Evaluation of the pozzolanic activity of fluid catalytic cracking catalyst residue (FC3R). Thermogravimetric analysis studies on FC3R-Portland cement pastes

Spent fluid catalytic cracking catalyst (FC3R) from a petrol refinery has shown a great pozzolanic activity in lime pastes as have been demonstrated in previous studies. Based on these results, the pozzolanic activity of the FC3R in Portland cement pastes has been investigated. This evaluation has been carried out by means of thermogravimetry (TG) of cured FC3R-Portland cement pastes. The influence of water/binder ratio and the replacement percentage of FC3R on the pozzolanic reaction were investigated. Due to the chemical composition of FC3R that is similar to metakaolin (MK), and knowing that MK has a high pozzolanic activity, the latter was used as a material of comparison in the study of the water/binder ratio influence. The scope of this study is the determination of pozzolanic activity of FC3R when incorporated to Portland cement, and the evaluation on amount and nature of pozzolanic products. FC3R has shown a similar reactivity to MK, yielding similar pozzolanic products: CSH, CAH and CASH. The optimum replacing percentage in Portland cement pastes was in the 15-20% range.     

Determination of the pozzolanic activity of fluid catalytic cracking residue. Thermogravimetric analysis studies on FC3R-lime pastes

Spent fluid catalytic cracking catalyst (FC3R) from a petrol refinery played a pozzolanic role in portland cement system as revealed by previous experimental data. In the present study, the pozzolanic activity of FC3R was investigated by means thermogravimetry (TG) of cured lime-FC3R pastes. The influence of pozzolan/lime ratio on the pozzolanic activity was investigated. Due to the chemical composition of FC3R is similar to metakaolin (MK), and knowing that MK has a high pozzolanic activity, the latter was used as a material of comparison in this study. The scope of the study is the determination of the pozzolanic activity of FC3R and the evaluation of amount and nature of pozzolanic products. The products obtained from the reaction between FC3R components (SiO₂/Al₂O₃) and calcium hydroxide (CH) have been characterized, finding that the main pozzolanic reaction product was similar to hydrated gehlenite (calcium aluminosilicate hydrate) CSH and CAH were also formed in the reaction. FC3R showed higher pozzolanic reactivity than metakaolin, for low-lime content pastes and early curing age. Thermogravimetry, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) became very useful techniques for evaluation of reactivity.     

The effect of high curing temperature on the reaction kinetics in MK/lime and MK-blended cement matrices at 60 °C

It is well known that the pozzolanic reaction between metakaolin (MK) and calcium hydroxide produces CSH, C₂ASH₈ (stratlingite), C₄AH₁₃ and C₃ASH₆ (hydrogarnet). However, the presence or absence of these hydrated phases depends on different parameters, such as curing temperature, matrix used, etc. This paper shows the results of a study in order to know the effect of high curing temperature (60 °C) on the kinetics of the pozzolanic reaction in different matrices. MK/lime (calcium hydroxide) and MK-blended cement matrices were studied in samples stored and cured at 60 °C and up to 123 days of hydration. The nature, sequence and crystallinity of the hydrated phases were analysed using differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques.Results showed that the sequence and formation of the hydrated phases was different in both matrices cured at 60 °C. In an MK/lime matrix, C₂ASH₈, C₄AH₁₃ and C₃ASH₆ were the main hydrated phases; while in an MK-blended cement, stratlingite was the sole hydrated phase issued from pozzolanic reaction. The DTA and XRD data also reveal an important fact: there is no evidence of the presence of hydrogarnet in blended cements.     

Mineral phases formation on the pozzolan/lime/water system

In Spain, the paper industry recycles large amounts of waste paper in the new paper production process. Paper sludge thermal activation (calcination at 700 °C for 2 h) is an environment-friendly alternative source for metakaolinite (MK) to be used for the manufacture of blended cements or cement based materials.This paper could contribute to standardization of the use of new pozzolanic products in cement based materials and its use mixed with saturated lime dissolution. In this process are obtained zeolite, CSH gel, hydrotalcite-like compounds, hydrated aluminate tetracalcium and stratlingite.These materials are formed in different times of pozzolanic reaction.     

Calcined oil sands fine tailings as a supplementary cementing material for concrete

In recent years, metakaolin (MK) has received considerable attention, as a high-performance pozzolanic supplementary cementing material for use in concrete. MK is produced by calcining kaolinite at temperatures between 600 and 1000 °C. In the province of Alberta, Canada, the oil sand mining industry produces millions of cubic metres of oil sand tailings that could become a major source of MK. This paper summarizes the behaviour of calcined fine tailings (CFT) as a supplementary cementing material in high-performance concrete and compares its performance to that of MK and silica fume (SF). It was found that CFT has excellent pozzolanic activity in concrete, making it an environmentally friendly and potentially cost effective supplement.     

High-temperature sorbents for Hg, Cd, Pb, and other trace metals: Mechanisms and applications

This paper is concerned with the sequestration of mercury, cadmium, lead, sodium and potentially other volatile and semi-volatile metals by high-temperature mineral, non-carbon based dispersed sorbents. The focus here is on kaolinite and lime powders (for Pb, Cd, and Na), and on intimate kaolinite/calcite/lime mixtures (for Hg), both of which undergo morphological and chemical changes when exposed to high temperatures. These changes play critical roles in the metal capture mechanisms, initially enhancing metal capture, either through a eutectic melt on the surface, or through some other transformation, but ultimately causing sorbent de-activation through a catastrophic melt that causes pore closure.Results and interpretation from two types of experiments are presented. The first employed a 20 kW downflow combustor, a low-pressure impactor and application of the aerosol fractionation method to quantitatively determine the fraction of metal sequestered by the sorbent at the sampling point. The second employed an externally heated quartz reactor and simulated flue gases containing mercury and injected sorbent. Quantitative, rate models have been extracted from the data to describe the global reactions of dispersed kaolinite with lead, sodium, and cadmium metal vapors. They have also been derived for the global reaction of cadmium with dispersed hydrated lime, which was ineffective for Na and Pb but very effective for Cd. Qualitative results showing the effective scavenging of Pb and Cd by the intimate kaolinite/calcite/lime mixture are also presented.The intimate kaolinite/calcite/lime mixture was also shown to capture metallic mercury through two mechanisms, namely, an in-flight mechanism and one involving interactions between Hg, the sorbent and the quartz reactor walls. The in-flight mechanism had similarities to those observed previously between kaolinite, lead, cadmium and sodium, in that mineral transformations played a key role in both sorbent activation and sorbent de-activation. At a constant residence time, the in-flight mechanism exhibited a maximum effectiveness at 900 °C, followed by apparent de-activation. Spent in-flight sorbent showed the presence of calcium silicates and calcium aluminosilicates. The wall deposit mechanism increased in efficacy with temperature and did not show a maximum, and showed the presence of substantial amounts of captured mercury. Adding to the complexity of this process is that Hg capture by this mixture required the presence of O₂ in the flue gas, albeit at low levels of 4000 ppm.     

Mineralogical and morphological changes of calcined paper sludge at different temperatures and retention in furnace

This work reports the project of thermal effects in mineralogy and texture of the paper sludge to employ them as pozzolanic material.For this reason, the chemistry and mineralogical composition has been studied, as well as its morphology by XRD, SEM and EDX.The initial sludge has been treated to 700, 750 and 800 °C during 2 and 5 h being observed that initial kaolinite becomes metakaolinite and that its pozzolanic activity with a paper sludge treated to 700 °C for 2 h is comparable to that of a commercial metakaolinite. The transformation of kaolinite after the dehydroxylation is to convert in amorphous metakaolinite. At the temperature mentioned above, calcite from the initial sludge is maintained active.It is concluded that the pozzolanic activity of metakaolinite is strongly related to the crystallinity of the original kaolinite. Well-ordered kaolinite is transformed into more reactive metakaolinite.     

Cement pastes of low water to solid ratio: An investigation of the polymerization of silicate anions in the presence of a superplasticizer and silica fume

Polymerization of silicate anions was investigated by the molybdate method in cement pastes with water to solid ratio of 0.28. Two series of samples - with and without superplasticizer admixture - were prepared using ordinary portland cement (OPC) in which 0, 5, 10, and 15 percent by weight was replaced by condensed silica fume (CSF). During the hydration ranging from 4 hours up to 50 days, the free lime content and insoluble residue were also determined. The 28 day compressive strengths of the hardened composites were between 79 and 108 MPa. The results from the molybdate complex confirm that the presence of CSF in hydrating blends and its pozzolanic activity influences the size dispersity of silica anions by increasing the proportion of polymers. It is also suggested that in the cement pastes of w/s ratio of 0.28, the conversion level of CSF by pozzolanic reaction decreased. Finally, a comparison is made between the polymerization characteristics of the 0.28 w/s-ratio pastes and pastes of w/s = 0.68 which have been hydrated for 6.3 years.     

The benefits of incorporating glycerol carbonate into an innovative pozzolanic matrix

A green admixture, glycerol carbonate (GC), has been incorporated into an alternative binder composed of hydraulic lime and metakaolin. The new properties achieved are rapid hardening, an improvement of compressive strength and a reduction in shrinkage. A study of the rheological behaviour and monitoring of conductivity, pH and organic compounds concentrations in diluted solutions led to the conclusion of an early precipitation of calcium carbonate due to GC decomposition. This phenomenon is believed to be responsible for the early stiffening of the paste. XRD and TG analyses showed changes in the mineralogical hydrated phases formed in the presence of GC: calcium aluminium oxide hemi-carbonate hydroxide hydrate is the only aluminate phase existing in this mineralogical system and more C-S-H are formed. These differences could explain the enhancement in the paste mechanical performance. The study concludes that this innovative pozzolanic matrix has considerable potential as a binder in building ecocomposites.     

Microtexture and Composition of Reaction Products in the System Kaolin–Lime–Water

Textural and compositional features of reaction products in the system kaolin–lime–water were examined by electron microscopy and electron diffraction. Electron micrographs of replicas of fracture surfaces of compacted mixtures and transmission electron micrographs of powdered compacts showed considerable attack of kaolinite particles by hydrated lime and indicated formation of significant amounts of calcium silicate hydrate phases. Electron diffraction of reaction products confirmed the presence of calcium silicate hydrates. The presence of these hydrates is undoubtedly responsible for the stabilizing effects of lime which have previously been reported in the literature.     

Effects of the secondary minerals of the natural pozzolans on their pozzolanic activity

Natural pozzolans have been widely used as substitutes for Portland cement, because of their binding properties. Some of them are natural volcanic rocks which contain secondary minerals such as clays and zeolites corresponding to products of the alteration of the rock. The objective of this study was to document the potential effect of the secondary minerals on the strength development of pozzolanic mortars. We chose to investigate this effect by thermally destabilising these minerals in three different pozzolanic deposits (poz-1, poz-2 and poz-3). We first did a detailed mineralogical study, to identify the occurrence and the nature of the different secondary minerals. Kaolinite is abundant in poz-1 and different types of zeolite were identified in poz-2 and poz-3. Thermal treatments were monitored by X-ray Diffraction (XRD) analysis, in order to document mineralogical transformations. The effect on the pozzolanic activity has been tested by strength measurements on normalised mortars at 1, 7 and 28 days. Strength of all blended cements is enhanced while destabilising secondary alteration minerals. For kaolinite, we showed that a strength improvement occurs as soon as it is destructured, even if it is not transformed in metakaolin. For zeolites, destabilisation takes place at low temperature (350 °C), but as recrystallisation products are easily formed, activation temperature window is narrow. Endly, we have evidence that the presence of calcite in pozzolans has an effect on early strength. Therefore this study is giving new perspectives for a better use of natural pozzolanic materials in the cement industry.     

Physico-chemical study of Cretan ancient mortars

Mortars from monuments of various periods in Crete, from Minoan up to now, have been studied (concerning mineralogical and chemical composition, grain size distribution, raw materials, tensile strength) in order to assess their durability in a marine and humid environment. The lime technology and raw materials, irrespective of the various historic periods, diversify the final composites into mortars, such as: (a) lime, (b) hydraulic lime, (c) lime with crushed brick, and (d) lime with pozzolanic material. These present binders in quantities ranging from 22% (pozzolanic mortars) to 29% (lime mortars). Hydraulic compounds, such as calcium silicate/aluminate hydrates, and tensile strength are higher in the pozzolanic mortars followed by crushed brick lime, hydraulic lime, and lime mortars. High quantities of water-soluble salts identified in the lime mortars indicate their risk of disintegration. A calculation procedure is presented herein, based on the combination of mineralogical and chemical analyses that allows the determination of the binder/aggregate proportion.     

Mineralogical Characterizations and Reaction Path Modeling of the Pozzolanic Reaction of Fly Ash–Lime Systems

Mineralogical studies show that fly ash–lime systems without NaOH produced Al-rich calcium silicate hydrates and a small amount of ettringite. The presence of NaOH accelerates the pozzolanic reaction of fly ash. Fly ash–lime systems with NaOH produced Al-rich calcium silicate hydrates, calcite, meixnerite, and NaX-type zeolite (or zeolite precursor) after 28 days of reaction time. Carbonation of alkali-activated fly ash–lime systems call for specific studies. The experimental work was supplemented with reaction path modeling, which provided a quantitative procedure to decipher the chemical nature of fly ash hydration and cementitious system formation.     

New Data on Thermal Decomposition of Kaolinite and Halloysite

Using single-crystal electron diffraction data it has been possible to demonstrate more directly the existence of considerable order in dehydroxylated kaolinite and halloysite. The two-dimensional ( a-b ) plane structure of dehydroxylated kaolinite is very similar to that of kaolinite. This phase, appropriately described by the term "metakaolinite," decomposes first at about 825°C., γ-Al₂O₃ being the chief crystalline product. In the case of halloysite the γ-Al₂O₃ appears first at about 650°C. The products observed on the dehydroxylation of kaolinite depend to a large extent on the particle size of the sample used. Electron microscope studies of dehydroxylated material and the same material treated under very mild hydrothermal conditions show that the main phenomena accompanying dehydroxylation apparently are disalignment along the c -axis, the appearance of discontinuities in the sheets themselves (not visible directly in the crude image of the electron microscope), and the reduction of the effective particle size. The cause of the exothermic peak cannot be the formation of γ-Al₂O₃ but is assigned to the formation of mullite which is not necessarily detected in an X-ray powder pattern.     

Physical, chemical and mineralogical characterisation of hydraulically disposed fine coal ash from SASOL Synfuels

Coal serves as the primary energy source in most parts of the world. It is a fact that coal combustion yields enormous quantities of fly ash some of which are either hydraulically placed or dry dumped. The current study attempts to provide a comprehensive characterisation of a disused alkaline fine coal ash dam (FCAD) towards assessing environmental impact, rehabilitation and utilisation potential. Fine coal ash refers to a combination of approximately 83% power station fly ash and 17% gasification and bottom ash fines (particles <250 μm) at SASOL Synfuels. The hydration products found in Weathered Fine Coal Ash (WFCA) using X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) are analcime, calcite, C-S-H gel, ettringite, hydrated gehlenite (Strätlingite), magnetite, periclase, pyrrhotite and sillimanite. High resolution Scanning Electron Microscope (SEM) results provide additional proof that hydration products are present in WFCA. No indication of appreciable leaching was given by X-ray Fluorescence (XRF) results except calcium and silicon. Thus evidence exists that pollutants from saline brines are immobilised in WFCA and an insight of reaction kinetics was obtained. High content of amorphous phase and lack of alteration in some geotechnical properties suggest that WFCA can be reutilised with lime addition to increase alkalinity and activate pozzolanic reactions.     

Influence of metakaolin on the properties of mortar and concrete: A review

Supplementary cementing materials (SCM) have become an integral part of high strength and high performance concrete mix design. These may be naturally occurring materials, industrial wastes, or byproducts or the ones requiring less energy to manufacture. Some of the commonly used supplementary cementing materials are fly ash, silica fume (SF), granulated blast furnace slag (GGBS), rice husk ash (RHA) and metakaolin (MK), etc. Metakaolin is obtained by the calcination of kaolinite. It is being used very commonly as pozzolanic material in mortar and concrete, and has exhibited considerable influence in enhancing the mechanical and durability properties of mortar and concrete. This paper presents an overview of the work carried out on the use of MK as partial replacement of cement in mortar and concrete. Properties reported in this paper are the fresh mortar/concrete properties, mechanical and durability properties.     

Lightweight bricks made of diatomaceous earth,lime and gypsum

Diatomaceous earth from Lampang Province in the north of Thailand composes of diatom, kaolinite, montmorillonite and illite, and has porous cellular structure. In this work, the diatomite, hydrated lime and gypsum are the main ingredients in making autoclaved lightweight bricks. Water content, pre-curing period, lime content, gypsum content and calcined temperature are the factors investigated. Mechanical and thermal properties are used to indicate their quality. The nature of hydration products and morphological characteristics of the lightweight bricks are also investigated.     

Use of ceramic industry milling and glazing waste as an active addition in cement

The beneficial effects of pozzolans on cement manufacture have encouraged their use in that industry. Traditional natural pozzolan have become less available of late, however, due to a decline in quarrying intensity aimed at minimizing the impact on the landscape. At the same time, environmental policies pursue the reduction or elimination of spoil heaps by valorizing industrial waste and by‐products as raw materials, in keeping with the principles of the circular economy. The quest for new types of waste and by‐products with pozzolanic properties has consequently become a priority line of research. This study explored the valorization of one such by‐product, the ceramic sludge resulting from fired clay industry milling and glazing, as a component in new, more eco‐sustainable cements. The sludge was characterized physically, chemically, morphologically, and mineralogically to determine its suitability as a pozzolanic addition in cement. The findings showed that ceramic sludge consists in clustered particles ranging in size from 100 μm to 1 μm. SiO₂, Al₂O₃, and Fe₂O₃ together comprise over 70% of the total composition, while the reactive silica content is greater than the 25% required by the existing legislation. The predominant minerals are quartz, kaolinite, and muscovite, with some zircon. A study of pozzolanic reaction kinetics in the ceramic sludge/lime system revealed that over time this waste can fix lime, generating products such as calcium aluminate hydrates and C–S–H gels. The cements made with ceramic sludge proved to be standard‐compliant in terms of water demand, setting, drying shrinkage and mechanical strength.     

Properties of Calcined Clay Waste and its Influence on Blended Cement Behavior

This paper describes research on clay wastes (CWs) produced in the paper manufacture process. Once activated under controlled thermal conditions, CW is transformed into calcined clay products providing added value as supplementary cementing materials. The obtention of a pozzolanic material (metakaolin (MK)) from valorized CW constitutes an alternative source of pozzolans for the elaboration of blended Portland cements, as well as a priority research line from the environmental point of view. This research work presents the properties of calcined CW (chemical, mineralogical, and pozzolanic) and its influence on Portland cements containing 10% calcined clay product. The results obtained with different characterization techniques (XRF, DTA, XRD, SEM-EDX) showed that the thermally activated CW exhibits acceptable properties to be used as supplementary cementing materials in the manufacture of commercial Portland cements. The derived MK can react with calcium hydroxide, from cement hydration, producing hydrated phases with hydraulic properties (calcium silicate hydrate gels, tobermorite, C₄AH₁₃, zeolite). These novel blended cements comply with the chemical, physical, and mechanical specifications established in the existing standards.     

Aging of Lime Putty: Effects on Traditional Lime Mortar Carbonation

The influence of storing slaked lime under water for extended periods of time (i.e., aging) on Ca(OH)₂ crystal morphology, texture, and carbonation evolution of various lime mortars has been studied by the combined use of X-ray diffractometry, phenolphthalein tests, porosity measurements, electron microscopy, and ultrasonic wave propagation analyses. Mortars prepared using traditional aged lime putties (up to 14 years storage under water) show rapid, extensive carbonation, resulting in porosity reduction and ultrasonic speed increase. The aged hydrated lime mortar carbonation reaction (i.e., Ca(OH)₂+ CO₂= CaCO₃+ H₂O) follows a complex diffusive path, resulting in periodic calcite precipitation as Liesegang rings. In this case, binder:aggregate ratios >1:4 result in crack development. Nonaged commercial hydrated lime mortars show slower carbonation and need a higher binder:aggregate ratio (1:3). The carbonation of nonaged lime mortars follows a normal diffusion-limited continuous path progressing from the mortar sample surface toward the core. Differences between aged and nonaged lime mortar carbonation evolution are explained considering Ca(OH)₂ crystal shape changes (from prisms to platelike crystals) and size reduction that occurs on aging of lime putty. Implications of these results on historic building conservation using traditional lime mortars are discussed.