AU2007200162A1 - A Process for the Production of Geopolymer Cement from Fly Ash and Granulated Blast Furnace Slag, Geopolymer Cement Made Thereby and Process of Making Products Thereof - Google Patents
A Process for the Production of Geopolymer Cement from Fly Ash and Granulated Blast Furnace Slag, Geopolymer Cement Made Thereby and Process of Making Products Thereof Download PDFInfo
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- AU2007200162A1 AU2007200162A1 AU2007200162A AU2007200162A AU2007200162A1 AU 2007200162 A1 AU2007200162 A1 AU 2007200162A1 AU 2007200162 A AU2007200162 A AU 2007200162A AU 2007200162 A AU2007200162 A AU 2007200162A AU 2007200162 A1 AU2007200162 A1 AU 2007200162A1
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- 238000000034 method Methods 0.000 title claims description 54
- 230000008569 process Effects 0.000 title claims description 51
- 239000011413 geopolymer cement Substances 0.000 title claims description 48
- 229920003041 geopolymer cement Polymers 0.000 title claims description 48
- 239000002893 slag Substances 0.000 title claims description 42
- 239000010881 fly ash Substances 0.000 title description 36
- 238000004519 manufacturing process Methods 0.000 title description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000004137 mechanical activation Methods 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910017976 MgO 4 Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000002440 industrial waste Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000013031 physical testing Methods 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000009970 fire resistant effect Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920000876 geopolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011178 precast concrete Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010891 toxic waste Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- 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
- 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
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT Name of Applicant: Address for Service: Invention Title: Council of Scientific and Industrial Research CULLEN CO.
Level 26 239 George Street Brisbane Qld 4000 A Process for the Production of Geopolymer Cement from Fly Ash and Granulated Blast Furnace Slag, Geopolymer Cement Made Thereby and Process of Making Products Thereof The following statement is a full description of the invention, including the best method of performing it, known to us: The present invention relates to a process for the production of geopolymer cement from fly ash and granulated blast furnace slag, geopolymer cement made thereby and process of making products thereof. The invention particularly relates to a process for the production of geopolymer cement from fly ash and granulated blast furnace slag, which is waste material of thermal power plant and iron steel plant respectively.
The products produced by the process of present invention will use fly ash and granulated blast furnace slag as the main component, which is industrial wastes and abundantly available in India and worldwide. The process does not require large energy consumption and also no CO 2 emission. Also the processing steps are simple and easy. The products produced by the process of present invention may gain good compressive strength in short time, have good volume stability, excellent durability and high fire resistance. The geopolymer cement of the present invention shall be useful as binder material, main ingredient in precast concrete blocks, fire resistant and insulated panels, decorative stone artefacts, building materials, cast ceramic tiles, and immobilization of toxic wastes.
The hitherto known processes to produce geopolymer cement use pure material such as silica and alumino-silicate minerals as main raw material Davidovits, Journal of Materials Education, Vol. 16, pp. 91-138, 1994). The silicates and hydroxides of sodium and potassium are used as alkaline activator for geopolymeric reactions. The existing possesses uses alumino-silicate mineral such as kaolinite as the main ingridient. Geopolymer cement is formed by calcination of kaolinite mineral followed by polycondensation in the highly alkaline environment. The existing process consisted of calcining of kaolinite in a gas fired or electrically heated furnace at a temperature in the range of 6500 1050 0 C for 2 to 8 hours, cooling to ambient temperature, mixing with alkaline activators such as silicates or hydroxides of potassium or sodium shaping in desired shape and then curing at a temperature in the range of 600 250oC Another known process to produce geopolymer cement use pure alumina and silica Barbosa et al., International Journal of Inorganic Materials, Vol, pp 309-317, 2000). The process consisted of through mixing of raw materials in a mechanical mixer, mixing with alkaline activators such as silicates or hydroxides of potassium or sodium, shaping in desired shape and then curing at room temperature for 1 to days followed by heating at temperature in the range of 600 2500C.
Yet another known process to produce geopolymer cement uses fly ash, kaolinite, sodium silicate and sodium hydroxide as raw material G. S. van Jaarsveld et al, Chemical Engineering Journal, Vol 89, pp 63-73, 2002). The process consisted of proportioning and blending of raw fly ash and kaoline, mixing with sodium based alkaline activators, vibro-casting in desired shape and then curing at a room temperature for minimum 7 days and then heating in the range of 600 2000C.
The hitherto known processes as referred herein above have the following limitations: a. The production cost of geopolymeric material is relatively high when it uses costly raw materials such as pure silica and alumina as main ingredient.
b. The formation of geopolymeric material is an energy intensive process when it uses naturally occurring kaolin. Calcination of kaolin at a temperature in the range 650° 10500C for 2 to 8 hours consumes high energy.
c. The setting of geopolymer cement takes more time when fly ash is used as one of the raw material.
Traditionally, geopolymer cement are produced by intermixing of alumino-silicate bearing minerals such as kaolin with sodium and potassium based alkaline activator, curing at room temperature followed by curing at elevated temperature (J.
Davodovits, Journal of Thermal Analysis, Vol 37, pp 1633-1656, 1991).
Reference may be made to U.S. Patent 4472199 on synthetic mineral polymer compound of the silico-aluminate family and preparation process by Davidovits et al, wherein cast or moulded geopolymers can be produced for zeolite application.
Another reference may be made to U.S. Patent 4509985 on Early high strength mineral polymer by Davidovits et al, wherein geopolymer can be produced by adding a reactant mixture consisting of alumino-silicate oxide with the aluminium cation in sodium or potassium based activators.
Yet another reference may be made to J. C. Swanepoel and C. A. Strydom "Utilisation of fly ash in a geopolymeric material, Applied Geochemistry Volume 17, Issue 8 pp 1143-1148, 2002" wherein fly ash was used as one of the ingredient of geopolymer cement.
Reference may also be made to A. Palomo et al, "Alkali-activated fly ashes, a cement for the future, Cem. Concr. Res.Vol 29, pp 1323-1329, 1999", wherein the potential for fly ash as raw material for geopolymer cement has been explored.
According to literature and patent survey and available information, it may be mentioned that at present no process is available to produce geopolymer cement using fly ash and granulated blast furnace slag. The purpose of this development is to use abundantly available waste materials such as fly ash and granulated blast furnace slag, which is causing environmental pollution, to produce value added product such as geopolymer cement for various application.
The main object of the present investigation is to provide a process for the production of geopolymer cement from fly ash and granulated blast furnace slag, geopolymer cement made thereby and process of making products thereof, which obviates the drawbacks as detailed above.
Another object of the present invention is to provide a process to produce geopolymer cement whereby use is made of abundantly available waste materials such fly ash and granulated blast furnace slag which is causing environmental pollution, to produce value added product such as geopolymer cement for various applications.
Still another object of the present invention is to provide a process to produce geopolymer cement whereby the energy consumption is significantly reduced.
Yet another object of the present invention is to provide a process to produce geopolymer cement whereby the cost of production is appreciably lowered and the properties of the product is improved.
Still yet another object of the present invention is to provide a process to produce geopolymer cement whereby the strength development and setting properties of the product is improved.
The present invention provides a process for the production of geopolymer cement from fly ash and granulated blast furnace slag, geopolymer cement made thereby and process of making products thereof. The products produced by the process of present invention will use very high proportion (60 95%) of industrial waste such as fly ash and granulated blast furnace slag. The process does not require large energy consumption and also no CO 2 emission. Also the processing steps are simple and easy. The products produced by the process of present invention may gain good comprehensive strength in short time, have good volume stability, excellent durability and high fire resistance. The geopolymer cement of the present invention shall be useful as binder material, main ingredient in precast concrete blocks, fire resistant and insulated panels, decorative stone artefacts, building materials, cast ceramic tiles and immobilization of toxic wastes. In the process of the present invention, the granulated blast furnace slag is fine grounded and/or mechanically activated in conventional grinding mills or high-energy mills. The fly ash, which is found in powder form and fine powder of granulated blast furnace slag, is thoroughly mixed with sodium or potassium based alkaline activator and water. The paste is cured at room temperature during which the dissolution of silica and alumina present if fly ash and granulated blast furnace slag starts. After the initial dissolution, the paste is heat treated at the temperature in the range of 60-200 0 C. Due to enhanced curing temperature two type of reaction mechanism takes place, first the dissolution reactions of silico aluminate, which proceeds simultaneously with the gel formation and poly-condensation reactions and results into formation of polymeric Si-O-AI-O bonds called polysialate. Formation of polysialate results into setting of geopolymer cement and strength development. Secondly the latent hydraulic property of granulated blast furnace slag is enhanced at elevated temperature curing. During the hydration reactions, the CaO and Si0 2 present in slag reacts with water and form the C-S-H gel (C=CaO, S=SiO 2
H=H
2 which is cementitious in nature. Formation of C-S-H gel accelerates the setting time at the earlier stage and also contribute towards strength development at later stage. Novelty of the present invention is that it gains-the very high compressive strength in short time (20-60 MPa in 4 hours and 30-120 MPa in 24 hours). Another novelty is that the geopolymer cement uses two major industrial waste, fly ash and granulated blast furnace slag, as the major raw Smaterial (up to 95% of total composition).
(-i SThe fly ash used in the present invention contains SiO 2 A1 2 0 3 and Fe20 3 and is
INO
5 partly crystalline and partly amorphous in nature.
r In the process of the present invention, the granulated blast furnace slag is fine
INO
grounded and/or mechanically activated in conventional grinding mills or high energy Smills. The fly ash, which is found in powder form and fine powder of granulated blast r- 10 furnace slag, is thoroughly mixed with sodium or potassium based alkaline activator Sand water. The paste is cured at room temperature during which the dissolution of silica and alumina present of fly ash and granulated blast furnace sla starts. After the initial dissolution, the paste is heat treated at the temperature in the range of 2000C. Due to enhanced curing temperature two type of reaction mechanism takes place, first the dissolution reactions of silico-aluminate, which proceeds simulataneously with the gel formation and poly-condensation reactions and results into formation of polymeric Si-O-AI-O bonds called polysialate. Formation of polysialate results into. setting of geopolymer cement and strength development.
Secondly the latent hydraulic property of granulated blast furnace slag is enhanced at elevated temperature curing. During the hydration reactions, the CaO and Si02 present.in slag reacts with water and form the C-S-H gel (C=CaO, S=Si02, which is cementitious in nature. Formation of C-S-H gel accelerates the setting time at the earlier stage and also contribute towards strength development at later stage.
Accordingly, the present invention provides a process for the production of geopolymer cement from fly ash and granulated blast furnace slag, which comprises: Subjecting granulated blast furnace slag to milling- to enable fine grinding and/or mechanical activation for a period in the range of 10-120 minutes and reducing the size below 100 microns; (ii) mixing intimately for a period in the range of 5 to 30 minutes in a mechanical mixer, the said ground granulated blast furnace slag obtained in step(i), with fly ash obtained from coal fired power plants and alkaline activator, wherein: the ground granulated blast furnace slag is 5 to 22% by weight; the fly ash is 60 to 90% by weight; and the alkaline activator is 3 to 20% by weight.
In an embodiment of the present invention, the granulated blast furnace slag is subjected to milling in either dry or wet condition.
In yet another embodiment of the present invention, the milling to enable fine grinding and /or mechanical activation is effected in a device such as ball mill, roller press, vibration mill, attrition mill, jet mill, planetary mill.
In still another embodiment of the present invention, the fly ash and granulated blast furnace is having the following composition range: Constituent (wt. Fly ash Granulated blast furnace slag SiO 2 40-70 25-35 A1 2 0 3 20-30 15-25 Fe 2 03 0-5 0-1 CaO 0-5 25-40 MgO 0-1 4-15 MnO 0-2 0-1 In a further embodiment of the present invention, alkaline activator is such as sodium oxide, sodium hydroxide, sodium silicate, sodium nitrate, potassium oxide, potassium hydroxide, potassium silicate, potassium nitrate.
Accordingly, the present invention provides, a geopolymer cement made by the process as detailed herein above.
Accordingly, the present invention provides a process of making products from geopolymer cement made by the process as detailed herein above, which comprises mixing intimately 65 to 85 by weight of geopolymer cement with 15 to35% by weight of water, for a period in the range of 5 to minutes, under mechanical stirring, to obtain a paste; casting the paste obtained in step in moulds by known methods; keeping the cast products in the said moulds for a period ranging between 1 to 8 hours, in a humid atmosphere; drying the cast products at ambient temperature for a period of 2 to 24 hours; curing the dried products in a drying oven at a temperature in the range of 50 to 2001C, for a period of 2 to 8 hours.
In an embodiment of the present invention, the cast product in mould is kept in a humid atmosphere, wherein humidity is in the range of 90 to 98%.
In another embodiment of the present invention, the curing of the dried products at a temperature in the range of 50 to 200 0 C for a period of 2 to 8 hours, is effected in a drying oven, such as an electrically heated or gas fired drying oven.
In still another embodiment of the present invention, geopolymeric cement has the following range of properties: setting time: initial setting 15-30 minutes final setting 60 -180 minutes Compressive strength: after 4 hours 20-60 MPa after 24 hours 30-120 MPa fire resistance withstand 800"C autoclave expansion <0.5 Novelty of the present invention is that it provides a very simple, energy efficient and eco-friendly process to produce a product which gains very high compressive strength in a short time 20-60 MPa in 4 hours and 30-120 MPa in 24 hours), is fire resistant, volume expansion 0.5% and hardness >5 on Mohs scale and. Another novelty is that the geopolymer cement uses two major industrial waste, fly ash and granulated blast furnace slag, as the major raw material (up to 95% of total composition).
3 One of the non-obvious inventive steps of the process of the present invention is fine grinding and/or mechanical activation of granulated blast furnace slag. Due to fine grinding and/or mechanical activation, the latent hydraulic activity of the slag is Sincreased. Further non-obvious steps are inclusion of an alkaline activator and
INO
5 thermal curing, which leads to enhanced dissolution of fly ash particles followed by co-precipitation and geo-polymerisation.
(N
INO
The following examples are given by way of illustration and should not be construed Sto limit the scope of invention.
S 10o EXAMPLE-1 C 200 grams of granulated blast furnace slag was ball milled for 120 minutes to get the particle size <100 jlm. 600 grams of fly ash, 200 grams of ball milled slag and 200 grams of sodium hydroxide was thoroughly mixed for 15 minutes in a mechanical mixer. 500 ml water was added into the mixture and mixed for 15 minutes in a mechanical stirrer. The paste obtained after mixing was casted into 2 inch cube mould The cube mould was kept in 95% humidity for 2 hours and then dried at ambient temperature for 4 hours. The dried samples were cured at 700C in an electrical oven for 6 hours and then cooled to ambient temperature for various tests.
Physical testing such as setting time, compressive strength, fire resistance, autoclave expansion and hardness was carried out as per standard test methods.
The properties of geopolymer cement obtained are furnished in table 1 below: Table 1 Properties of geopolymer cement discussed above Properties Values Setting time (minute) Initial Final Compressive strength (MPa) 4 hours 24 hours 110 Autoclave expansion 0.02 Fire resistance withstand 900C Hardness (Mohs scale) EXAMPLE-2 150 grams of granulated blast furnace slag was attrition milled for 20 minutes to get the particle size <100 gm. 700 grams of fly ash, 150 grams of attrition milled slag and 150 grams of sodium silicate was thoroughly mixed for 25 minutes in a mechanical mixer. 400 ml water was added into the mixture and mixed for minutes in a mechanical stirrer. The paste obtained after mixing was casted into 2 inch cube mould The cube mould was kept in 95% humidity for 2 hours and then dried at ambient temperature for 6 hours. The dried samples were cured at 1000C in an electrical oven for 8 hours and then cooled to ambient temperature for various tests. Physical testing such as setting time, compressive strength, fire resistance, autoclave expansion and hardness was carried out as per standard test methods.
The properties of geopolymer cement obtained are furnished in table 2 below: Table 2 Properties of geopolymer cement discussed above Properties Values Setting time (minute) Initial Final Compressive strength (MPa) 4 hours 24 hours Autoclave expansion 0.02 Fire resistance withstand 9000C Hardness (Mohs scale) EXAMPLE -3 150 grams of granulated blast furnace slag was vibratory milled for 30 minutes to get the particle size <100 pm. 750 grams of fly ash, 150 grams of vibratory milled slag and 100 grams of potassium hydroxide was thoroughly mixed for 30 minutes in a mechanical mixer. 500 ml water was added into the mixture and mixed for minutes in a mechanical stirrer. The paste obtained after mixing was casted into 2 inch cube mould. The cube mould was kept in 95% humidity for 4 hours and then dried at ambient temperature for 4 hours. The dried samples were cured at 1500C in an electrical oven for 2 hours and then cooled to ambient temperature for various tests. Physical testing such as setting time, compressive strength, fire resistance, autoclave expansion and hardness was carried out asper standard test methods.
The properties of geopolymer cement obtained are furnished in table 3 below: Table 3 Properties of geopolymer cement discussed above Properties Values Setting time (minute) Initial Final Compressive strength (MPa) 4 hours 24 hours Autoclave expansion Fire resistance Hardness (Mohs scale) 120 0.02 withstand 900 0
C
EXAMPLE -;4 grams of granulated blast furnace slag was jet milled for 30 minutes to get the particle size <100 pjm. 900 grams of fly ash, 50 grams of jet milled slag and grams of sodium hydroxide was thoroughly mixed for 30 minutes in a mechanical mixer. 300 ml water was added into the mixture and mixed for 15 minutes in a mechanical stirrer. The paste obtained after mixing was casted into 2 inch cube mould The cube mould was kept in 95% humidity for 2 hours and then dried at ambient temperature for 8 hours. The dried samples were cured at 180 0 C in an electrical oven for 6 hours and then cooled to ambient temperature for various tests.
Physical testing such as setting time, compressive strength, fire resistance, autoclave expansion and hardness was carried out as per standard test methods.
The properties of geopolymer cement obtained are furnished in table 4 below.
Properties Properties Setting time (minute) Initial Final Compressive strength (MPa) 4 hours 24 hours Autoclave expansion Fire resistance Hardness (Mohs scale) Table 4 of geopolymer cement discussed above Values 150 120 0.02 withstand 900 0
C
The main advantages of the present invention are: 1. Utilises very high proportion of abundantly available industrial waste (fly ash and granulated blast furnace slag) as major raw material to produce geopolymer cement, thereby the cost of production is considerably reduced in comparison to the known process.
2. Helpful in resource conservation by replacing costly raw materials e.g.
alumina, silica, kaolin etc which are main source of A1 2 0 3 and SiO 2 for its production by the industrial wastes.
3. Replaces alumina and silica powder, which is produced by an energy intensive grinding process and replaces kaolin which is calcined at high temperature, by an industrial wastes, thereby considerable reduction in energy consumption in comparison to the known process.
4. Involves low temperature processing (50-2000C), thereby very less to no C02 emission and energy conservation.
5. The products obtained are superior in terms of strength development in short time span.
The term "comprise" and variants of the term such as "comprises" or "comprising" are used herein to denote the inclusion of a stated integer or stated integers but not to exclude any other integer or any other integers, unless in the context or usage an exclusive interpretation of the term is required.
Any reference to publications cited in this specification is not an admission that the disclosures constitute common general knowledge in Australia.
Claims (8)
- 2. A process according to claim 1, wherein the granulated blast furnace slag is subjected to milling in either dry or wet condition.
- 3. A process according to in claim 1-2, wherein the milling to enable fine grinding and/or mechanical activation is effected in a device such as ball mill, roller press, vibration mill, attrition mill, jet mill, planetary mill.
- 4. A process according to claim 1-3, wherein the granulated blast furnace slag has the following composition range SiO 2 25 to 35%, A1 2 0 3 15 to 25%, Fe20 3 0 to CaO 25 to 40%, MgO 4 to 15%, MnO 0 to 1%. A process according to claim 1-4 wherein the granulated blast furnace slag has the following composition range SiO 2 40 to 70%, A 2 0 3 20 to 30%, Fe20 3 0 to CaO 0 to MgO 0 to MnO 0 to 2%.
- 6. A process according to claim 1-5, wherein the alkaline activator is such as sodium oxide, sodium hydroxide, sodium silicate, sodium nitrate, potassium oxide, potassium hydroxide, potassium silicate, potassium nitrate.
- 7. Geopolymer cement made by the process according to claiml-6 detailed herein above.
- 8. A process according to claim 1-7, wherein the geopolymeric cement has the following range of properties: setting time initial setting 15 to 30 minutes; final setting 60 to 180 minutes; compressive strength: after 4 hours 20-60 MPa; after 24 hours 30-120 MPa; fire resistance can withstand 8000C autoclave expansion <0.5
- 9. A process of making products from geopolymer cement according to claim 1- 8, which comprises mixing intimately 65 to 85 by weight of geopolymer cement with 15 to by weight of water, for a period in the range of 5 to 15 minutes, under mechanical stirring, to obtain paste; (ii) casting the paste obtained in step in moulds by known methods; keeping the cast products in the said moulds for a period ranging between 1 to 8 hours, in a humid atmosphere; (iii) drying the cast products at ambient temperature for a period of 2 to 24 hours; (iv) curing the dried products in a drying oven at a temperature in the range of to 2000C for a period of 2 to 8 hours. A process according to claim 9, wherein the cast product in mould is kept in a humid atmosphere, wherein humidity is in the range of 90 to 98%.
- 11. A process according to claim 9-10, wherein the curing of the dried products at a temperature in the range of 50 to 2000C for a period of 2 to 8 hours, is effected in a drying oven, such as an electrically heated or gas fired drying oven. Date: 16 January 2007
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN728/DEL/2006 | 2006-03-20 | ||
| IN728DE2006 | 2006-03-20 |
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| AU2007200162A1 true AU2007200162A1 (en) | 2007-10-04 |
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| AU2007200162A Abandoned AU2007200162A1 (en) | 2006-03-20 | 2007-01-16 | A Process for the Production of Geopolymer Cement from Fly Ash and Granulated Blast Furnace Slag, Geopolymer Cement Made Thereby and Process of Making Products Thereof |
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| WO2012172138A1 (en) * | 2011-06-17 | 2012-12-20 | Consejo Superior De Investigaciones Científicas (Csic) | Method for the production of alkali cements from industrial and urban waste glass |
| US8864901B2 (en) | 2011-11-30 | 2014-10-21 | Boral Ip Holdings (Australia) Pty Limited | Calcium sulfoaluminate cement-containing inorganic polymer compositions and methods of making same |
| US20160137551A1 (en) * | 2014-11-13 | 2016-05-19 | Colas | Geosynthsesis binder comprising a calcium- alkaline activator and a silico-aluminous compound |
| US9745224B2 (en) | 2011-10-07 | 2017-08-29 | Boral Ip Holdings (Australia) Pty Limited | Inorganic polymer/organic polymer composites and methods of making same |
| CN109776003A (en) * | 2018-01-26 | 2019-05-21 | 桂林电子科技大学 | A kind of calcium based geopolymer cementitious material of multiple elements design powder and preparation method thereof |
| WO2019170963A1 (en) * | 2018-03-09 | 2019-09-12 | Betolar Oy | Binder composition and hardenable mixture |
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|---|---|---|---|---|
| FR2489291A1 (en) | 1980-09-03 | 1982-03-05 | Davidovits Joseph | MINERAL POLYMERIC COMPOUND AND PROCESS FOR OBTAINING THE SAME |
| US4509985A (en) | 1984-02-22 | 1985-04-09 | Pyrament Inc. | Early high-strength mineral polymer |
-
2007
- 2007-01-16 AU AU2007200162A patent/AU2007200162A1/en not_active Abandoned
- 2007-02-02 KR KR1020070011158A patent/KR100857616B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
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| KR20070095187A (en) | 2007-09-28 |
| KR100857616B1 (en) | 2008-09-09 |
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