WO2013023949A2 - Poudre contenant de l'oxyde de calcium, production et utilisation de ladite poudre - Google Patents

Poudre contenant de l'oxyde de calcium, production et utilisation de ladite poudre Download PDF

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Publication number
WO2013023949A2
WO2013023949A2 PCT/EP2012/065365 EP2012065365W WO2013023949A2 WO 2013023949 A2 WO2013023949 A2 WO 2013023949A2 EP 2012065365 W EP2012065365 W EP 2012065365W WO 2013023949 A2 WO2013023949 A2 WO 2013023949A2
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WO
WIPO (PCT)
Prior art keywords
calcium
weight
powder
calcium oxide
zone
Prior art date
Application number
PCT/EP2012/065365
Other languages
German (de)
English (en)
Other versions
WO2013023949A3 (fr
Inventor
Stipan Katusic
Peter Kress
Ulrich Fischer
Armin Wiegand
Original Assignee
Evonik Degussa Gmbh
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 Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Publication of WO2013023949A2 publication Critical patent/WO2013023949A2/fr
Publication of WO2013023949A3 publication Critical patent/WO2013023949A3/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
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1074—Silicates, e.g. glass
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/22—Carbonation resistance
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

  • the invention relates to a calcium oxide, silica and others
  • the doping used is metal alcoholates such as, for example, tetraethyl orthosilicate.
  • the silicon-containing particles have a BET surface area of 78 m 2 / g and a ratio of silicon to calcium of 1:10. In addition to calcium oxide, calcium carbonate is also detected in the particles.
  • the technical problem was therefore to provide a powder containing calcium oxide, which increased protection against storage
  • the invention relates to a calcium oxide, silica and others
  • Calcium compounds based on the total weight of the powder, at least 95 wt .-% makes up, i. wherein this proportion by weight comprises 10 to 25% by weight of silicon dioxide and 75 to 90% by weight of crystalline calcium-containing substances, ii. where the phase proportions of the crystalline calcium-containing
  • the proportion of silicon dioxide in the powder according to the invention is the proportion of silicon dioxide in the powder according to the invention.
  • the silica content can be determined wet-chemically, for example by means of inductively coupled plasma optical emission spectrometry (ICP-OES).
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • the identification of the crystalline constituents of the powder according to the invention is carried out by means of X-ray diffractometry.
  • the proportion of different phases in the crystalline portion of the powder is calculated using the programs
  • phase is meant a crystalline compound which can be detected by means of X-ray diffractometry on the basis of its characteristic reflections. Pure phase means that all reflections in the X-ray diffractogram can be clearly assigned to only one crystalline compound.
  • the powder containing calcium oxide, silicon dioxide and other calcium compounds is characterized by a core-shell structure. This is constructed so that the core consists essentially of the crystalline calcium-containing
  • Compounds exists and at least the calcium oxide is surrounded by an envelope of amorphous silica.
  • all calcium compounds are surrounded by silium dioxide.
  • the powder according to the invention is built up in layers, wherein the other calcium compounds, the calcium onion-like surrounded and the outermost layer of silicon dioxide is formed.
  • all calcium-containing compounds are separated from each other and pure phase and are each from a shell
  • the layer thickness of the silicon dioxide shell is 2 - 20 nm, preferably 5 - 12 nm. It is determined by TEM images.
  • the BET surface area is determined according to DIN 66131 with nitrogen. It may be 5 to 30 m 2 / g, preferably 10 to 25 m 2 / g, more preferably 15 to 20 m 2 / g.
  • Primary particles are to be understood as meaning, for example, sintered necks, interconnected primary particles.
  • the powder of the invention is essentially chloride-free, the chloride content based on the total weight is ⁇ 500 ppm. Preferred is a
  • Another object of the invention is a process for the preparation of the powder according to the invention comprising in a reactor comprising the successive zones mixing zone, combustion zone, cooling zone and separation zone, a) in the mixing zone an aerosol by atomizing at least one
  • hydrolyzable and / or oxidizable calcium compound as such in liquid form or in solution, corresponding to a content of 75-90% by weight of calcium oxide, based on the weight of calcium hydroxide
  • Convicted combustion zone there ignites and under adiabatic Conditions can react at temperatures of 900 - 1200 ° C and a mean residence time of 10 ms to 10 s, via a nozzle a stream, vapor or in the form of an aerosol of an oxidizable and / or hydrolyzable substantially
  • halide-free silicon compound corresponding to a content of 10 - 25 wt .-% of silica based on the weight of the
  • the calcium compounds may be of organometallic and / or inorganic nature, with organometallic compounds may be preferred.
  • organometallic compounds may be preferred.
  • metal alkoxides and / or metal carboxylates can be used as organometallic compounds.
  • alcoholates can be used as alcoholates.
  • ethylates preferably ethylates, n-propylates, iso-propylates, n-butylates and / or tert-butylates are used.
  • carboxylates those of acetic acid, propionic acid, butanoic acid, hexanoic acid, oxalic acid, malonic acid,
  • Succinic acid glutaric acid, adipic acid, octanoic acid, 2-ethylhexanoic acid, valeric acid, capric acid and / or lauric acid
  • Calcium acetate and calcium 2-ethylhexanoate can be used particularly advantageously.
  • inorganic compounds calcium hydroxides, calcium nitrates and other essentially halide-free calcium compounds can be used; calcium hydroxide is preferred.
  • the inorganic starting compounds may preferably be present dissolved in water, the organometallic starting compounds in organic solvents.
  • organic solvents or as part of
  • organic solvent mixtures may preferably alcohols such as
  • C 1 -C 20 -carboxylic acids such as, for example, acetic acid, propionic acid, butanoic acid, hexanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid,
  • silicon compounds volatile or liquid substances, but also colloidal silica, can be used. Substances which are essentially halide-free are preferred, alkoxides such as
  • Tetraethylorthosilicate and tetramethylorthosilicate are Tetraethylorthosilicate and tetramethylorthosilicate.
  • the atomizing gas used in the process according to the invention is a reactive gas such as air, oxygen-enriched air and / or an inert gas such as nitrogen.
  • air is used as a sputtering gas.
  • the reaction temperature of more than 700 ° C. necessary in the process according to the invention can preferably be obtained by means of a flame produced by reaction of a hydrogen-containing fuel gas with (primary) air, optionally enriched with oxygen.
  • Suitable fuel gases may be hydrogen, methane, ethane, propane, butane and / or natural gas, with hydrogen being particularly preferred.
  • the reaction temperature is defined as that which occurs 0.2 m behind the burner mouth. Furthermore, it may be advantageous if in addition secondary air in the
  • the amount of secondary air will be such that the ratio of secondary air to primary air is 0.1 to 10. It is particularly advantageous if lambda> 1, 2, wherein lambda calculated from the quotient of the sum of the oxygen content of the air used (primary air, secondary air and atomizing air) divided by the sum of the oxygen content of the starting materials and the hydrogen-containing fuel gas, respectively in mol / h. 'The average droplet diameter of the aerosol is not restricted.
  • Particularly preferred is a mean droplet diameter of the aerosol of 20-200 ⁇ .
  • the separation of the powder from the reaction mixture is usually preceded by a cooling process.
  • This process can be realized directly, for example by means of a quench gas, or indirectly, for example via external cooling. Nitrogen is preferably used as the quench gas.
  • Another object of the invention is a hydraulic binder containing the powder of the invention
  • Another object of the invention is the use of the
  • the silicon compounds used are silicon tetrachloride, tetraethyl orthosilicate and octamethyltetracyclosiloxane.
  • the calcium compounds used are calcium acetate and calcium octoate.
  • the calcium acetate is used as a solution of 26.82 wt .-% calcium acetate in
  • the calcium octoate used is Octa-Soligen Calcium 10, a mixture of calcium salts of C6-Cig fatty acids and naphtha (petroleum), of OMG Borchers containing 14% by weight of calcium oxide.
  • EXAMPLE 1 From a calcium acetate solution (26.82% by weight of calcium acetate in 73.1 1% by weight of water), corresponding to 340 g / h of calcium oxide, and a stream of 4 Nm 3 / h of air as sputtering gas, at room temperature ( 23 ° C) generates an aerosol by means of a two-fluid nozzle in the mixing zone of a reactor.
  • This aerosol is in the combustion zone of the reactor in a flame, which by ignition of a mixture of 5.7 Nm 3 / h of hydrogen and
  • a second stream in the form of an aerosol of tetraethylorthosilicate (TEOS), corresponding to 63 g / h of silica, is fed at the location of the combustion zone via an annular die at which a temperature of 720-750 ° C prevails.
  • TEOS tetraethylorthosilicate
  • Reaction mixture cooled by introducing 30 Nm 3 / h of N 2 to ⁇ 600 ° C.
  • the solid obtained is deposited in the separation zone on a filter and thus separated from the gaseous substances.
  • Example 2 The procedure is analogous to Example 1, but octamethylcyclotetrasiloxane (D4) is used as the silicon compound instead of TEOS.
  • Example 3 The procedure is analogous to Example 1, but octa-Soligen calcium 10 from OMG Borchers as calcium compound
  • Example 4 The procedure is analogous to Example 3, but is hydrolyzed with an indirect flame.
  • Example 5 The procedure is analogous to Example 4, but the flame parameters are changed according to Table 1.
  • Comparative Example 1 (VG1): The procedure is analogous to Example 1 instead. However, it is based on the supply of a second stream with a
  • Silica source dispensed so that forms no silicon dioxide shell.
  • Comparative Example 2 (VG2): The procedure is analogous to Example 1, but silicon tetrachloride is used as the silicon compound instead of TEOS. To test the storage stability, the samples are stored at room temperature and a relative humidity of 60% for 60 days in plastic containers. Subsequently, X-ray diffraction patterns of the powders are recorded again and the measured values are compared with the initial values.
  • Table 2 Levels of calcium compounds obtained from Röntgendiffraktogrannnnen
  • the powders of Examples 1 to 5 show only slight changes in the levels of calcium oxide, calcium carbonate and calcium hydroxide. They are therefore distinguished by increased protection against storage-related carbon dioxide uptake (see Table 2).
  • the calcium oxide content decreases sharply from 43% by weight to 18% by weight and on the other hand the calcium carbonate content increases from 47% by weight to 59% by weight and the calcium hydroxide content from 10% by weight to 23% by weight. -% too.

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

Abstract

La présente invention concerne une poudre contenant de l'oxyde de calcium, du dioxyde de silicium et d'autres composés de calcium, ainsi que la production de ladite poudre. La présente invention concerne en outre un liant hydraulique à base de ladite poudre contenant du calcium, ainsi que son utilisation dans du ciment, du béton ou du mortier.
PCT/EP2012/065365 2011-08-18 2012-08-06 Poudre contenant de l'oxyde de calcium, production et utilisation de ladite poudre WO2013023949A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011110999 2011-08-18
DE102011110999.8 2011-08-18

Publications (2)

Publication Number Publication Date
WO2013023949A2 true WO2013023949A2 (fr) 2013-02-21
WO2013023949A3 WO2013023949A3 (fr) 2013-05-23

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017137791A1 (fr) * 2016-02-11 2017-08-17 Services Petroliers Schlumberger Agent de dilatation encapsulé sensible au ph pour cimentation de puits
WO2017174208A1 (fr) * 2016-04-08 2017-10-12 Schlumberger Technology Corporation Boue comprenant un agent d'expansion encapsulé pour la cimentation de puits
EP3235890A1 (fr) * 2016-04-18 2017-10-25 Services Pétroliers Schlumberger Agent d'expansion encapsulé dans de la silice pour la cimentation de puits
WO2017182296A1 (fr) * 2016-04-18 2017-10-26 Basf Se Agents d'expansion enrobés de silice et leur utilisation dans des systèmes cimentaires
WO2019076585A1 (fr) 2017-10-13 2019-04-25 Basf Se Agents d'expansion à noyau et enveloppe et leur utilisation dans des systèmes cimentaires
US10526523B2 (en) 2016-02-11 2020-01-07 Schlumberger Technology Corporation Release of expansion agents for well cementing
CN111087009A (zh) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 一种氧化硅和氧化钙复合材料及其合成方法
US11130899B2 (en) 2014-06-18 2021-09-28 Schlumberger Technology Corporation Compositions and methods for well cementing

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Publication number Priority date Publication date Assignee Title
DE10260718A1 (de) * 2002-12-23 2004-07-08 Degussa Ag Mit Siliziumdioxid umhülltes Titandioxid
EP1678268B1 (fr) * 2003-10-02 2009-09-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composant d'agent d'ignifugation de materiaux et procede d'ignifugation
CN101225245A (zh) * 2008-01-31 2008-07-23 上海卓越纳米新材料股份有限公司 核壳型二氧化硅包覆纳米碳酸钙的制备方法
DE102008010349A1 (de) * 2008-02-13 2009-08-20 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg(ZSW) Als CO2-Absorbens und zur Anwendung als Bettmaterial in Wirbelschichten geeignetes Material und dessen Herstellung
DE102008044384A1 (de) * 2008-12-05 2010-06-10 Evonik Degussa Gmbh Eisen-Silicium-Oxidpartikel mit einer Kern-Hülle-Struktur

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Title
CHEM. COMMUN., 2005, pages 648
CHEM. ENG. SCI., vol. 64, 2009, pages 1936
ENERGY & FUELS, vol. 23, no. 2, 2009, pages 1093 - 1100
P.G. SMIRNIOTIS, FINAL TECHNICAL REPORT 2003 - 2007 DES CHEMICAL & MATERIALS ENGINEERING, 2003

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11130899B2 (en) 2014-06-18 2021-09-28 Schlumberger Technology Corporation Compositions and methods for well cementing
WO2017137791A1 (fr) * 2016-02-11 2017-08-17 Services Petroliers Schlumberger Agent de dilatation encapsulé sensible au ph pour cimentation de puits
US10526523B2 (en) 2016-02-11 2020-01-07 Schlumberger Technology Corporation Release of expansion agents for well cementing
WO2017174208A1 (fr) * 2016-04-08 2017-10-12 Schlumberger Technology Corporation Boue comprenant un agent d'expansion encapsulé pour la cimentation de puits
US10941329B2 (en) 2016-04-08 2021-03-09 Schlumberger Technology Corporation Slurry comprising an encapsulated expansion agent for well cementing
EP3235890A1 (fr) * 2016-04-18 2017-10-25 Services Pétroliers Schlumberger Agent d'expansion encapsulé dans de la silice pour la cimentation de puits
WO2017182296A1 (fr) * 2016-04-18 2017-10-26 Basf Se Agents d'expansion enrobés de silice et leur utilisation dans des systèmes cimentaires
CN109071350A (zh) * 2016-04-18 2018-12-21 巴斯夫欧洲公司 二氧化硅涂覆的膨胀剂及其在水泥体系中的用途
US11008256B2 (en) 2016-04-18 2021-05-18 Basf Se Silica-coated expanding agents and their use in cementitious systems
WO2019076585A1 (fr) 2017-10-13 2019-04-25 Basf Se Agents d'expansion à noyau et enveloppe et leur utilisation dans des systèmes cimentaires
CN111087009A (zh) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 一种氧化硅和氧化钙复合材料及其合成方法

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Publication number Publication date
DE102012204148A1 (de) 2013-02-21
WO2013023949A3 (fr) 2013-05-23

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