Patent Application
20220396527
The present invention relates to a mechanically carboxylated fly ash. The invention further relates to methods of its production and uses thereof, for example as a filler. The invention further relates to compositions comprising the mechanically carboxylated fly ash and a further material selected from the group consisting of asphalt, cement, polymers and combinations thereof and methods of their production.
Concrete is a composite material, comprising a matrix of aggregate (typically a rocky material) and a binder (typically Portland cement or asphalt), which holds the matrix together. Concrete is one of the most frequently used building materials and is said to be the second most widely used material on earth, after water.
In order to reduce the cost of concrete and the CO2 emissions generated by global cement production, much research effort has been dedicated to identifying cheap material which can be used as a filler or alternative binder to replace the binder component without (detrimentally) affecting the properties of concrete. Such secondary cementitious materials are an area of broad industry interest.
An example of a widely employed cement filler is limestone. A comprehensive overview of fillers in cementitious materials can be found in John, Vanderley M., et al. “Fillers in cementitious materials—Experience, recent advances and future potential.” Cement and Concrete Research 114 (2018): 65-78.
The production of Portland cement contributes to about 10% of world carbon dioxide emissions. According to Vanderley et al. the traditional mitigation strategies for CO2 emissions in the cement industry are not sufficient to ensure the necessary mitigation in a scenario of increasing cement demand. Therefore, the adoption of expensive and environmentally risky carbon capture and storage (CCS) has been considered an unavoidable solution by cement industry leaders.
Hence, there remains a need to develop affordable filler technology which can combine both the CO2 emission reduction achieved by reduced cement production and the CO2 emission reduction achieved by carbon capture technology and which does not detrimentally affect the properties of concrete.
It is an object of the present invention to provide improved fillers for cement or asphalt binder.
It is a further object of the present invention to provide improved fillers for cement or asphalt binder which are cheap to produce.
It is a further object of the present invention to provide improved fillers for cement or asphalt binder which are produced using CO2 storage technology.
It is a further object of the present invention to provide improved fillers for cement or asphalt binder which improve the properties of the resulting concrete, such as the compressive strength.
In a first aspect the present invention provides a mechanochemically carboxylated fly ash which has a BET surface area of less than 50 m2/g and a CO2 content of more than 1 wt. %, wherein the CO2 content is determined as the mass loss above 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min and then decreased to room temperature at a rate of 15° C./min.
As will be shown in the appended examples, it was found that when such a mechanochemically carboxylated fly ash is used as a filler in cement the compressive strength of the resulting concrete is surprisingly increased beyond the values obtained when pure cement is employed. In addition, the set time for the strength development is decreased. Furthermore, a much higher amount of this mechanochemically carboxylated fly ash can be used as a filler while still resulting in acceptable concrete properties.
Additionally, the production of said mechanochemically fly ash filler relies on a cheap CO2 capture technology platform, such that a filler is provided which can be produced in an economically viable manner and which combines both the CO2 emission reduction achieved by reduced cement production and the CO2 emission reduction achieved by carbon capture technology.
It was furthermore found that the durability of the concrete produced using said mechanochemically fly ash filler is considerably increased. Without wishing to be bound by any theory, the present inventors believe that this is due to enhanced micro and sub-microscale hydration, a reduced chloride permeability and/or reduced porosity of the concrete. Finally, the increased oxygen content as compared to untreated feedstocks may result in better dispersion in polar solvents, and better compatibility with materials that have epoxy and carboxyl functional groups.
In a further aspect, the invention provides a method for producing mechanochemically carboxylated fly ash, preferably mechanochemically carboxylated fly as described herein, comprising the following steps:
In another aspect the invention provides the mechanochemically carboxylated fly ash obtainable by the method for producing mechanochemically carboxylated fly ash described herein.
In another aspect the invention provides a composition comprising a mechanochemically carboxylated fly ash as described herein and a further material selected from the group consisting of asphalt, cement, polymers and combinations thereof.
In another aspect the invention provides a method for preparing a composition as described herein, said method comprising the following steps:
In another aspect the invention provides a method for preparing concrete, said method comprising the following steps:
In another aspect the invention provides concrete obtainable by the method for preparing concrete described herein.
In another aspect the invention provides the use of a mechanochemically carboxylated fly ash as described herein:
In a first aspect the invention provides a mechanochemically carboxylated fly ash which has a BET surface area of less than 50m2/g and a CO2 content of more than 1 wt. %, wherein the CO2 content is determined as the mass loss above 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min and then decreased to room temperature at a rate of 15° C./min.
In accordance with the invention, the BET surface area, the BJH desorption cumulative surface area of pores and the desorption average pore width (4V/A by BET) as referred to herein are determined at a temperature of 77K using a sample mass of 0.5-1 g. A preferred analysis method to determine the BET surface area, the BJH desorption cumulative surface area of pores and the desorption average pore width (4V/A by BET) comprises heating samples to 400° C. for a desorption cycle prior to surface area analysis.
TGA-MS as used herein refers to Thermogravimetric Analysis coupled to Mass Spectrometry, a technique known to the person skilled in the art. A preferred TGA-MS apparatus setup to determine the CO2 content of the feedstocks and mechanochemically carboxylated materials in the context of the present invention is a Setaram TAG 16 TGA/DSC dual chamber balance coupled to an Ametek Dycor Proline MS employing a 0.1-2 mg sample
In preferred embodiments the mechanochemically carboxylated fly ash has one, two or three, preferably three of the following characteristics:
In preferred embodiments the mechanochemically carboxylated fly ash has one, two or three, preferably three of the following characteristics:
In highly preferred embodiments the mechanochemically carboxylated fly ash has one, two or three, preferably three of the following characteristics:
A preferred method of determining the mineral content, such as the SiO2, Al2O3, Fe2O3 or CaO content is by X-ray fluorescence spectroscopy, preferably employing a Bruker Tracer 5G. As will be understood by the skilled person, the SiO2, Al2O3, Fe2O3 and CaO content of both the raw feedstock and the mechanochemically carboxylated fly ash referred to herein is preferably determined using X-ray fluorescence spectroscopy as described herein.
In embodiments of the invention, the particle size distribution of the mechanochemically carboxylated fly ash has one, two, three or all, preferably all, of the following characteristics:
In accordance with the invention, the particle size distribution characteristics such as D10, D50, D90 and D(4:3) are determined by measuring with a laser light scattering particle size analyzer utilizing the Fraunhofer theory of light scattering, such as the Fritsch Analysette 22 Nanotec or another instrument of equal or better sensitivity and reporting the data using a volume equivalent sphere model. As is known to the skilled person, the D50 is the mass median diameter, i.e. the diameter at which 50% of a sample's mass is comprised of smaller particles. Similarly, the D10 and D90 represent the diameter at which 10 or 90% of a sample's mass is comprised of smaller particles. As is known to the skilled person, the D(4:3) is the volume mean diameter.
In embodiments of the invention, the mechanochemically carboxylated fly ash has a density of more than 2.5 g/cm3, preferably more than 2.7 g/cm3, more preferably more than 3 g/cm3.
In preferred embodiments of the invention, the mechanochemically carboxylated fly ash has a density of more than 2.5 g/cm3, a D10 of less than 1 μm, a D50 of less than 10 μm and a D90 of less than 50 μm.
In a further aspect, the invention provides a method for producing mechanochemically carboxylated fly ash, preferably mechanochemically carboxylated fly as described herein, comprising the following steps:
It is within the capacity of one skilled in the art, in light of the guidance provided in the present disclosure, to adapt the relevant process parameters such that a mechanochemically carboxylated fly ash is obtained which has the properties recited herein.
In preferred embodiments of the invention, the BET surface area of the mechanochemically carboxylated fly ash is at least 110%, preferably at least 120%, more preferably at least 150%, of the BET surface area of the solid feedstock.
Without wishing to be bound by any theory, the present inventors believe that the BET surface area increase observed with the mechanochemical carboxylation of fly ash in accordance with the present invention may largely be attributed to an increase in the number of pores, observed by a decrease in the average pore width and an increase in the total pore surface area. Hence, in embodiments of the invention, the BJH desorption cumulative surface area of pores of the mechanochemically carboxylated fly ash is at least 110%, preferably at least 120%, more preferably at least 150%, of the BJH desorption cumulative surface area of pores of the solid feedstock and the desorption average pore width (4V/A by BET) of the mechanochemically carboxylated fly ash is no more than 90%, preferably no more than 85%, more preferably no more than 80%, of the desorption average pore width (4V/A by BET) of the solid feedstock.
In preferred embodiments of the invention, the Fe2O3 content of the mechanochemically carboxylated fly ash is at least 150%, preferably at least 200%, most preferably at least 250% of the Fe2O3 content of the solid feedstock.
In preferred embodiments of the invention, the CO2 content of the mechanochemically carboxylated fly ash is more than 2 wt. % (by total weight of the mechanochemically carboxylated fly ash), preferably more than 5 wt. %, most preferably more than 7 wt. %, wherein the CO2 content is determined as the mass loss above 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min and then decreased to room temperature at a rate of 15° C./min.
In highly preferred embodiments of the invention, the CO2 content of the solid feedstock is less than 0.5 wt. % (by total weight of the solid feedstock), preferably less than 0.2 wt. %, most preferably less than 0.1 wt. %, wherein the CO2 content is determined as the mass loss above 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min and then decreased to room temperature at a rate of 15° C./min.
The term “fly ash” as used herein refers to any type of fly ash, including coal fly ash and oil fly ash. Without wishing to be bound by any theory, the present inventors have found that improved performance can be obtained when the solid feedstock is low in carbonaceous fly ash. Carbonaceous fly ash is a particularly characteristic kind of fly ash which constitutes a large portion of the oil fly-ash.
Hence, in preferred embodiments the fly ash is coal fly ash, such as lignite coal fly ash, subbituminous coal fly ash, anthracite coal fly ash, bituminous coal fly ash and combinations thereof. In highly preferred embodiments of the invention, the solid feedstock comprises or consists of fly ash which meets the ASTM C618 (2019) requirements, preferably fly ash which meets the class C ASTM C618 (2019) requirements.
In embodiments, the solid feedstock has a combined SiO2, Al2O3 and Fe2O3 content of more than 60 wt. % (by total weight of the solid feedstock), preferably more than 70 wt. %, more preferably more than 75 wt. %.
Without wishing to be bound by any theory, the present inventors have found that improved mechanochemical carboxylation and filler performance results are obtained when the feedstock comprises at least some CaO. Thus, in embodiments of the invention, the solid feedstock comprises more than 0.5 wt. % (by total weight of the solid feedstock), preferably more than 1 wt. %, more preferably more than 3 wt. % CaO. In preferred embodiments of the invention, the solid feedstock comprises more than 5 wt. % (by total weight of the solid feedstock) or more than 8 wt. % CaO.
In embodiments of the invention, the particle size distribution of the solid feedstock has one, two, three or all, preferably all, of the following characteristics:
In embodiments of the invention, the oxidizing gas provided in step (b) comprises more than 80 mol % CO2, preferably more than 95 mol% CO2. In preferred embodiments of the invention, the oxidizing gas provided in step (b) comprises more than 80 mol % CO2, preferably more than 95 mol % CO2 and less than 1000 ppm (v/v) H2O, preferably less than 100 ppm (v/v) H2O.
In embodiments of the invention, step (d) is performed at a pressure of more than 3 atm, preferably more than 6 atm. In embodiments of the invention, step (d) is performed at a temperature of less than 100° C., preferably less than 60° C., more preferably less than 30° C. In embodiments of the invention, step (d) is performed for at least 1 hour, preferably for at least 4 hours, more preferably for at least 8 hours. In preferred embodiments of the invention, step (d) is performed at a pressure of more than 3 atm, preferably more than 6 atm; at a temperature of less than 100° C., preferably less than 60° C., more preferably less than 30° C.; and for at least 1 hour, preferably for at least 4 hours, more preferably for at least 8 hours.
The present inventors have furthermore found that the mechanochemical carboxylation methods described herein may advantageously be performed without employing additional oxidizing agents such as acids. Hence, the mechanochemical carboxylation methods described herein are preferably performed without employing a strong acid, preferably without employing any further oxidizing agent other than the oxidizing gas provided in step (b).
In preferred embodiments of the invention, the mechanochemical agitation operation of step (d) comprises grinding, milling, mixing, stirring (low-speed stirring or high-speed stirring), shearing (high-torque shearing), shaking, blending, a fluidized bed or ultrasonication, preferably grinding, milling, mixing, stirring (low-speed stirring or high-speed stirring), shearing (high-torque shearing), ultrasonication. The present inventors have found that the mechanochemical carboxylation process is facilitated if the mechanochemical agitation operation of step (d) the mechanochemical agitation operation of step (d) is performed in the presence of inert grinding or milling media, preferably inert balls or beads. A preferred inert material is stainless steel.
In preferred embodiments of the invention, step (d) is performed in the presence of a catalyst, preferably a transition metal oxide catalyst, more preferably a transition metal dioxide catalyst, most preferably a transition metal dioxide catalyst selected from the group consisting of iron oxides, cobalt oxides, ruthenium oxides, titanium oxides and combinations thereof.
Hence, as will be understood from the above, in highly preferred embodiments of the invention, step (d) comprises a mechanical agitation operation, preferably grinding, milling, mixing, stirring (low-speed stirring or high-speed stirring), shearing (high-torque shearing), shaking, blending, a fluidized bed or ultrasonication, in the presence of inert grinding or milling media and a transition metal oxide catalyst. The present inventors have found that it is advantageous with a view to the efficiency of the mechanochemical carboxylation (e.g. reaction time, CO2 absorption and particle size reduction) to employ inert media as described herein before coated with said transition metal oxide catalyst.
In another aspect the invention provides the mechanochemically carboxylated fly ash obtainable by the method for producing mechanochemically carboxylated fly ash described herein.
As will be understood by the skilled person in light of the present disclosure, the mechanochemically carboxylated fly ash of the present invention constitutes an excellent filler for many applications, combining distinct mechanical properties with a cost-efficient CO2 capture technology.
Hence, in another aspect the invention provides a composition comprising a mechanochemically carboxylated fly ash as described herein and a further material selected from the group consisting of asphalt, cement, polymers and combinations thereof.
In embodiments, the further material is a polymer selected from thermoplastic polymers and thermosetting polymers. In preferred embodiments, the further component is a polymer selected from the group consisting of epoxide resin, phenol-formaldehyde resin, polyethylene terephthalate, aromatic polyamide, polyacrylonitrile, polyimide, aromatic polyester, polyethylene, polypropylene, polyurethane, polyisocyanurate, polyamide, polyether, polyester, polyhydroxyalkanoate, polylactic acid, polyvinylidene fluoride, polyvinyl acetate, polyvinyl chloride, polystyrene, polytetrafluoroethylene, acrylonitrile-butadiene-styrene, nitrile rubber, styrene-butadiene, ethylene-vinyl acetate and combinations thereof. The term “polymer” as used herein includes copolymers, such as block copolymers.
In highly preferred embodiments the further material is selected from cement, asphalt or combinations thereof.
In accordance with the invention, the cement may be a hydraulic or non-hydraulic cement. In preferred embodiments, the cement is a hydraulic cement, such as Portland cement. In highly preferred embodiments of the invention, the cement is one of the cements defined in EN197-1 (2011), preferably Portland cement as defined in EN197-1 (2011).
In embodiments of the invention, the composition comprises more than 0.1 wt. % (by total weight of the composition), preferably more than 1 wt. %, more preferably more than 5 wt. % of the mechanochemically carboxylated fly ash and/or more than 0.1 wt. % (by total weight of the composition), preferably more than 1 wt. %, more preferably more than 20 wt. % of the further material.
In embodiments of the invention, the composition comprises less than 60 wt. % (by total weight of the composition), preferably less than 50 wt. %, more preferably less than 45 wt. % of the mechanochemically carboxylated fly ash and/or less than 95 wt. % (by total weight of the composition), preferably less than 90 wt. %, more preferably less than 80 wt. % of the further material.
In embodiments of the invention, the composition is provided wherein the weight:weight ratio of the mechanochemically carboxylated fly ash to the further material is within the range of 1:9 to 2:1, preferably within the range of 1:8 to 1:1, more preferably within the range of 1:6 to 5:6.
In embodiments of the invention, the composition comprises 5-70 wt. % (by total weight of the composition), preferably 10-60 wt. %, more preferably 20-50 wt. % of the mechanochemically carboxylated fly ash and 30-95 wt. % (by total weight of the composition), preferably 40-90 wt. %, preferably 50-80 wt. % of the further material.
In embodiments of the invention, the composition comprises less than 5 wt. % (by total weight of the composition water, preferably less than 1 wt. %, more preferably less than 0.1 wt. %. The amount of water can suitably be determined as the mass loss up to 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min.
In embodiments of the invention, the composition consists of the mechanochemically carboxylated fly ash and the further material.
In another aspect the invention provides a method for preparing a composition as described herein, said method comprising the following steps:
In another aspect the invention provides a method for preparing concrete, said method comprising the following steps:
In another aspect the invention provides concrete obtainable by the method for preparing concrete described herein.
In embodiments of the invention, the construction aggregate is selected from the group consisting of sand, gravel, crushed stone, slag, recycled concrete, clay, pumice, perlite, vermiculite and combinations thereof. In preferred embodiments the construction aggregate is one of the aggregates defined in EN 13043 (2002), EN 13383 (2019), EN 12620 (2013) or EN 13242 (2013), preferably the construction aggregate is one of the aggregates defined in EN 12620 (2013).
In preferred embodiments of the invention, step (iii) further comprises contacting, preferably mixing the composition of step (i) with the construction aggregate of step (ii) and water. In accordance with the invention, the composition of step (i), the construction aggregate of step (ii) and the water may be contacted, preferably mixed at substantially the same time, or in a step-wise manner wherein the composition of step (i) is first contacted, preferably mixed with water, before being contacted, preferably mixed with the construction aggregate of step (ii).
In another aspect the invention provides the use of a mechanochemically carboxylated fly ash as described herein:
It will be understood by the skilled person that the embodiments of the invention described herein in the context of the mechanochemically carboxylated fly ash or the composition, especially in relation to the features of the mechanochemically carboxylated fly ash or in relation to the features of the further material, are equally applicable to the method for preparing said composition described herein, the method for preparing concrete described herein and the uses of the mechanochemically carboxylated fly ash described herein.
The BET surface area, the BJH desorption cumulative surface area of pores and the desorption average pore width (4V/A by BET) were determined at a temperature of 77K using a sample mass of 0.5-1 g wherein samples were heated to 400° C. for a desorption cycle prior to surface area analysis.
Particle Size Distribution measurements were carried out on a Fritsch Analysette 22 Nanotec using Fraunhofer diffraction theory.
The mineral content (SiO2, Al2O3, Fe2O3 and CaO) was determined by X-ray fluorescence spectroscopy employing a Bruker Tracer 5G.
The CO2 content was determined as the mass loss above 120° C. measured by TGA-MS employing a temperature trajectory wherein the temperature was increased from room temperature to 800° C. at a rate of 10° C./min and then decreased to room temperature at a rate of 15° C./min employing a Setaram TAG 16 TGA/DSC dual chamber balance coupled to an Ametek Dycor Proline MS and a 0.1-2 mg sample.
Compressive strength was tested in accordance with ISO 1920:2005, part 4.
Mechanochemically carboxylated fly ash was produced by inserting a 10 gram sample of fly ash into a pressure cell with 500 grams of inert media (stainless steel balls) coated with titanium dioxide. The cell is pressurized to 1 MPa (9.87 atm), placed in a high energy ball mill for and rotated at 5000 RPM for 48 hours. The reaction was initiated at room temperature and no heating or cooling was applied.
Two raw fly ash samples A and B were mechanochemically carboxylated (‘treated’) with a process according to example 1, wherein the mechanical agitation and CO2 pressure were adapted such that a product with the characteristics set out in the below table was obtained. Raw sample A was obtained from the Gennessee, Alberta (Canada) coal plant and complies with class F ASTM C618 (2019) requirements. Raw sample B was obtained from the Civita Vecchia (Italy) coal plant. Raw sample C was obtained from the Cordemais (France) coal plant. The raw fly ash of samples B and C are generally considered an inferior fly ashes which are unsuitable for use as a concrete filler at concentrations above 10 wt. %.
The mechanochemically carboxylated fly ashes A and B were used as a filler by mixing with portland cement at a weight:weight ratio of 1:5 (filler:cement).
The obtained mixtures of mechanochemically carboxylated fly ashes and portland cement were each mixed with fine gravel and water (employing identical ratios for every sample) to obtain a concrete slurry. The compressive strength of the resulting concrete was monitored after 2, 7 and 28 days.
For comparison, a similar concrete slurry was prepared using raw fly ashes samples A and B and pure portland cement.
As can be observed from the compressive strength measurements, the mechanochemically carboxylated mineral fillers of the present invention provide an unexpectedly large performance increase compared with the raw materials (such as fly ashes). Furthermore, it was surprisingly found that the mechanochemically carboxylated mineral fillers of the present invention even outperform pure cement mixtures.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19207206.4 | Nov 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2020/051493 | 11/4/2020 | WO |
