan Process for the manufacture of artificial stone articles
DE1197369B (de) 1963-10-19 1965-07-22 Habil Ernst Rossmann Dr Ing Verfahren zur Verbesserung der Carbonisation von Calciumhydroxyd in Bau- und Anstrichstoffen
US4362679A (en) 1978-01-03 1982-12-07 Roman Malinowski Method of casting concrete
WO1995004010A1 (fr) 1993-07-29 1995-02-09 W.R. Grace & Co.-Conn Ciment a faible retrait
EP0650940A1 (fr) 1993-10-29 1995-05-03 Toyo Chemical Co., Ltd. Composition inorganique durcissante
US5650562A (en) 1995-06-07 1997-07-22 Materials Technology, Limited Cement treated with high-pressure CO2
US5744078A (en) 1996-09-03 1998-04-28 Dpd, Inc. Accelerated processing of cement-bonded particleboard and fiberboard
WO2010130712A1 (fr) * 2009-05-13 2010-11-18 Universiteit Gent Réglage autogène de mortiers de chaux non hydrauliques par production de carbonate microbien

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2046867A (en) 1935-10-05 1936-07-07 Vacuum Concrete Corp Method of and apparatus for treating concrete
GB774432A (en) 1954-01-04 1957-05-08 Nissan Zelmanoff Artificial stone and building elements and process for their manufacture
US3149986A (en) 1961-03-13 1964-09-22 Zelmanoff Nissan Process for the manufacture of artificial stone articles
DE1197369B (de) 1963-10-19 1965-07-22 Habil Ernst Rossmann Dr Ing Verfahren zur Verbesserung der Carbonisation von Calciumhydroxyd in Bau- und Anstrichstoffen
US4362679A (en) 1978-01-03 1982-12-07 Roman Malinowski Method of casting concrete
WO1995004010A1 (fr) 1993-07-29 1995-02-09 W.R. Grace & Co.-Conn Ciment a faible retrait
EP0650940A1 (fr) 1993-10-29 1995-05-03 Toyo Chemical Co., Ltd. Composition inorganique durcissante
US5650562A (en) 1995-06-07 1997-07-22 Materials Technology, Limited Cement treated with high-pressure CO2
US5744078A (en) 1996-09-03 1998-04-28 Dpd, Inc. Accelerated processing of cement-bonded particleboard and fiberboard
WO2010130712A1 (fr) * 2009-05-13 2010-11-18 Universiteit Gent Réglage autogène de mortiers de chaux non hydrauliques par production de carbonate microbien

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
0. MATSUDA; H. YAMADA: "Experimental Study of the Manufacture of Building Materials by Carbonation of Slaked Lime", GYPSUM & LIME, vol. 125, 1973, pages 8 - 17
BOND ET AL., ENERGY&FUELS, vol. 15, 2001, pages 309 - 316
CULTRONEY ET AL., CEMENT AND CONCRETE RESEARCH, vol. 35, 2005, pages 2278 - 2289
DE SILVA ET AL.: "Carbonate binders: Reaction kinetics, strength and microstructure", CEMENT& CONCRETE COMPOSITES, vol. 28, 2006, pages 613 - 620, XP024963476, DOI: doi:10.1016/j.cemconcomp.2006.03.004
FABRE ET AL., JOURNAL OF MOLECULAR CATALYSIS B: ENZYMATIC, vol. 60, 2009, pages 163 - 170
MIRJAFARI ET AL., INDUSTRIAL ENGINEERINGCHEMISTRYRESEARCH, vol. 46, 2007, pages 921 - 926
W. USCHMANN: "Production of Compact Construction Elements from Lime and Admixtures by Treatment with Carbon Dioxide Gas", TRANSLATION FROM SR BST, vol. 29, 1974, pages 7 - 23
YADAVY ET AL., CURRENTSCIENCE, vol. 100, 2011, pages 520 - 524

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446620A (zh) * 2014-11-14 2015-03-25 安徽中龙建材科技有限公司 钢纤维蒸压加气混凝土(alc)板及其制备方法
CN104446618A (zh) * 2014-11-14 2015-03-25 安徽中龙建材科技有限公司 玻璃纤维蒸压加气混凝土(alc)板及其制备方法
CN110461556A (zh) * 2017-03-29 2019-11-15 楠石灰株式会社 使用水硬性石灰的成型体及其制造方法
EP3603911A4 (fr) * 2017-03-29 2020-12-23 Kusunoki Sekkai Co. Ltd. Article moulé utilisant de la chaux hydraulique et procédé pour sa fabrication

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