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WO1998018739A1 - Procede de production d'une composition d'acceleration de prise de ciment - Google Patents

Procede de production d'une composition d'acceleration de prise de ciment Download PDF

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Publication number
WO1998018739A1
WO1998018739A1 PCT/NO1996/000258 NO9600258W WO9818739A1 WO 1998018739 A1 WO1998018739 A1 WO 1998018739A1 NO 9600258 W NO9600258 W NO 9600258W WO 9818739 A1 WO9818739 A1 WO 9818739A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction composition
calcium nitrate
composition
cement
ammonia
Prior art date
Application number
PCT/NO1996/000258
Other languages
English (en)
Inventor
Harald Justnes
Original Assignee
Nyfotek As
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
Priority to NO952096A priority Critical patent/NO300588B1/no
Application filed by Nyfotek As filed Critical Nyfotek As
Priority to AU76840/96A priority patent/AU7684096A/en
Priority to PCT/NO1996/000258 priority patent/WO1998018739A1/fr
Publication of WO1998018739A1 publication Critical patent/WO1998018739A1/fr

Links

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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/61—Corrosion inhibitors

Definitions

  • the invention concerns a method for the manufacture of a set accelerating and corrosion inhibiting composition for cement, as described in the introductory part of claim 1.
  • the polyalkanol component comprised mainly of diethanolamine and triethanolamine, is also known to have an accelerating effect on the hardening of the cement, and is added according to this publication directly to an aqueous calcium nitrate solution.
  • the primary purpose of this patent seems to be the achievement of the combination of the accelerating effect on the hardening together with use of a cheap raw material in the form of an alkanol distillate composition.
  • Rettvin and Masdal The use of Calcium Nitrate Solutions as a Set-Accelerating Admixture in Slipforming of High Strength Concrete", Proc.
  • the main objective with the present invention is to obtain a method for the manufacturing of a set-accelerator for cement, which will render it possible to use a technical calcium nitrate as a set-accelerator.
  • An underlying objective is to provide a substance which also can exercise a corrosion inhibiting effect on the reinforcement steel in concrete and promote the setting process further.
  • the invention concerns a method for the manufacture of a set-accelerating and corrosion inhibiting composition for use in cement containing technical calcium nitrate.
  • R,, R 2 , R 3 and R 4 may independently from each other, be hydrogen, substituted or unsubstituted, saturated or unsaturated alkyl; aralkyl, phenyl; or a heteroatomic group, preferentially under alkaline conditions, whereby the epoxy compound reacts with ammonia absorbed in the solution of the technical calcium nitrate, thereby forming on or more amine containing compounds.
  • the epoxy- or epoxide group is a very reactive group, and all epoxide-functional compounds may in principle be used, alone or in combinations, for the purpose of the present invention.
  • the reaction with ammonia runs very easily in aqueous solutions and the reaction is generally exothermic.
  • the reactivity of the epoxy compound decreases however with increasing substitution of the epoxy ring, and thus the reactivity will decrease in the order: propylene oxide > isobutylene oxide > trimethyl-ethylene oxide > tetramethyl-ethylene oxide.
  • ethylene oxide and propylene oxide reacts at room temperatures, a temperature of about 100 °C is required to achieve a satisfactory reaction rate with tetramethyl-ethylene oxide.
  • epoxy compounds the following can be mentioned as examples of other epoxide-functional compounds: 2,3-epoxy-propane-l-ol, epichlorohydrin, 2,3 epoxypropyl- isopropylether, 3-hydroxy-pyrrolidine, phenyl-oxacyclopropane, 1,2 diphenyl- oxacyclopropane, b-chlor-ethyl-oxacyclopropane.
  • the temperature for the reaction composition will consequently vary according to the epoxy compound's structure.
  • the pressure in the reaction composition will, with the exception of ethylene oxide as described below, generally be atmospheric.
  • the primary reaction product from the reaction between ammonia and the epoxy compounds are mono-, di- and tri-alkanolamines, but different by-products are also conceivable.
  • Alkan in this context consequently means not only linear or branched alkanes with epoxy-functional groups, but also substituted variants and aromatic groups, alkenyl groups and heteroatomic groups.
  • One of the central aspects with the present invention is that the method according to the invention gives an immobilisation of ammonium in technical calcium nitrate under formation of alkanolamine compounds, which are generally known to have a corrosion inhibiting effect on the reinforcement steel in concrete, as described in more detail below.
  • the reaction is carried out under alkaline conditions. This may be obtained e.g. with an addition of calcium hydroxide or magnesium hydroxide, which after completed reaction will be present as nitrate salts, depending upon what form the ammonium component in the technical calcium nitrate has.
  • alkali- metal hydroxides or -carbonates as a pH-adjusting additive, but these compounds should be avoided in order to minimise unwanted alkali aggregate reactions in the concrete at later use.
  • alkaline compounds e.g. 80% of the ammonium content.
  • the pH-level of the reaction mixture should be in the basic range, but should on the other hand not be too high as one in such a case will risk formation of alcohols in a reaction with water, whereby ammonia or ammonium remains unreacted in the set-accelerator admixture.
  • the pH-level of the reaction composition will however vary in dependence with the ammonium concentration in the composition and the kind of epoxy compound that is used. It is, however, preferred to use ethylene oxide (CH 2 CH 2 O) which on reaction with ammonia forms a mixture of monoethanolamine (MEA), diethanolamine (DEA) and tetraethanolamine (TEA).
  • MEA monoethanolamine
  • DEA diethanolamine
  • TEA tetraethanolamine
  • the later two ethanolamines DEA and TEA are especially known to promote the setting reaction of cement.
  • the first mentioned reaction product, MEA, which does not give any significant set-accelerating effect, is on the other hand known to be an effective corrosion inhibitor for steel; this later property applies for alkanolamines in general, see e.g. H. Maeder, "A New Class of Corrosion Inhibitors ", Proceedings of the International Conference on Corrosion and Corrosion Protection of Steel in Concrete, 25-28 July 1994, vol II, page 851, Sheffield, UK.
  • the by-product hydroxyethylether R 1 R 2 N-(CH 2 CH 2 O)n-CH 2 CH 2 -OH
  • the ethanolamines are moreover preferred due to their low toxicity. Since ethylene oxide has a low boiling point (13,5°C at atmospheric pressure), it is preferred to conduct the reaction under a moderately raised pressure, preferentially with the aid of an inert atmosphere, e.g. nitrogen, in order to maintain the reaction mixture in a liquid phase at room temperature. Alternatively the reaction composition can be maintained at a temperature below the boiling point of ethylene oxide, but this will slow down the reaction rate. Epoxy compounds are generally toxic, and for that reason one should avoid using epoxy compounds in excess with respect to the concentration of ammonia in the calcium nitrate solution.
  • the ratio between the epoxy compounds and ammonia in the reaction composition should be less than or equal to 3. If on the other hand the epoxy compound is added in excess, any remaining unreacted epoxy will in any event be rendered harmless when the set-accelerator composition is added to cement, as the pH of the setting concrete will cause the epoxy compounds to react with water under formation of alcohol compounds.
  • the achieved set-accelerator composition can be used as it is, but from considerations of transportability it is preferred to remove the liquid component, e.g. by vapourization in order to get a set- accelerator composition in a solid state.
  • the solid set-accelerator composition may if, one so wishes be given further treatment like granulating, pelletisation or the like.
  • This example has the intention to illustrate the reaction process for immobilising ammonia in technical calcium nitrate by the use of ethylene oxide as a reactant.

Landscapes

  • 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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Ce procédé de fabrication d'une composition d'accélération de prise et d'inhibition de la corrosion, destinée au ciment, comprend de l'ammonium contenant du nitrate de calcium technique, et il consiste à obtenir une composition de réaction comportant: (i) de l'ammonium contenant du nitrate de calcium technique dissous dans de l'eau, et de préférence en présence d'un composé alcalin, (ii) un composé époxy correspondant à la formule générale (I), dans laquelle R1, R2, R3 et R4 représentent indépendamment hydrogène, alkyle saturé ou insaturé, substitué ou non, aralkyle, phényle, ou un groupe à hétéroatome. On maintient la composition de réaction résultante sous une pression et à une température conçues pour conserver cette composition en phase liquide, et pendant une période suffisante pour convertir au moins des parties de l'ammoniaque dissoutes dans la composition de réaction, en produits contenant des amines, notamment en composés contenant alcanol.
PCT/NO1996/000258 1995-05-26 1996-10-30 Procede de production d'une composition d'acceleration de prise de ciment WO1998018739A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NO952096A NO300588B1 (no) 1995-05-26 1995-05-26 Framgangsmåte for framstilling av herdeakselerende blanding for sement
AU76840/96A AU7684096A (en) 1996-10-30 1996-10-30 Method for production of a set-accelerating composition for cement
PCT/NO1996/000258 WO1998018739A1 (fr) 1995-05-26 1996-10-30 Procede de production d'une composition d'acceleration de prise de ciment

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO952096A NO300588B1 (no) 1995-05-26 1995-05-26 Framgangsmåte for framstilling av herdeakselerende blanding for sement
PCT/NO1996/000258 WO1998018739A1 (fr) 1995-05-26 1996-10-30 Procede de production d'une composition d'acceleration de prise de ciment

Publications (1)

Publication Number Publication Date
WO1998018739A1 true WO1998018739A1 (fr) 1998-05-07

Family

ID=26648577

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO1996/000258 WO1998018739A1 (fr) 1995-05-26 1996-10-30 Procede de production d'une composition d'acceleration de prise de ciment

Country Status (2)

Country Link
NO (1) NO300588B1 (fr)
WO (1) WO1998018739A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999002465A1 (fr) * 1997-07-10 1999-01-21 Nyfotek As Melange accelerant la prise du beton
NL1027239C2 (nl) * 2004-10-13 2006-04-18 Cementbouw Betonmortel B V Werkwijze voor het bereiden van betonspecie voor corrosiebestendig gewapend beton.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4897120A (en) * 1988-01-19 1990-01-30 Gifford-Hill & Company, Inc. Accelerator for portland cement derived from fertilizer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4897120A (en) * 1988-01-19 1990-01-30 Gifford-Hill & Company, Inc. Accelerator for portland cement derived from fertilizer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999002465A1 (fr) * 1997-07-10 1999-01-21 Nyfotek As Melange accelerant la prise du beton
NL1027239C2 (nl) * 2004-10-13 2006-04-18 Cementbouw Betonmortel B V Werkwijze voor het bereiden van betonspecie voor corrosiebestendig gewapend beton.
WO2006041288A3 (fr) * 2004-10-13 2006-10-12 Cementbouw Betonmortel B V Procede de preparation de beton frais pour un beton arme resistant a la corrosion

Also Published As

Publication number Publication date
NO300588B1 (no) 1997-06-23
NO952096D0 (no) 1995-05-26
NO952096L (no) 1996-11-27

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