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
  • 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
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/02—Alcohols; Phenols; Ethers
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
  • C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/121—Amines, polyamines
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/122—Hydroxy amines
• • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2641—Polyacrylates; Polymethacrylates
  • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
• • 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
  • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
  • C04B2103/0088—Compounds chosen for their latent hydraulic characteristics, e.g. pozzuolanes
• • 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
  • C04B2103/40—Surface-active agents, dispersants
  • C04B2103/406—Surface-active agents, dispersants non-ionic
• • 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
  • C04B2103/52—Grinding aids; Additives added during grinding
• • 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
• • 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 a novel process for manufacturing high performance cements, a novel grinding aid composition comprising an ester and/or ether polycarboxylate, to method for producing such composition and to use of such composition in the production of cement with or without other additives.
• clinker is firstly produced by pulverizing at high heat a mixture of silica, alumina and limestone containing materials in a rotary kiln. Said high heat is more than 1.400°C. Then, cements are produced by grinding clinker and gypsum in a suitable mill. 27 types of cement are listed in DIN-EN 197-1.
• Cement production is accompanied by the release of a significant amount of carbon dioxide caused by the energy consumption in the rotary kiln while producing the clinker and also caused by the calcining of limestone.
• 1 ton of carbon dioxide can be released.
• the release of carbon dioxide is tried to be reduced via the reduction of clinker production.
• Carbon dioxide emission in cement production could be reduced if the quantity of clinker is reduced by about 35%.
• mineral additives are added to the cement.
• the low amount of clinker and higher number of mineral additives cause to a reduction in the required specifications of cement and concrete such as strength, hardness and time of setting.
• additives are known in the prior art in order to minimize the energy utilization by accelerating of grinding or milling process.
• additives can be plasticizers, retarders, accelerators and/or stabilizers and they are generally used in order to increase the efficiency of the grinding step of the cement production by lowering the energy used.
• U.S. Patent No. 2,673,810 discloses that potassium nitrate is an effective retarder.
• Organic amines such as trialkanolamines are examples of accelerators used in the grinding of the clinker as disclosed in "Cement and Concrete Research", Ramachandran, (1973).
• polycarboxylates are also used as grinding aid during the production of cement.
• the present invention provides a grinding aid composition for use in the production of high-performance cement wherein the composition comprises a first additive comprising at least one organic amine and at least one amino alcohol and a second additive comprising at least one alkanolamine and at least one glycol.
• the present invention provides a grinding aid composition for use in the production of high-performance cement, wherein the composition is an aqueous composition comprising at least one polycarboxylate polymer and at least one surfactant.
• the present invention provides a method for manufacturing high performance cement comprising the following steps; a) providing a first additive by mixing at least one organic amine and at least one amino alcohol, b) providing a second additive by mixing at least one alkanolamine and at least one glycol, c) mixing first additive with second additive in order to obtain an additive composition, d) providing an aqueous composition of polycarboxylate polymer comprising at least one surfactant, and e) introducing together or separately said additive composition and said aqueous composition of polycarboxylate polymer into the grinding of cement clinker.
• the present invention provides a high-performance cement obtained by the method according to the present invention, wherein the cement comprises 5 to 45% of mineral additives or preferably 10 to 35% of mineral additives by weight of the cement.
• the present invention provides a novel aqueous composition for use as grinding aid in the production of high-performance cement, wherein the composition comprises at least one polycarboxylate polymer and at least one surfactant.
• the surfactant may be a non-ionic surfactant such as modified fatty alcohol or non-ionic fatty acid ester.
• the surfactant may also include 1 to 10% glycol.
• polycarboxylate polymer means the polymer having carboxy groups. Said polycarboxylate polymer can be obtained by means of polymer-like reaction.
• Polycarboxylate polymers according to the present invention may be polycarboxylate ether or polycarboxylate ester polymer.
• polycarboxylate polymers with the addition of surfactant enhances the grinding efficiency and the strength of the cement.
• the dispersibility of cement clinker during grinding is improved by the addition of polycarboxylate polymer composition according to the present invention.
• this composition used as a grinding aid results in a reduced energy consumption.
• said aqueous composition of polycarboxylate polymer is obtained by diluting the polycarboxylate polymer with non-ionized water and with a surfactant by mixing during 30 to 40 minutes.
• the dilution is preferably performed at 30°C.
• the present invention also provides a novel method for producing a high-performance cement comprising the following steps; a) providing a first additive by mixing at least one organic amine and at least one amino alcohol, b) providing a second additive by mixing at least one alkanolamine and at least one glycol, c) mixing first additive with second additive in order to obtain an additive composition, d) providing an aqueous composition of polycarboxylate polymer according to any one of the claims 1 to 5, and e) introducing together or separately said additive composition and said aqueous composition of polycarboxylate polymer into the grinding of cement.
• novel method according to the present invention provides an increase in the substitution amount of minerals and additives to the clinker.
• Second additive is prepared by mixing at least one alkanolamine and at least one glycol in reactor.
• the temperature of said mixing step of alkanolamine with glycol is preferably between 30° C to 50°C and most preferably 40°C.
• the mixing time of alkanolamine with glycol is preferably 1 hour in order to obtain a homogenous mixture.
• first additive and/or second additive may further comprise a non-ionic surfactant.
• the surfactant is between 0,1% to 0.5 and preferably 0,2% to 0,3% by weight of the grinding aid composition.
• Amino alcohol according to the present invention is selected from the group consisting of 1- (N,N-Bis(2-hydroxyethyl)amino)propan-2-ol (Diethanolisopropanolamine, also known as DEIPA), ethanolamine, diethanolamine, triethanolamine, N-butyldiethanolamine, M- methyldiethanolamine, diaminomethanal (urea), N-ethyldiethanolamine, diisopropanolamine, methyl diisopropanolamine, tetrahydroxypropylethylenediamin, trimethylaminoethylethanolamine and combinations thereof.
• Preferred amino alcohol is diethanolisopropanolamine (DEIPA).
• Amino alcohol is in an amount of 30 to 50% by weight of the first additive.
• Organic amine according to the present invention is selected from the group consisting of 2- ethyldiisopropylamine (DIPEA/EDIPA), diethylamine, triethylamine, dimethylamine pyridine, ethyldiisopropylamine, procaine, dibenzylamine, N-methylmorpholine, dihydroabietylamine, 1-ephenamine, methyl-piperidine and combinations thereof.
• Preferred organic amine is 2-ethyldiisopropylamine (DIPEA).
• Organic amine is in an amount of 50 to 70% by weight of the first additive.
• Alkanolamine according to the present invention is selected from the group consisting of 2,2,2-nitrilotriethanol (triethanolamine), l,l,l-nitrilopropan-2-ol (triisopropanolamine), diethanolamine, diethoxylated isopropylamine and combinations thereof.
• Preferred alkanolamine is triethanolamine.
• Alkanolamine is in an amount of 70 to 90% by weight of second additive.
• Glycol according to the present invention is selected from the group consisting of 2- (hydroxyethoxy)ethan-2-ol (diethylene glycol), ethylene glycol, propylene glycol, glycerol (propan- 1, 2, 3-triole), polyethylene glycol, monopropylene glycol and combinations thereof.
• Preferred glycol is glycerol and/or diethylene glycol.
• Glycol is in an amount of 10 to 30% by weight of second additive.
• first additive may further comprise diaminomethanal (urea).
• urea diaminomethanal
• the amount of urea used in the production method is between 5% to 25% by weight on the weight of the first additive and preferably between 10% to 20% by weight.
• the step of mixing first and second additive is occurred at 30 to 65°C and preferably 40 to 60°C.
• the ratio of first additive to second additive is between 1:0.5 and 4:1. It has been surprisingly found that the method according to the present invention enables the mill to grind the clinker to a smaller size with less energy and within a short time. The reduction in amount of energy necessary allows the carbon dioxide emissions from the production of cement clinker to be greatly reduced by substution of mineral(s).
• the method and polycarboxylate polymer composition that has a density of 1.0 -1.10 g/cm and a pH of between 7 to 9, also provide the cement having an increased 1-day, 2-day, 7-day and 28-day compressive strength.
• the method may further comprises adding other additives during or before grinding such as retarders, anti-corrosion agents, dryers, fluidizer, anti-foaming, anti-freezing agents and water reducing agents.
• Said polycarboxylate polymer composition and said mixture of first and second additive in the production method of high-performance cement can be defined as grinding aid and cement chemical admixture compositions. These admixture compositions are suitable for use on conventional grinding mills such as ball mills or roller mills. Thus, grinding of cement clinker is performed in those grinding mills.
• the present invention provides the use of the aqueous composition of polycarboxylate polymer and the mixture of first additive and second additive according to the present invention in the production of cement, as grinding aids.
• Said compositions increase the normal setting time and the normal compressive strength of a cement and a concrete mixture. The strength is enhanced both in the near-term, first day, and in the long-term, after 28 days.
• the tests can be performed with respect to the standard tests in the prior art such as EN 197-1, EN 197-2 or ASTMC150/150 M-18. More specifically, EN196-7, EN 196-2, EN 196-3, EN 196-6, EN 196-1 or ASTM C595/C595M, ASTM C109/C109M, ASTM C150.
• Cements may further comprise mineral additives selected from the group consisting of siliceous fly ash, calcareous fly ash, blast-furnace slag, limestone (as calcium carbonate), silicon dioxide (as silica sand), natural pozzolan, industrial pozzolan and burnt shale.
• the kind and percentage of cement's composition determine the type of cement. Accordingly, 27 types of cement in total are specified.
• Basic cement types are portland cement (CEM I), Portland composite cement (CEM II), blast furnace cement (CEM III), pozzolanic cement (CEM IV), hydraulic cement, slag cement or composite cement (CEM V).
• cement is preferably portland cement and others.
• Clays and limestone are raw materials to produce the clinker which is the hydraulic compound mainly used in the production of cement.
• Clinker comprises calcium silicates which can be tricalcium silicate, dicalcium silicate, tricalcium aluminate and aluminoferrite.
• cements may further comprise nano- sized minerals such as micro and nano particles of silica, aluminum and ferrite oxides.
• Clinker process according to the present invention is the conventional process utilizing a rotary kiln.
• Cement raw materials such as calcareous material is firstly grinded into fine powder. Then, they are introduced in the kiln in which said raw materials are mixed to produce a uniform composition and are heated at 1000°C - 1500°C and preferably 1350°C - 1450°C. Finally, the mixture which can be named as clinker is cooled in the cooler.
• cement production method comprises the step of grinding a clinker in the presence of said aqueous composition of polycarboxylate polymer and the mixture of first additive and second additive according to the present invention.
• the clinker amount can be reduced in the cements, being this a reduction of specific energy consumption and CO2 emission is provided.
• the amount of grinding aid in the cement is between 100 and 3000 g/ton and preferably between 500 and 2500 g/ton by weight of the cement.
• the clinker is introduced into a grinding apparatus and grinding is affected until the desired fineness of cement is obtained.
• Degrees of fineness of the cement comprising the grinding aid of the present invention are between 2000 to 10000 g/cm , preferably between 3000 to 6000 g/cm 2 and more preferably between 3500 to 4500 g/cm 2.
• the addition of the polycarboxylate polymer composition and/or first and second additive mixture may be performed by spraying onto the clinker.
• the spraying is performed by a conventional dosing pump.
• the polycarboxylate polymer composition and the mixture of first and second additive can be added separately onto the clinker.
• first additive and second additive can be added separately without mixing to the clinker in order to perform the grinding step.
• Gypsum In the grinding of cement production process, gypsum may be added with the clinker. Gypsum is sulfate mineral comprising calcium sulfate dihydrate. Gypsum is added in the grinding process in order to regulate the setting time.
• These grinding aid compositions in the cement production method is between 0.1% and 5% and preferably 0.3% to 2.5% by weight of the cement.
• Aqueous composition of polycarboxylate polymer Production method of the aqueous composition of polycarboxylate polymer - providing polycarboxylate polymer which is synthesized by etherification reaction of carboxylated acrylic acid monomer, - diluting polycarboxylate polymer with non-ionized water and non-ionic surfactant in mixer during 40 minutes and at 30°C. (pH is neutral at 7)
• Said mixture and composition are introduced together during the grinding of cement.

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• 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)

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• 2019
  • 2019-11-13 EP EP19952883.7A patent/EP4073013A4/de active Pending
  • 2019-11-13 KR KR1020227019951A patent/KR20220104191A/ko not_active Application Discontinuation
  • 2019-11-13 WO PCT/TR2019/050945 patent/WO2021096445A1/en unknown

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