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WO2017089899A1 - Ciment activé chimiquement à l'aide de déchets industriels - Google Patents

Ciment activé chimiquement à l'aide de déchets industriels Download PDF

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Publication number
WO2017089899A1
WO2017089899A1 PCT/IB2016/001859 IB2016001859W WO2017089899A1 WO 2017089899 A1 WO2017089899 A1 WO 2017089899A1 IB 2016001859 W IB2016001859 W IB 2016001859W WO 2017089899 A1 WO2017089899 A1 WO 2017089899A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
composition according
composition
weight
optionally
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.)
Ceased
Application number
PCT/IB2016/001859
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English (en)
Inventor
Ramkumar Natarajan
Satheesh Kumar Kartheesan Thiyagarajan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eko Tech4trans Pvt Ltd
Original Assignee
Eko Tech4trans Pvt Ltd
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 Eko Tech4trans Pvt Ltd filed Critical Eko Tech4trans Pvt Ltd
Publication of WO2017089899A1 publication Critical patent/WO2017089899A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C04B28/06—Aluminous 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
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • 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
    • C04B2111/60—Flooring materials
    • 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
    • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
    • 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

  • This invention relates to process and composition of producing high performance cement using industrial wastes, more specifically, cements incorporating fly ash.
  • Fly ash is a pozzolan.
  • Class C fly ash contains silica, aluminium and calcium in combinations which makes it cementitious and self hardening and has been used as a strengthening additive in Portland cement.
  • Class C fly ash is sub-bituminous and has higher sulphur content.
  • the chemical attributes of the Class C fly ash are defined in ASTM C-61 8 which a person of ordinary skilled in the art is knowledgeable about. Adding water to Class C fly ash causes it to harden, but the same does not have significant strength. Similarly, when Class C fly ash is mixed with Portland cement there are limitations to the quantity that can be added.
  • US Patent No. 4,997,484 as well as US Patent No. 7,288,148 disclose a composition of fly ash with acid-base reacting system utilizing the combined effect of citric acid and alkali hydroxide or metal carbonate.
  • the composition does not exhibit the required working time and releases lot of heat during the setting of the cement which, in turn, causes durability issues.
  • US Patent No. 8,016,937 discloses a composition containing industrial pozzolan powder with a neutral pH activator without the use of any hydrocarboxylic acids like citric acid or metal carbonate or alkali metal stannate or alkali metal chloride in a weight proportion greater than 50% of total activator content of its cement composition and less than 30% by weight content of acidic activator in association with 95 parts of Class C fly ash to achieve high strength in short time.
  • the use of increased percentage alkali metal salt of citric acid to achieve setting not only results in increasing the cost of the final cement but also results in the quick setting of the cement creating several drawbacks, for example quick loss of slump associated with such setting. As a result, the present invention cannot be used for many applications except for rapid concrete repairs.
  • Some of the drawbacks of the prior art include: cements having quick setting time and hence limited applications; the use of hazardous alkalis such as potasium hydroxide; the quick loss of flowability resulting in difficult placement; the inability to use Class C fly ash having low amount of calcium oxide; the creation of expansive forces during setting making the cement self stressing; the difficulty in using fly ashes having high water absorption; and the high cost.
  • the inventors after years of trials have surprisingly and unexpectedly discovered that with the use of alkali metal stannate or alkali metal chloride or alkali metal phosphate along with alkali metal salt of hydro carboxylic acid in the cement composition, the working time of the cement can extend beyond three hours depending on the composition of the fly ash. This enables the cement to be used for normal construction uses.
  • this invention relates to a process and product of an activated cement composition
  • an activated cement composition comprising: industrial waste such as ground granulated blast furnace slag, cement kiln dust, lime kiln dust, and Class C fly ash having a specific surface area between 2500-7000 cm 2 /gram and/or high alumina cement; an alkali metal hydroxide; an alkali metal salt of hydro carboxylic acid and/or a source of alkali salt of hydro carboxylic acid; alkali metal fluoride; alkali metal chloride such as MgCl 2 , NaCl and KG, preferred is MgC ⁇ ; a retarder such as an alkali metal phosphate and/or an alkali metal stannate; and nano alkali metal carbonate that does not require clinkering and can be used for a broad range of applications.
  • the required surface area of the industrial byproducts can be obtained by mechanical grinding followed by classification of same.
  • a rapid setting hydraulic cement composition comprising: an industrial byproduct containing calcium oxide ranging from 10 to 50 wt %; optionally, an alkali metal hydroxide;
  • a rapid setting hydraulic cement composition comprising:
  • a controlled setting hydraulic cement composition comprising:
  • an industrial byproduct containing calcium oxide ranging from 10 to 50 wt %; optionally, an alkali metal hydroxide;
  • a retarder selected from the group consisting of: an alkali metal phosphate an alkali metal stannate, alkali metal titanate and combinations thereof;
  • an alkali metal carbonate optionally, an alkali metal carbonate.
  • a controlled setting hydraulic cement composition comprising:
  • an alkali metal hydroxide optionally, an alkali metal hydroxide
  • a retarder selected from the group consisting of: an alkali metal phosphate an alkali metal stannate, alkali metal titanate and combinations thereof;
  • an alkali metal carbonate optionally, an alkali metal carbonate
  • a rapid setting hydraulic cement composition for use in concrete road repair comprising: - an industrial byproduct containing calcium oxide ranging from 10 to 50 wt %;
  • an alkali metal hydroxide optionally, an alkali metal hydroxide
  • a sand such as quartz sand
  • a rapid setting hydraulic cement composition for use in concrete road repair comprising:
  • an alkali metal hydroxide optionally, an alkali metal hydroxide
  • a sand such as quartz sand
  • a controlled setting hydraulic cement composition comprising:
  • an alkali metal hydroxide optionally, an alkali metal hydroxide
  • a retarder selected from the group consisting of: an alkali metal phosphate an alkali metal stannate, and combinations thereof;
  • an alkali metal carbonate optionally, an alkali metal carbonate
  • a sand such as quartz sand
  • a cement composition comprising fly ash and the use of an activator such as a fluoride.
  • the fluoride is sodium fluoride.
  • a cement composition comprising fly ash and retarders to prevent a sudden loss in flowability.
  • the cement composition of the present invention uses chlorides as retarders as they are cheaper than borates or tartrates.
  • the cement composition comprising fly ash has an extended working time through the use of low cost retarders such as magnesium chloride.
  • a cement composition comprising fly ash and a retarder selected form the group consisting of: alkali metal phosphate, alkali metal stannate and a combination thereof.
  • a cement composition comprising fly ash and which does not require the use of harsh alkalis.
  • a cement composition comprising fly ash having low calcium oxide in combination with calcium aluminate cement.
  • a cement composition comprising fly ash whereby the self stressing nature thereof is prevented or limited by using of quartz sand powder as additive.
  • a cement composition comprising fly ash having high water absorption which is ground and classified and mixed with water reducing agents such as polycarboxylate ethers.
  • the present invention provides for the use of industrial waste such as fly ash to prepare both rapid setting cement composition and controlled setting cement composition.
  • the rapid setting hydraulic cement composition for use in concrete road repair comprising;
  • an alkali metal hydroxide optionally, an alkali metal hydroxide
  • a granular material such as sand (preferably quartz sand) and water.
  • the composition further comprises an high alumina content cement when the calcium oxide content in the industrial byproduct is less than 10%.
  • the controlled setting hydraulic cement composition comprising:
  • an industrial byproduct containing calcium oxide ranging from 5 to 50 wt %; optionally, an alkali metal hydroxide;
  • a retarder selected from the group consisting of: an alkali metal phosphate an alkali metal stannate, and combinations thereof;
  • an alkali metal carbonate optionally, an alkali metal carbonate
  • a granular material such as sand (preferably quartz sand) and water.
  • the cement composition has a setting time ranging between 3 minutes to 5 hours depending on the composition chosen.
  • the industrial byproducts containing lime may be selected from the group of Class C fly ash, Ground Granulated Blast Furnace Slag (GGBFS), Cement Kiln Dust or Lime Kiln Dust.
  • Class F fly ash can used in combination with any one of Ground Granulated Blast Furnace Slag (GGBFS), Cement Kiln Dust and Lime Kiln Dust.
  • ASI Aluminum Saturation Index
  • Industrial waste having calcium oxide in the range of 5-50% having a specific surface area between 2500- 7000 cm 2 /g is preferably present in an amount ranging from 80 to 95% by weight of the total composition; quartz sand powder is preferably present in an amount ranging from 0.1 to 20% by weight of the total composition; alkali metal oxide is preferably present in an amount ranging from 0.1 to 5% by weight of the total composition; nano alkali metal carbonate is preferably present in an amount ranging from 0.1 to 4% by weight of the total composition; alkali metal of hydrocarboxylic acid is preferably present in an amount ranging from 0.1 to 7% by weight of the total composition; alkali metal fluoride is preferably present in an amount ranging from 0.1 to 5% by weight of the total composition; alkali metal phosphate is preferably present in an amount ranging from 0.1 to 7% by weight of the total composition; alkali metal chloride is preferably present in an amount ranging from 0.1 to 3% by weight of the total composition; hydrocarboxy
  • alkali metal stannate is preferably present in an amount ranging from 0.1 to 4% by weight of the total composition and/or alkali metal titanate is preferably present in an amount ranging from 0.1 to 4% by weight of the total composition.
  • the surface area of the unclassified fly ash used ranged from 2000- 4000 cm 2 /gram.
  • the classified fly ash preferably has a surface area ranging from 3300 to 4000 cm 2 /gram. It is preferable to use fly ash within those particle size ranges as uniform particle size distribution is preferable for the performance of the cement.
  • cements according to the present invention can be used to make concretes by the addition of various types of aggregates commonly used in the field.
  • the purposes disclosed herein are understood to be examples of the breadth of use the present invention can be applied and should not be construed to be limited to such.
  • Example 1 The following examples are included to illustrate the present invention and are not to be considered limiting thereof. In each of the examples, the amount of water was carefully controlled, as would be understood by the person of ordinary skill in the art, to ensure an efficient mixing and reaction and also to ensure that the cement created was of sufficient strength. The person skilled in the art will understand the scope of the invention is defined by the claims appended hereto. Example 1
  • a cementitious composition was prepared according to the following composition:
  • a cementitious composition was prepared according to the following composition:
  • the final setting time was 2 hours.
  • the cement hardness was monitored and recorded over a range of time of up to 4 weeks.
  • the results of the hardness testing for example 2 are listed below:
  • a cementitious composition was prepared according to the following composition:
  • the final setting time was 24 minutes.
  • the cement hardness was monitored and recorded over a range of time of up to 4 weeks.
  • the results of the hardness testing for example 3 are listed below:
  • a cementitious composition was prepared according to the following composition:
  • a cementitious composition was prepared according to the following composition:
  • the final setting time was 15 minutes.
  • the cement hardness was monitored and recorded over a range of time of up to 4 weeks.
  • the results of the hardness testing for example 5 are listed below:
  • a cementitious composition was prepared according to the following composition:
  • Nano Calcium Carbonate - 20 g (Particle size between 5 to 10 microns)
  • the final setting time was 12 minutes.
  • the cement hardness was monitored and recorded over a range of time of up to 4 weeks.
  • the results of the hardness testing for example 6 are listed below:
  • a cementitious composition was prepared according to the following composition:
  • the final setting time was 2 hours.
  • the cement hardness was monitored and recorded over a range of time of up to 4 weeks.
  • the results of the hardness testing for example 7 are listed below:
  • a cementitious composition was prepared according to the following composition:
  • a cementitious composition was prepared according to the following composition:
  • the final setting time was 20 minutes.
  • the cement hardness was monitored and recorded of time of up to 4 weeks.
  • the results of the hardness testing for example 9 are listed below:
  • a cementitious binder was prepared according to the following composition:
  • the final setting time was 4 hours.
  • the cement hardness was monitored and recorded of time of up to 4 weeks.
  • the results of the hardness testing for example 10 are listed below:

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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)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne un procédé et un produit d'une composition de ciment activé comprenant : des déchets industriels tels qu'un laitier de haut-fourneau granulé broyé, de la poussière de four à ciment, de la poussière de four à chaux, et des cendres volantes de classe C ayant une surface spécifique entre 2 500 et 7 000 cm2/g et/ou du ciment alumineux ; un hydroxyde de métal alcalin ; un sel de métal alcalin d'acide hydrocarboxylique et/ou une source de sel alcalin d'acide hydrocarboxylique ; un fluorure de métal alcalin ; un chlorure de métal alcalin tel que du MgCl2, du NaCl et du KCl, de préférence du MgCl2 ; un retardateur tel qu'un phosphate de métal alcalin et/ou un stannate de métal alcalin ; et un nano-carbonate de métal alcalin qui ne nécessite pas de scorification et qui peut être utilisé dans une large gamme d'applications.
PCT/IB2016/001859 2015-11-26 2016-11-16 Ciment activé chimiquement à l'aide de déchets industriels Ceased WO2017089899A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA2913306A CA2913306A1 (fr) 2015-11-26 2015-11-26 Ciment active chimiquement au moyen de dechets industriels
CA2,913,306 2015-11-26

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WO2017089899A1 true WO2017089899A1 (fr) 2017-06-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024205584A1 (fr) * 2023-03-30 2024-10-03 Green Cement Inc. Matériaux cimentaires à base de poussière de four à ciment (ckd) et de poussière de four à chaux (lkd), béton, et techniques associées

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10981828B2 (en) * 2018-08-22 2021-04-20 The Catholic University Of America High strength class C fly ash cementitious compositions with controllable setting

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538036A (en) * 1968-04-25 1970-11-03 Harry T Campbell Sons Corp Concrete composition containing polymeric acrylic resin
US4434192A (en) * 1977-09-13 1984-02-28 Easy-Do Products Limited Process for making water activatable tiles
US5106423A (en) * 1988-12-02 1992-04-21 Geochemical Corporation Formation grouting method and composition useful therefor
US5584926A (en) * 1992-04-13 1996-12-17 Aalborg Portland A/S Cement compostion
US20040040474A1 (en) * 2002-08-29 2004-03-04 Marianela Perez-Pena Very fast setting cementitious composition
US20050092210A1 (en) * 2003-10-30 2005-05-05 Radtke Clifford J.Jr. Method of forming hydraulic cement protective coatings
US20080302276A1 (en) * 2007-06-06 2008-12-11 United States Gypsum Company Very fast setting cementitious composition with high early-age compressive strength

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538036A (en) * 1968-04-25 1970-11-03 Harry T Campbell Sons Corp Concrete composition containing polymeric acrylic resin
US4434192A (en) * 1977-09-13 1984-02-28 Easy-Do Products Limited Process for making water activatable tiles
US5106423A (en) * 1988-12-02 1992-04-21 Geochemical Corporation Formation grouting method and composition useful therefor
US5584926A (en) * 1992-04-13 1996-12-17 Aalborg Portland A/S Cement compostion
US20040040474A1 (en) * 2002-08-29 2004-03-04 Marianela Perez-Pena Very fast setting cementitious composition
US20050092210A1 (en) * 2003-10-30 2005-05-05 Radtke Clifford J.Jr. Method of forming hydraulic cement protective coatings
US20080302276A1 (en) * 2007-06-06 2008-12-11 United States Gypsum Company Very fast setting cementitious composition with high early-age compressive strength

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024205584A1 (fr) * 2023-03-30 2024-10-03 Green Cement Inc. Matériaux cimentaires à base de poussière de four à ciment (ckd) et de poussière de four à chaux (lkd), béton, et techniques associées

Also Published As

Publication number Publication date
CA2913306A1 (fr) 2017-05-26

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