WO2022203642A1 - Production method of geopolymer binder - Google Patents

Production method of geopolymer binder Download PDF

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Publication number
WO2022203642A1
WO2022203642A1 PCT/TR2022/050271 TR2022050271W WO2022203642A1 WO 2022203642 A1 WO2022203642 A1 WO 2022203642A1 TR 2022050271 W TR2022050271 W TR 2022050271W WO 2022203642 A1 WO2022203642 A1 WO 2022203642A1
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Prior art keywords
production method
geopolymer
geopolymer binder
washing sludge
blast furnace
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PCT/TR2022/050271
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French (fr)
Inventor
Nihat KABAY
Hakan OZKAN
Nausad MIYAN
Original Assignee
Yildiz Teknik Universitesi
Oyak Beton Sanayi Ve Ticaret Anonim Sirketi
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Publication of WO2022203642A1 publication Critical patent/WO2022203642A1/en

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006Compositions 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 mineral polymers, e.g. geopolymers of the Davidovits type
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24Compositions 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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26Silicates of the alkali metals

Definitions

  • This invention relates to the production of geopolymer binders by using the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries.
  • BFS blast furnace slag
  • Aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries is disposed of at the waste sites.
  • the object of this invention is to develop a method that enables the production of geopolymer binders by using the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries.
  • Another object of this invention is to develop a method that enables the use of aggregate washing sludge, which is stored in waste sites and poses a significant environmental problem, in the production of geopolymer binder.
  • Another object of this invention is to develop a method that enables the production of geopolymer binders with high compressive strength. It is aimed that the produced geopolymer binders will exhibit strength at least comparable to the Portland cement.
  • Another object of this invention is to develop a method for producing geopolymer binders suitable for use in various engineering applications such as mortar, screed, concrete and precast segment concrete production.
  • Another object of the invention is to develop a geopolymer binder in the form of paste produced from blast furnace slag and aggregate washing sludge.
  • the production method of geopolymer binder of the invention basically, the mixture of the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries is mixed with aqueous sodium hydroxide and sodium silicate solution as alkali activator.
  • aqueous sodium hydroxide and sodium silicate solution as alkali activator.
  • the chemical composition of aggregate washing sludge also varies depending on the mineralogical properties of the respective quarries and the details of the crushing and washing processes.
  • the aggregate washing sludge which generally consists of minerals such as quartz, illite, kaolinite, feldspar, chlorite, calcite, dolomite, etc. mainly contains SiCk, AI2O3 and Fe203.
  • the steps of the production method of the geopolymer binder of the invention includes the steps of
  • the geopolymer binder in the form of paste is cured without requiring any special process.
  • the grinding step of the blast furnace slag may also be applied prior to the step of preparing the mixture.
  • the Blaine specific surface of the blast furnace slag is in the range of 5000 ⁇ 500 cm 2 /g.
  • the aggregate washing sludge can usually be obtained in wet or partially dried condition.
  • the flocculation is also observed in the partially dried aggregate washing sludge.
  • the drying and grinding step of the aggregate washing sludge is applied.
  • the maximum particle size of the aggregate washing sludge obtained as a result of the grinding process is less than 200 pm.
  • a mixture containing dried and ground aggregate washing sludge in the range between 40% and 70% by volume is used.
  • an aqueous solution containing sodium hydroxide with a molarity in the range between 6 and 10 M and sodium silicate with a silica modulus between 0.8 and 1.6 is used.
  • the mixture of the blast furnace slag and aggregate washing sludge and sodium hydroxide and sodium silicate aqueous solution are mixed in such a way that the solution/(blast furnace slag and aggregate washing sludge) ratio is between 0.25 and 0.35 by weight.
  • the tests were also carried out on samples in the form of paste, which were stored for certain periods. During these tests, the blast furnace slag and ground aggregate washing sludge with chemical compositions given in Table 1, were used.
  • the mixtures containing aggregate washing sludge between 20% and 80% by volume and aqueous solution comprising of sodium hydroxide with molarity in the range between 4 and 12 M and sodium silicate to adjust silica modulus between 0.6 and 2.0 were mixed with a solution / (blast furnace slag and aggregate washing sludge) ratio in the range between 0.20 and 0.40 by weight to produce paste samples. Then, the prepared paste samples were kept in ambient conditions at 60 ⁇ 10% relative humidity and 22 ⁇ 5°C for certain periods. Compression tests were carried out on the samples that were kept for 1, 7 and 28 days and their compressive strengths are given in Table 2.
  • the invention paved the way for the production of geopolymer binders with properties comparable to Portland cement by using sodium hydroxide and sodium silicate solution as activators of blast furnace slag, which is wastes of the iron and steel industry, and aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries, without requiring special curing processes.
  • the comparison of the compressive strength of the geopolymer binders according to the invention with the geopolymer binders known in the prior art can also be seen in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

This invention relates to the production of geopolymer binders by using the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries. With this invention, geopolymer binders that do not require processes such as thermal curing, water curing, steam curing and showing high compressive strength can be produced. With the invention, it is possible to use the aggregate washing sludge, which is stored in waste sites and poses a significant environmental problem, as a geopolymer binder material and to reduce the environmental and economic problems it causes. A geopolymer binder in the form of paste obtained by the said method is also disclosed. In addition, the geopolymer binder obtained according to the invention can be used in the production of screed, mortar, concrete and precast concrete by mixing with fine and/or coarse aggregates.

Description

PRODUCTION METHOD OF GEOPOLYMER BINDER
Technical Field
This invention relates to the production of geopolymer binders by using the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries.
Prior Art
There are various solutions and studies for the evaluation of blast furnace slag (BFS), which is waste of the iron and steel industry. The blast furnace slag is also among the inputs of cement production.
Aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries is disposed of at the waste sites.
Since a large amount of fossil fuel is consumed during its production and high carbon dioxide emissions are realized, there is a need to develop alternative materials to cement. For this, geopolymers are particularly emphasized. Some studies are carried out on the use of blast furnace slag in the production of geopolymer binders. The widespread use of such binders requires that they have at least similar strength to Portland cement.
The Objects of the Invention
The object of this invention is to develop a method that enables the production of geopolymer binders by using the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries. Another object of this invention is to develop a method that enables the use of aggregate washing sludge, which is stored in waste sites and poses a significant environmental problem, in the production of geopolymer binder. Another object of this invention is to develop a method that enables the production of geopolymer binders with high compressive strength. It is aimed that the produced geopolymer binders will exhibit strength at least comparable to the Portland cement.
Another object of this invention is to develop a method for producing geopolymer binders suitable for use in various engineering applications such as mortar, screed, concrete and precast segment concrete production.
Another object of the invention is to develop a geopolymer binder in the form of paste produced from blast furnace slag and aggregate washing sludge.
Detailed Description of the Invention
According to the production method of geopolymer binder of the invention, basically, the mixture of the blast furnace slag generated during iron and steel production and the aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries is mixed with aqueous sodium hydroxide and sodium silicate solution as alkali activator. With this method, geopolymer binders with high compressive strength can be obtained. The chemical composition of blast furnace slag varies depending on the ore, fuel and flux content and the details of the process. As a result of the reduction of iron oxides in the ore content, this slag is rich in oxides of mainly flux-derived elements such as silica, calcium oxide and aluminum oxide. The chemical composition of aggregate washing sludge also varies depending on the mineralogical properties of the respective quarries and the details of the crushing and washing processes. The aggregate washing sludge, which generally consists of minerals such as quartz, illite, kaolinite, feldspar, chlorite, calcite, dolomite, etc. mainly contains SiCk, AI2O3 and Fe203. The steps of the production method of the geopolymer binder of the invention includes the steps of
- preparing the mixture of blast furnace slag and aggregate washing sludge,
- preparing an aqueous solution containing sodium hydroxide and sodium silicate,
- preparing paste by mixing a mixture of blast furnace slag and aggregate washing sludge with sodium hydroxide and sodium silicate solution
The geopolymer binder in the form of paste is cured without requiring any special process.
Depending on the initial particle sizes, the grinding step of the blast furnace slag may also be applied prior to the step of preparing the mixture. Preferably, the Blaine specific surface of the blast furnace slag is in the range of 5000±500 cm2/g.
The aggregate washing sludge can usually be obtained in wet or partially dried condition. The flocculation is also observed in the partially dried aggregate washing sludge. Before the preparation of the mixture, the drying and grinding step of the aggregate washing sludge is applied. Preferably, the maximum particle size of the aggregate washing sludge obtained as a result of the grinding process is less than 200 pm.
In the preferred embodiment of the invention, a mixture containing dried and ground aggregate washing sludge in the range between 40% and 70% by volume is used.
In the preferred embodiment of the invention, an aqueous solution containing sodium hydroxide with a molarity in the range between 6 and 10 M and sodium silicate with a silica modulus between 0.8 and 1.6 is used.
In the preferred embodiment of the invention, the mixture of the blast furnace slag and aggregate washing sludge and sodium hydroxide and sodium silicate aqueous solution are mixed in such a way that the solution/(blast furnace slag and aggregate washing sludge) ratio is between 0.25 and 0.35 by weight. In order to evaluate the effectiveness of the method of the invention and the geopolymer binder obtained by this method, the tests were also carried out on samples in the form of paste, which were stored for certain periods. During these tests, the blast furnace slag and ground aggregate washing sludge with chemical compositions given in Table 1, were used.
Table 1 - Chemical compositions of blast furnace slag and aggregate washing sludge
Figure imgf000005_0001
For the tests, the mixtures containing aggregate washing sludge between 20% and 80% by volume and aqueous solution comprising of sodium hydroxide with molarity in the range between 4 and 12 M and sodium silicate to adjust silica modulus between 0.6 and 2.0 were mixed with a solution / (blast furnace slag and aggregate washing sludge) ratio in the range between 0.20 and 0.40 by weight to produce paste samples. Then, the prepared paste samples were kept in ambient conditions at 60±10% relative humidity and 22±5°C for certain periods. Compression tests were carried out on the samples that were kept for 1, 7 and 28 days and their compressive strengths are given in Table 2. The invention paved the way for the production of geopolymer binders with properties comparable to Portland cement by using sodium hydroxide and sodium silicate solution as activators of blast furnace slag, which is wastes of the iron and steel industry, and aggregate washing sludge generated as a result of washing the crushed sand (stone dust) obtained as the final product from the aggregate quarries, without requiring special curing processes. The comparison of the compressive strength of the geopolymer binders according to the invention with the geopolymer binders known in the prior art can also be seen in Table 2.
Table 2 - Compressive strengths of geopolymer binders measured at different days according to the invention and prior art
Figure imgf000006_0001
References
[1] Kiatsuda Somna, Chai Jaturapitakkul, Puangrat Kajitvichyanukul, Prinya Chindaprasirt, (2011). NaOH-activated ground fly ash geopolymer cured at ambient temperature, Fuel ,
90(6), 2118-2124 [2] J. Temuujin, R.P. Williams, A. van Riessen, (2009). Effect of mechanical activation of fly ash on the properties of geopolymer cured at ambient temperature, Journal of Materials Processing Technology , 209(12-13), 5276-5280 [3] Samantasinghar, S., Singh, S.P. (2019) Fresh and Hardened Properties of Fly Ash-Slag
Blended Geopolymer Paste and Mortar. IntJ Concr Struct Mater 13, 47

Claims

1. A production method of geopolymer binder, characterized in that a mixture of blast furnace slag and ground aggregate washing sludge is mixed with sodium hydroxide and sodium silicate aqueous solution.
2. A production method of geopolymer binder according to claim 1, characterized in that the aggregate washing sludge containing mainly SiC , AI2O3, and Fe2C>3 is used.
3. A production method of geopolymer binder according to claim 1, characterized in that dried and ground aggregate washing sludge with a maximum particle size less than 200 pm is used.
4. A production method of geopolymer binder according to claim 1, characterized in that the blast furnace slag with a Blaine specific surface of 5000±500 cm2/g is used.
5. A production method of geopolymer binder according to claim 1, characterized in that a mixture containing dried and ground aggregate washing sludge between 20% and 80% by volume is used.
6. A production method of geopolymer binder according to claim 5, characterized in that a mixture containing dried and ground aggregate washing sludge between 40% and 70% by volume is used.
7. A production method of geopolymer binder according to claim 1, characterized in that a solution containing sodium hydroxide with a molarity in the range between 4 and 12 M and sodium silicate with a silica modulus between 0.6 and 2.0 is used.
8. A production method of geopolymer binder according to claim 7, characterized in that a solution containing sodium hydroxide with a molarity in the range between 6 and 10 M and sodium silicate with a silica modulus between 0.8 and 1.6 is used.
9. A production method of geopolymer binder according to claim 1, characterized in that a mixture of blast furnace slag and dried and ground aggregate washing sludge is mixed with sodium hydroxide and sodium silicate solution at a solution / (blast furnace slag and aggregate washing sludge) ratio between 0.20 and 0.40 by weight.
10. A production method of geopolymer binder according to claim 9, characterized in that the solution / (blast furnace slag and aggregate washing sludge) ratio is between 0.25 and 0.35 by weight.
11. A production method of geopolymer binder according to claim 1; characterized by the steps of; preparing the mixture of blast furnace slag and aggregate washing sludge, preparing an aqueous solution containing sodium hydroxide and sodium silicate, preparing paste by mixing a mixture of blast furnace slag and aggregate washing sludge with sodium hydroxide and sodium silicate solution.
12. A geopolymer binder in the form of paste produced with the production method of geopolymer binder according to claim 11.
13. Production of geopolymer screed, mortar, concrete and precast concrete by mixing the binder in the form of paste produced with the production method of geopolymer binder according to claim 11 with fine aggregate and/or coarse aggregate.
PCT/TR2022/050271 2021-03-26 2022-03-25 Production method of geopolymer binder WO2022203642A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974503A (en) * 2023-03-17 2023-04-18 中建材中岩科技有限公司 Underwater anti-dispersion fluid sludge curing agent and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5349118A (en) * 1990-09-04 1994-09-20 Joseph Davidovits Method for obtaining a geopolymeric binder allowing to stabilize, solidify and consolidate toxic or waste materials
US20080178525A1 (en) * 2007-01-29 2008-07-31 Comrie Douglas C Binder composition for waste materials
WO2014075134A1 (en) * 2012-11-13 2014-05-22 Cement Australia Pty Limited Geopolymer cement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5349118A (en) * 1990-09-04 1994-09-20 Joseph Davidovits Method for obtaining a geopolymeric binder allowing to stabilize, solidify and consolidate toxic or waste materials
US20080178525A1 (en) * 2007-01-29 2008-07-31 Comrie Douglas C Binder composition for waste materials
WO2014075134A1 (en) * 2012-11-13 2014-05-22 Cement Australia Pty Limited Geopolymer cement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974503A (en) * 2023-03-17 2023-04-18 中建材中岩科技有限公司 Underwater anti-dispersion fluid sludge curing agent and preparation method and application thereof

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