EP3802461A1 - Verfahren zur verflüssigung von belit-calciumsulfoaluminat-ferrit-haltigen zementen - Google Patents
Verfahren zur verflüssigung von belit-calciumsulfoaluminat-ferrit-haltigen zementenInfo
- Publication number
- EP3802461A1 EP3802461A1 EP19724853.7A EP19724853A EP3802461A1 EP 3802461 A1 EP3802461 A1 EP 3802461A1 EP 19724853 A EP19724853 A EP 19724853A EP 3802461 A1 EP3802461 A1 EP 3802461A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- calcium
- ferrite
- belite
- weight
- composition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/16—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 calcium sulfate cements containing anhydrite, e.g. Keene's cement
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Definitions
- the invention relates to a process for the liquefaction of compositions containing belite-calcium sulfoaluminate-ferrite cement.
- Dispersants or flow agents are used in the construction industry as liquefiers or water-reducing agents for cementitious compositions, e.g. Concrete, mortar and cement.
- the dispersants are generally organic polymers which are added to the make-up water or added as a solid to a dry cementitious composition. As a result, both the consistency of the composition during processing and the properties in the cured state can be advantageously changed.
- Particularly effective dispersants are, for example, polycarboxylate-based comb polymers.
- Such comb polymers have a polymer backbone and side chains attached thereto.
- Corresponding polymers are e.g. in EP 1 138 697.
- the cements used in the construction industry typically contain
- Heating material but also to a large extent from the decarboxylation of the necessary as raw material calcium carbonate. It is therefore the cement manufacturers' ambition to provide alternative cements that generate less CO2 during production.
- belite-rich cements such as typically belite-calcium sulfoaluminate-ferrite cement (BCSAF cement).
- BCSAF cement typically belite-calcium sulfoaluminate-ferrite cement
- the clinker is ground. Because the ground BCSAF clinker sets and / or stiffens very rapidly with water, an appropriate amount of calcium sulfate and retarders, such as boric acid or borax, are typically still added to the clinker during milling or after milling
- Retarders such as boric acid or borax, in combination with condensers, often have a different behavior compared to
- Portland cements Concrete or mortar mixtures with BCSAF cement often have a strong secondary liquefaction when a superplasticizer is used, even if this superplasticizer in Portland cement little or no
- Post-liquefaction means that the flowability of the mixture increases from the time of mixing with water to 30 or 60 or more minutes after mixing and is significantly higher than directly after mixing with water. Such post-liquefaction is very undesirable in mortar and concrete works, especially in ready-mixed concrete, because the properties of the mixture are not constant and predictable.
- Re-liquefaction is significantly worse than a stiffening of the mixture.
- a stiffening of the mixture the fluidity decreases over time.
- the flowability can be improved again by adding water and / or further condenser.
- too much water is typically added during production because initially the processability of the mixture is lower. If the processability then increases due to a post-liquefaction after some time, for example during transport, this can lead to sedimentation and bleeding, but this is bad for the concrete quality. Since the concrete then also contains too much water, this leads to a lower strength of the mixture after curing.
- compositions containing BCSAF cement which reduces or prevents the re-liquefaction.
- BCSAF cement belite-calcium sulfoaluminate-ferrite cement
- this composition should have no or only a very small secondary liquefaction.
- the addition of the post-condensation reducing agent causes a mortar or concrete made with BCSAF cement, particularly a BCSAF cement, containing a retarder, such as boric acid or borax, or mixed with the retarder and a superplasticizer , no or very little after-liquefaction has.
- BCSAF cement particularly a BCSAF cement, containing a retarder, such as boric acid or borax, or mixed with the retarder and a superplasticizer , no or very little after-liquefaction has.
- Superplasticizer produced concrete or mortar thereby typically has comparable processing properties as a concrete or mortar made with Portland cement and superplasticizer.
- the process is cost effective and can increase the acceptance of the new cements in the construction industry, which is highly desirable from an environmental point of view.
- the process can save costs for the development of new condenser for BCSAF cement, and in concrete plants, the same condenser can be used for Portland cement and BCSAF cement, reducing storage costs and logistics costs. Further aspects of the invention are the subject of further independent
- the invention relates to a process for liquefying a composition comprising a belit-calcium sulfoaluminate-ferrite cement by adding at least one polymeric dispersant, wherein the composition comprises a means for reducing the secondary liquefaction.
- Belit-calcium sulfoaluminate-ferrite cement is understood to mean a cement obtained by milling belite-calcium sulfoaluminate-ferrite clinker (BCSAF clinker), optionally with the addition of further additives.
- Belit-calcium sulfoaluminate-ferrite clinker is also Belit-Ye'el imit-ferrite clinker (BYF clinker). Accordingly, the cement is also called BYF cement.
- the BCSAF clinker is a clinker which is preferably composed of at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, of the mineral phases belite (dicalcium silicate), calcium sulfoaluminate and calcium aluminoferritite.
- the BCSAF cement typically contains calcium sulfate to control setting. Typically, the proportion of calcium sulfate in the BCSAF cement is up to 40% by weight.
- the calcium sulfate is typically calcium sulfate hemihydrate, calcium sulfate dihydrate or anhydrite.
- BCSAF cements quickly stiffen and can not or only poorly be processed. Therefore, typically a
- Retarder added to ensure good processability.
- the process of the invention is very effective in reducing or preventing post-liquefaction when using a polymeric dispersant.
- the process according to the invention is preferably used for a belite-calcium sulfoaluminate-ferrite cement comprising ground belite-calcium sulfoaluminate-ferrite clinker, calcium sulfate and a retarder.
- the retarder comprises at least one substance which reduces the pFI of a slurry of a milled belite-calcium sulfoaluminate-ferrite clinker in water.
- the retarder is boric acid or borax.
- the proportion of the retarder in the BCSAF cement is
- the means for reducing the secondary liquefaction comprises at least one compound selected from the group comprising water-soluble calcium salts, water-soluble magnesium salts, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, lithium hydroxide, sodium hydroxide and
- water-soluble calcium or magnesium salt is advantageously used together with an alkaline compound, in particular an alkaline earth or alkali metal hydroxide.
- the means for reducing the Nachverminuteung comprises
- Calcium hydroxide, calcium oxide and / or alkali metal hydroxide are examples of calcium hydroxide, calcium oxide and / or alkali metal hydroxide.
- the means for reducing the Nachverminuteung comprises
- the means for reducing the secondary liquefaction comprises calcium hydroxide and / or calcium oxide and at least one alkali metal hydroxide, in particular sodium hydroxide. Such a combination is particularly effective for suppressing the
- the means for reducing the Nachverroughung in 0.05 to 5
- % By weight, more preferably 0.08 to 3% by weight, especially 0.1 to 2% by weight, in particular 0.15 to 1% by weight, based on the weight of the milled belite-calcium sulfoaluminate-ferrite clinker, present in the composition.
- the redilution reducing agent is present in addition to possible alkali or alkaline earth hydroxides or oxides used for possible neutralization of the polymeric dispersant.
- the means for reducing the secondary liquefaction is preferably present in the BCSAF cement.
- the means for reducing the Nachverroughung can also be used.
- Composition may be added separately from the cement, in particular in or together with the polymeric dispersant.
- this mixture may be present as a powder or as an aqueous solution.
- the polymeric dispersant comprises an anionic polymer comprising -COOM, -SO2-OM, -O-PO (OM) 2 and / or -PO (OM) 2 groups, wherein M, each independently, is FT, alkali metal ion, alkaline earth metal ion, divalent or trivalent metal ion, ammonium ion or an organic ammonium group.
- Suitable anionic polymers are, for example, in the concrete technology known condenser or superplasticizer such as in particular lignosulfonates, sulfonated naphthalene-formaldehyde condensates, sulfonated melamine-formaldehyde aldehyde condensates, sulfonated vinyl copolymers, polyalkylene glycols with
- Phosphonate groups polyalkylene glycols with phosphate groups, polycarboxylates or comb polymers having anionic groups on the polymer backbone and
- the polymeric dispersant preferably comprises a comb polymer comprising anionic groups on the polymer backbone and polyalkylene glycol side chains, the molar ratio of anionic groups to polyalkylene glycol side chains preferably being 0.7-15: 1, more preferably 1-6: 1, in particular 1-4. 1, is.
- the comb polymer preferably comprises structural units of the formula I.
- R 1 each independently of one another, is -COOM, -SO 2 -OM, -O-PO (O) 2 and / or -PO (OM) 2, preferably -COOM,
- R 2 and R 5 each independently, is Fl, -CFI 2 -COOM or a
- R 3 and R 6 are Fl or an alkyl group having 1 to 5 carbon atoms
- R 4 and R 7 are Fl, -COOM or an alkyl group having 1 to 5 carbon atoms,
- M each independently, for FT, alkali metal ion, alkaline earth metal ion, two or trivalent metal ion, ammonium ion or an organic
- n 0 or an integer from 1 to 4,
- n 2-250, especially 10-200,
- X in each case independently of one another, represents -O- or -NH-
- R 8 each independently, is H, a C 1 to C 20 alkyl group, cyclohexyl group or alkylaryl group, and
- A is C 2 to C 4 alkylene.
- the polymeric dispersant comprises a comb polymer comprising carboxylate groups and polyethylene glycol side chains.
- the polymeric dispersant is a comb polymer composed of structural units I derived from ethylenically unsaturated
- Carboxylic acids in particular monocarboxylic acids, or salts thereof, and structural units II derived from ethylenically unsaturated
- Polyalkylene glycols in particular polyethylene glycols, are.
- the comb polymer preferably contains no further structural units otherwise.
- the weight average molecular weight M w of the comb polymer measured against polyethylene glycol standards at pH 12, between 8 ⁇ 00 and 200 ⁇ 00 g / mol, more preferably between 10 ⁇ 00 and 150 ⁇ 00 g / mol, in particular between 12 ⁇ 00 and 130 ⁇ 00 g / mol, in particular between 15 ⁇ 00 and 80 ⁇ 00 g / mol.
- the comb polymer is advantageously prepared by free radical copolymerization of monomers containing acid groups and monomers containing polyether chains.
- Corresponding polymers are described, for example, in EP 2 522 680.
- the comb polymer by polymer-analogous esterification and / or amidation of polymers containing carboxyl groups with
- Polyethers having at one end a hydroxyl group or an amino group have to be produced.
- Corresponding polymers are described, for example, in EP 1 138 697.
- the comb polymer is a block or gradient polymer.
- Such polymers are typically obtained by living radical polymerization.
- Corresponding polymers are described, for example, in WO 2015/144886 and in WO 2017/050907.
- the polymeric dispersant is present in 0.04 to 2.5% by weight, calculated as a solid by weight of the belite-calcium sulfoaluminate-ferrite cement.
- Another aspect of the present invention relates to the use of a polymeric dispersant for liquefying a composition
- composition comprising a belite-calcium sulfoaluminate-ferrite cement, the composition comprising a means for reducing the after-liquefaction.
- the polymeric dispersant may be added to the composition as a powder or as an aqueous solution.
- Another aspect of the present invention relates to a composition
- a composition comprising
- a retarder in particular comprising boric acid or borax
- a means for reducing the secondary liquefaction in particular comprising
- a polymeric dispersant in particular a comb polymer comprising carboxylate groups and polyethylene glycol side chains.
- composition comprising
- ingredients and their proportions of the composition are as previously described for the process.
- composition may also contain additives, additives or additives.
- additives are known in the art.
- Suitable aggregates are in principle all sands, gravel and stones that are commonly used for concrete and mortar.
- Suitable additives are, in particular, fly ash, flash sand, metakaolin, silica fume, quartz flour, fine calcium carbonate and / or inert rock flour. Suitable additives are in particular further dispersants, defoamers, wetting agents, dyes, preservatives, flow agents, retarders,
- Another aspect of the present invention relates to a composition
- a composition comprising a belite-calcium sulfoaluminate ferrite cement, a polymeric dispersing agent, a post-liquefaction reducing agent and water, wherein the belite-calcium sulfoaluminate-ferrite cement is a milled belite-calcium sulfoaluminate-ferrite clinker , Calcium sulfate and a retarder.
- such a composition is prepared for use by mixing the dry ingredients with water.
- composition of the invention is very suitable for the
- An additional aspect of the present invention relates to a
- Shaped body in particular a building or a part of a building, obtainable by curing the composition with water.
- a building can e.g. a bridge, a building, a tunnel, a lane, or a runway.
- W / Z stands for water-cement value and indicates the weight ratio of water to cement.
- BCSAF cement BCSAF cement containing 4% by weight of anhydrite and 0.36% by weight of boric acid.
- Condenser V1 30% by weight solution of a comb polymer composed of structural units a) derived from acrylic acid and structural units b) the side chains of polyethylene glycol (average molecular weight of
- Polyethylene glycol chain about 2,500 g / mol), with a molar ratio of carboxylic acid groups to polyether chains of 2.3 and a middle
- the mortar mixture used for test purposes has the in Table 1
- the slump of prepared mortar mixtures was measured at different times.
- the slump of the mortar was determined according to DIN-EN 1015-3. Before each measurement, the mortar mix was mixed for 15 seconds with the Hobart mixer.
- Ao is the slump measured in mm immediately after mixing with water
- AQO is the slump measured in mm 60 minutes after mixing with water.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18175428 | 2018-05-31 | ||
PCT/EP2019/063195 WO2019228882A1 (de) | 2018-05-31 | 2019-05-22 | Verfahren zur verflüssigung von belit-calciumsulfoaluminat-ferrit-haltigen zementen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3802461A1 true EP3802461A1 (de) | 2021-04-14 |
Family
ID=62495647
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19724853.7A Pending EP3802461A1 (de) | 2018-05-31 | 2019-05-22 | Verfahren zur verflüssigung von belit-calciumsulfoaluminat-ferrit-haltigen zementen |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3802461A1 (de) |
CN (1) | CN112105591A (de) |
WO (1) | WO2019228882A1 (de) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1138696A1 (de) | 2000-03-29 | 2001-10-04 | Sika AG, vorm. Kaspar Winkler & Co. | Polymere für Zementdipergierende Zusammensetzungen |
EP2105419A1 (de) * | 2008-03-28 | 2009-09-30 | Lafarge | Zusätze für Zement |
TR201908413T4 (tr) * | 2008-09-02 | 2019-07-22 | Construction Research & Technology Gmbh | Plastikleştirici-içerikli sertleşmeyi hızlandırıcı kompozisyonun kullanımı. |
ES2426730T3 (es) | 2011-05-10 | 2013-10-24 | Sika Technology Ag | Polímero de ácido maleico, éteres alílicos y compuestos de ácido (met)acrílico, su preparación y su utilización |
US20150166691A1 (en) * | 2012-06-06 | 2015-06-18 | Sika Technology Ag | Hydrolysable polycarboxylate esters |
FR3007757B1 (fr) * | 2013-06-28 | 2015-06-05 | Lafarge Sa | Fluidifiant pour liant hydraulique comprenant un clinker sulfoalumineux |
ES2777302T3 (es) | 2014-03-27 | 2020-08-04 | Sika Tech Ag | Copolímero de bloque |
BR112018005624B1 (pt) | 2015-09-24 | 2022-12-20 | Sika Technology Ag | Copolímero, processo para a preparação de um copolímero, uso de um copolímero, composição de ligante mineral e corpo moldado |
-
2019
- 2019-05-22 WO PCT/EP2019/063195 patent/WO2019228882A1/de unknown
- 2019-05-22 CN CN201980030435.1A patent/CN112105591A/zh active Pending
- 2019-05-22 EP EP19724853.7A patent/EP3802461A1/de active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2019228882A1 (de) | 2019-12-05 |
CN112105591A (zh) | 2020-12-18 |
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