Utilization of steel slag for Portland cement clinker production

The aim of the present research work is to investigate the possibility of adding steel slag, a by-product of the conversion of iron to steel process, in the raw meal for the production of Portland cement clinker. Two samples of raw meals were prepared, one with ordinary raw materials, as a reference sample ((PC)(Ref)), and another with 10.5% steel slag ((PC)(S/S)). Both raw meals were sintered at 1450 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the steel slag did not affect the mineralogical characteristics of the so produced Portland cement clinker. Furthermore, both clinkers were tested by determining the grindability, setting times, compressive strengths and soundness. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of the steel slag did not negatively affect the quality of the produced cement.     

Examination of the jarosite-alunite precipitate addition in the raw meal for the production of sulfoaluminate cement clinker

The aim of the present research work was to investigate the possibility of adding a jarosite-alunite chemical precipitate, a waste product of a new hydrometallurgical process developed to treat economically low-grade nickel oxides ores, in the raw meal for the production of sulfoaluminate cement clinker. For that reason, two samples of raw meals were prepared, one contained 20% gypsum, as a reference sample ((SAC)Ref) and another with 11.31% jarosite-alunite precipitate ((SAC)J/A). Both raw meals were sintered at 1300 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the jarosite-alunite precipitate did not affect the mineralogical characteristics of the so produced sulfoaluminate cement clinker and there was confirmed the formation of the sulfoaluminate phase (C4A3S), the most typical phase of this cement type. Furthermore, both clinkers were tested by determining the grindability, setting time, compressive strength and expansibility. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of jarosite-alunite precipitate did not negatively affect the quality of the produced cement.     

Potential use of pyrite cinders as raw material in cement production: Results of industrial scale trial operations

Pyrite cinders, which are the waste products of sulphuric acid manufacturing plants, contain hazardous heavy metals with potential environmental risks for disposal. In this study, the potential use of pyrite cinders (PyCs) as iron source in the production of Portland cement clinker was demonstrated at the industrial scale. The chemical and mineralogical analyses of the PyC sample used in this study have revealed that it is essentially a suitable raw material for use as iron source since it contains >87% Fe₂O₃ mainly in the form of hematite (Fe₂O₃) and magnetite (Fe₃O₄). The samples of the clinkers produced from PyC in the industrial scale trial operation of 6 months were tested for the conformity of their chemical composition and the physico-mechanical performance of the resultant cement products. The data were compared with the clinker products of the iron ore, which is used as the raw material for the production Portland cement clinker in the plant. The chemical compositions of all the clinker products of PyC appeared to conform to those of the iron ore clinker, and hence, a Portland cement clinker. The mechanical performance of the mortars prepared from the PyC clinker was found to be consistent with those of the industrial cements e.g. CEM I type cements. It can be inferred from the leachability tests (TCLP and SPLP) that PyC could be a potential source of heavy metal pollution while the mortar samples obtained from the PyC clinkers present no environmental problems. These findings suggest that the waste pyrite cinders can be readily used as iron source for the production of Portland cement. The availability of PyC in large quantities at low cost provides further significant benefits for the management/environmental practices of these wastes and for the reduction of mining and processing costs of cement raw materials.     

Utilization of flotation wastes of copper slag as raw material in cement production

Copper slag wastes, even if treated via processes such as flotation for metal recovery, still contain heavy metals with hazardous properties posing environmental risks for disposal. This study reports the potential use of flotation waste of a copper slag (FWCS) as iron source in the production of Portland cement clinker. The FWCS appears a suitable raw material as iron source containing >59% Fe(2)O(3) mainly in the form of fayalite (Fe(2)SiO(4)) and magnetite (Fe(3)O(4)). The clinker products obtained using the FWCS from the industrial scale trial operations over a 4-month period were characterised for the conformity of its chemical composition and the physico-mechanical performance of the resultant cement products was evaluated. The data collected for the clinker products produced using an iron ore, which is currently used as the cement raw material were also included for comparison. The results have shown that the chemical compositions of all the clinker products including those of FWCS are typical of a Portland cement clinker. The mechanical performance of the standard mortars prepared from the FWCS clinkers were found to be similar to those from the iron ore clinkers with the desired specifications for the industrial cements e.g. CEM I type cements. Furthermore, the leachability tests (TCLP and SPLP) have revealed that the mortar samples obtained from the FWCS clinkers present no environmental problems while the FWCS could act as the potential source of heavy metal contamination. These findings suggest that flotation wastes of copper slag (FWCS) can be readily utilised as cement raw material due to its availability in large quantities at low cost with the further significant benefits for waste management/environmental practices of the FWCS and the reduced production and processing costs for cement raw materials.     

Waste with chrome in the Portland cement clinker production

Hazardous wastes, coming from industries are usually used in the Portland cement production in order to save energy, costs and/or stabilize toxic substances and heavy metals inside the clinker. This work focuses on the effect produced on the Portland cement clinker when it is obtained using tanned leather shavings whit chrome salts as part of the process. The raw materials were clinkered in laboratory with different percentages of shavings, which contained 2% of Cr(2)O(3). DTA-TG of the raw mixtures was performed to evaluate the thermal behavior changes that can take place during the clinkering process, analyzing the crystalline phases obtained by XRD. The milling behavior of clinkers was studied, analyzing also the refractoriness variation on those clinkers. The chrome retention was evaluated by leaching tests. The structural modification determined by the chrome presence in the silicate structure brought consequences in the hydration speed, mechanical resistance and pore distribution.     

Utilization of municipal solid waste incineration ash in Portland cement clinker

Municipal solid waste incineration (MSWI) ash is used in part as raw materials for cement clinker production by taking advantage of the high contents of SiO₂, Al₂O₃, and CaO. It is necessary for environmental reasons to establish a material utilization system for the incineration waste ash residue instead of disposing these ashes into landfill. The aim of this paper is to study the feasibility of replacing clinker raw materials by waste ash residue for cement clinker production. MSWI bottom ash and MSWI fly ash are the main types of ashes being evaluated. The ashes were mixed into raw mixture with different portions of ash residue to produce cement clinker in a laboratory furnace at approximately 1400°C. X-ray diffraction and X-ray florescence techniques were used to analyze the phase chemistry and chemical composition of clinkers in order to compare these ash-based clinkers with commercial Portland cement clinker.     

Reduction of clinkerization temperature by using phosphogypsum

Valorization of phosphogypsum as mineralizer in the burning of Portland cement clinker was studied in our laboratory. X-ray fluorescence, optical microscope technique and powder X-ray diffraction were then used to characterize the synthesized clinker and its raw mixture in terms of chemical composition and clinker mineralogical composition. The effects of phosphogypsum on structural and morphological properties of clinker minerals and on the presence of alite were followed by scanning electron microscopy combined with microprobe analysis. The addition of phosphogypsum to the cement raw mixture shows that the burning temperature decreases and therefore improves the production process of clinker. The addition of 10% phosphogypsum permits a complete clinkerization at low burning temperature (1200 degrees C), instead of 1470 degrees C, which increases the cement factory efficiency by 25% and extends the service life of furnace fire brick. Structural and morphological analysis of clinker produced under the new conditions show that phosphogypsum preserve perfectly the crystalline structure of silicate phases, which leads to the improvement of physical and mechanical properties of cement.     

Incorporation of coal combustion residuals into calcium sulfoaluminate-belite cement clinkers

In recent years, calcium sulfoaluminate-belite (CSAB) cement has been promoted as a sustainable alternative to Portland cement due to lower energy used and less CO₂ emitted during production, while providing comparable performance. However, a potential problem facing the widespread adoption and production of CSAB cement is the cost and availability of raw materials and it is therefore desirable to find alternative raw materials to keep costs competitive. In this study, two CSAB cement clinkers with a similar target phase composition were synthesized from combinations of natural and waste materials (coal combustion residuals). The two CSAB cement clinkers were compared against a CSAB clinker made from reagent-grade chemicals, enabling examination of the effects of impurities on performance. Cements made from the clinkers were examined for hydration rate, hydration product formation, dimensional stability, and compressive strength.     

Belite cements obtained from ceramic wastes and the mineral pair CaF2/CaSO4

The cement industry is seeking alternative approaches to reduce the high energy and environmental costs of Portland cement manufacture. One such alternative is belite cement. In the present study clinkers with high (36–60%) belite contents were obtained at 1350 °C from raw mixes consisting of ceramic waste and the fluxing/mineralised pair CaF₂/CaSO₄. The factors found to affect the mineralogical composition and the clinker phase polymorphs obtained were the lime saturation factor (LSF), the presence of ceramic waste and the addition of CaF₂ and CaSO₄.The reactivity of these belite clinkers with water was analysed with isothermal conduction calorimetry. A statistical study was then conducted on the findings to determine the effect of each variable when the response signals were peak heat flow rate and the time needed to reach that peak. The statistical analysis identified the optimal experimental conditions to be a LSF of 90%, a CaSO₄ content of 2.60%, and the absence of both ceramic waste and CaF₂.     

Preparation of calcium sulphoaluminate cement using fertiliser plant wastes

Phosphochalks from fertiliser plants contain significant amount of calcium sulphate along with P(2)O(5) and fluorine. The presence of these impurities makes them unsuitable for most applications and, hence its availability in millions of tons. We demonstrate that it is possible to prepare calcium sulphoaluminate-aluminoferrite based special cements having strength values comparable to ordinary Portland cement (OPC) using these waste chalks. Such cements are insensitive to the presence of impurities in the raw mixture, clinker at low temperatures (1,230 degrees C) and the clinkers produced are soft and friable. An empirical technique has been developed to predict the phase composition of the clinkers given the chemical composition of the starting raw mixture. The proposed low temperature clinkering route appears to be a promising method for converting waste phosphochalks into construction grade cements.     

The effect of clinker and limestone quality on the gas permeability,water absorption and pore structure of limestone cement concrete

In this paper the effect of clinker and limestone quality on the air permeability, water absorption and pore structure of limestone cement concrete is investigated. Portland limestone cements of different fineness and limestone content have been produced by intergrinding clinker, gypsum and limestone. Two clinkers with different chemical composition, mineralogical composition and strength development as well as three limestones, differing by their calcite, dolomite, quartz and clay contents, have been used. It is shown that the clinker quality significantly affects the gas permeability and sorptivity of the limestone cement concrete. Limestone cements with high C₃A and alkalis content seem to be more appropriate for improving the permeability properties of concrete. In addition, the effect of the limestone quality on the concrete permeability is not well established. The pore size distribution and more specifically the mean pore size affects the gas permeability and the sorptivity of the concrete. Finally it is concluded that, depending on the clinker quality and the cement fineness, limestone cement concrete, with an optimum limestone content, can give lower gas permeability and water absorption rate as compared with pure cement concrete.     

Utilization of ferroalumina as raw material in the production of Ordinary Portland Cement

Red mud (RM), the digestion by-product of bauxite processing from “Aluminum Hellas”, was dewatered by means of a filter press. The filtrand with water content from 28 to 32 wt% was named ferroalumina (FA). In order to utilize it as a raw material in the production of Ordinary Portland Cement (OPC), mixtures were prepared with limestone, sandstone and 1, 3 and 5 wt% FA addition, respectively. The design of the mixtures was based on the cement's compositional indexes LSF, AM and SM. Burnability tests showed that less than 1 wt% free lime can be obtained in all cases for firing at 1450 °C, except for the mixture with 1 wt% FA addition, which requires 1550 °C. XRD analysis and optical microscopy examination showed that FA addition did not affect the mineralogical phases of the produced clinkers. The characterisation of the produced Portland cements indicated that differences on surface area, water requirement and setting time are negligible. Compressive strength results after 28 days of curing varies from 55 to 63 MPa, which ranks the produced cements in CEM I 42.5N category. More specifically, the cements with FA addition due to their relatively high 2-day strengths (>20 MPa) can be ranked in CEM I 52.5N category. Addition of FA increases the amount of water-soluble chromium proportionally to the amount of total chromium to the mixture; however, conversion of total Cr to hexavalent Cr remains practically constant, in the range of 32–35 wt%. The results indicate that FA can be used as raw material in the production of OPC up to 5 wt% according to the chemical composition of the other raw materials.     

Evaluation of blends bauxite-calcination-method red mud with other industrial wastes as a cementitious material: properties and hydration characteristics

Red mud is generated from alumina production, and its disposal is currently a worldwide problem. In China, large quantities of red mud derived from bauxite calcination method are being discharged annually, and its utilization has been an urgent topic. This experimental research was to evaluate the feasibility of blends red mud derived from bauxite calcination method with other industrial wastes for use as a cementitious material. The developed cementitious material containing 30% of the bauxite-calcination-method red mud possessed compressive strength properties at a level similar to normal Portland cement, in the range of 45.3-49.5 MPa. Best compressive strength values were demonstrated by the specimen RSFC2 containing 30% bauxite-calcination-method red mud, 21% blast-furnace slag, 10% fly ash, 30% clinker, 8% gypsum and 1% compound agent. The mechanical and physical properties confirm the usefulness of RSFC2. The hydration characteristics of RSFC2 were characterized by XRD, FTIR, (27)Al MAS-NMR and SEM. As predominant hydration products, ettringite and amorphous C-S-H gel are principally responsible for the strength development of RSFC2. Comparing with the traditional production for ordinary Portland cement, this green technology is easier to be implemented and energy saving. This paper provides a key solution to effectively utilize bauxite-calcination-method red mud.     

A study on the parameters affecting the properties of Portland limestone cements

In this paper the parameters affecting the properties of Portland limestone cements are investigated. Portland limestone cements of different fineness and limestone content have been produced by intergrinding clinker, gypsum and limestone. Two kinds of clinker of different chemical composition, mineralogical composition and strength development and three limestones, with different contents of calcite, dolomite, quartz and clay, have been used. It is concluded that the appropriate choice of the clinker quality, limestone quality, % limestone content and cement fineness can lead to the production of a limestone cement with the desired properties. Limestone cements, having up to 10% limestone content and fineness up to a limit value, develop almost the same compressive strength, as the corresponding pure cements. The limestone cements, generally have lower paste water demand than the relative pure cements and the water demand decrease is mainly affected by the clinker type and limestone quality. In any case the properties of the limestone cements are affected by the interaction of the two components rather than their individual properties.     

Waste ammunition as secondary mineralizing raw material in Portland cement production

This paper presents a laboratory scale simulation that aims to investigate the possibility of partially substituting ordinary cement raw mix with waste ammunition materials (WAM), originated from a shooting range in Athens, Greece, in Portland cement clinker production. One reference and twelve modified mixtures, containing 0.5%, 1.0%, 1.5% and 2.0% w/w of three blends of corresponding types of waste ammunition materials, were examined. It was concluded that the three used WAM blends, improve remarkably the burnability of the cement raw mixture, even though in a different extent, without affecting considerably the hydration rate and the cement properties. In spite of the high volatile matter in the WAM, primarily due to high levels of lead present, incorporation degree of the heavy metals present in the WAM blends in the mineralogical clinker compounds was rather high during the sintering process. Leaching tests showed that the heavy metal concentrations in the leachates were kept low.     

Utilization of oil shale in the production of Portland clinker

Oil shale can potentially be utilized in manufacturing the Portland cement. In addition to the utilization of the spent oil shale after combustion, it can also reduce the required temperature for the clinkering reactions during the production of Portland clinker. A study on the Jordanian oil shale was performed to maximize the use of oil shale ash in the manufacturing of Portland cement. It was found that Jordanian oil shale can be used up 15% with the typical raw materials to produce Portland clinker without altering its principle properties. The corresponding temperature required to generate the required liquid for the clinkering reactions as well as the essential ingredients for clinker was found to be around 1300 °C. The optimized blend ratio obtained was equal to of 16% oil shale ash, 18% kaolinite, and 66% calcite. The operating temperatures for this optimized blend ratio were found to be between 1300 and 1350 °C. The resulting Portland clinker from this ratio will need further testing in accordance with international standards for Portland cement to examine properties like strength, setting time, etc.     

Synthesis and hydration of calcium sulfoaluminate-belite cements with varied phase compositions

The production of portland cement is energy intensive and contributes significantly to greenhouse gas emissions. One method of reducing the environmental impact of concrete production is the use of an alternative binder, such as calcium sulfoaluminate-belite (CSAB) cement. The relatively low lime requirement of CSAB cement compared to portland cement reduces energy consumption and carbon dioxide emissions from cement production. Moreover, CSAB cement can be produced at temperatures approximately 200 °C lower than portland cement, further reducing energy and carbon dioxide. Major drawbacks to the implementation of CSAB cements are the lack of standard phase composition and published data on composition-processing-performance relationships. In this study, three CSAB cement clinkers with different phase compositions were synthesized from reagent-grade chemicals. The synthetic clinkers were analyzed for phase composition using X-ray diffraction and phase distribution using scanning electron microscopy. The synthetic clinkers were then tested for hydration rate using isothermal conduction calorimetry to investigate the effects of phase composition and gypsum addition on early-age hydration behavior. A proportioning method for predicting phase composition was refined and an equation for calculating the minimum gypsum content for CSAB cement clinker was developed.     

Reuse of water purification sludge as raw material in cement production

The feasibility of partial replacement of siliceous raw material for cement production with water purification sludge (WPS) was investigated by X-ray diffraction, free-lime analysis, compressive strength testing and toxicity characteristics leaching procedure (TCLP). It is found that WPS has no negative effects on the consumption of free lime and the formation of clinker minerals. The samples with WPS from 4 to 10 wt.% have higher 3 days and 7 days strengths than the control. After 28 days, however, only WPS replacements <7% increased the strength of samples. It is noteworthy that heavy metals in WPS were almost completely incorporated into the clinkers, and up to 28 days the heavy metals were not detected in the leachates. From the above results of clinker minerals, compressive strength and leaching tests, it can be concluded that WPS has the potential to be utilized as an alternative raw material in cement production.     

Ceramic wastes as alternative raw materials for Portland cement clinker production

The cement industry has for some time been seeking procedures that would effectively reduce the high energy and environmental costs of cement manufacture. One such procedure is the use of alternative materials as partial replacements for fuel, raw materials or even clinker. The present study explores the reactivity and burnability of cement raw mixes containing fired red or white ceramic wall tile wastes and combinations of the two as alternative raw materials.The results showed that the new raw mixes containing this kind of waste to be technically viable, and to have higher reactivity and burnability than a conventional mix, providing that the particle size of the waste used is lower than 90 μm. The mineralogical composition and distribution in the experimental clinker prepared were comparable to the properties of the clinker manufactured with conventional raw materials. Due to the presence of oxides such as ZnO, ZrO₂ and B₂O₃ in tile glazing, the content of these oxides was higher in clinker made with such waste. The mix of red and white ceramic wall tile waste was found to perform equally or better than each type of waste separately, a promising indication that separation of the two would be unnecessary for the purpose described above.     

Effects of mix composition and water–cement ratio on the sulfate resistance of blended cements

This paper presents an experimental investigation on the sulfate resistance of blended cements containing various amounts of natural pozzolan and/or Class-F fly ash. The performance of blended cements was monitored by exposing the prepared mortar specimens to a 5% Na₂SO₄ solution for 78 weeks. For comparison, an ordinary Portland cement (produced with the same clinker as blended cements) and a sulfate resistant Portland cement (produced from a different clinker) were also used. In addition to the cement chemistry, water–cement (w/c) ratio of mortars was another parameter selected that will presumably affect the performance of mortars. The experimental results of expansion measurements showed that the effect of w/c ratio was more pronounced for the low sulfate resistant cements with higher C₃A amounts, while the blended cements were less affected by an increase in the w/c ratio.