Red mud addition in the raw meal for the production of Portland cement clinker

The aim of the present research work was to investigate the possibility of adding red mud, an alkaline leaching waste, which is obtained from bauxite during the Bayer process for alumina production, in the raw meal for the production of Portland cement clinker. For that reason, two samples of raw meals were prepared: one with ordinary raw materials, as a reference sample ((PC)Ref), and another with 3.5% red mud ((PC)R/M). The effect on the reactivity of the raw mix was evaluated on the basis of the unreacted lime content in samples sintered at 1350, 1400 and 1450 degrees C. Subsequently, the clinkers were produced by sintering the two raw meals at 1450 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the red mud did not affect the mineralogical characteristics of the so produced Portland cement clinker. 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 the red mud 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.     

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.     

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.     

KHM170型卧辊磨制备钢渣超细粉工业试验研究

基于KHM170型卧辊磨的钢渣超细粉制备终粉磨工业试验系统,在给定钢渣粉、矿渣粉、水泥熟料粉的质量和粒度范围内,进行用钢渣粉部分代替矿渣粉制作水泥混凝土的强度试验。结果表明,KHM卧辊磨终粉磨系统可以实现钢渣超细粉终粉磨,可用于以热焖渣、滚筒渣为原料制备钢渣微粉的工业化生产;矿渣粉中掺加质量分数不超过30%的钢渣粉,且在满足钢渣粉比表面积大于矿渣粉比表面积和水泥熟料粉比表面积时,可以作为优选的混合材料大量用于混凝土。     

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.     

Efficient utilization of cementitious materials to produce sustainable blended cement

To achieve sustainable development of cement industry, cementitious efficiency of different cement clinker and supplementary cementitious materials (SCMs) fractions, in terms of hydration process and strength contribution ratio, was characterized. The results show that blast furnace slag and steel slag should preferably be arranged in fine fractions due to their desirable hydration processes and high strength contribution ratios. Cement clinker should be positioned in intermediate fraction (8–24 μm) due to its proper hydration process. Replacement of cement clinker by SCMs with low activity or inert fillers in coarse fractions was also suggested, because coarse cement clinker fractions gave very low hydration degrees and little strength contribution. Both early and late properties of gap-graded blended cements prepared can be comparable with or higher than those of Portland cement, indicating both cement clinker and SCMs were used more efficiently. These blended cements also give additional cost savings and reduced environmental impact.     

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.     

富硅镁镍渣粉磨细度和掺量对硅酸盐水泥水化特性的影响

通过机械粉磨,将富硅镁镍渣(简称"镍渣")粉磨至微米级,制得的镍渣用作水泥混合材部分替代硅酸盐水泥熟料。测试并分析了镍渣的化学组成、细度、筛余量、体积安定性及孔结构。结果表明:4种镍渣的细度均大于硅酸盐水泥熟料,使得水泥颗粒密度随着镍渣掺量增加而减小;镍渣的胶凝活性低于硅酸盐水泥熟料,使得掺有镍渣的水泥粉末水化反应放热量降低,并伴随有缓凝现象,但随镍渣细度提高,有助于改善其反应活性;掺入镍渣不利于硬化水泥砂浆的抗压强度、抗折强度发挥,提高镍渣细度,则由于紧密堆积效应可改善力学性能;镍渣中的MgO不以f-MgO形式存在,使得硬化水泥浆体的体积安定性合格。     

Clinkers and cements obtained from raw mix containing ceramic waste as a raw material. Characterization,hydration and leaching studies

A clinker and a cement obtained from a raw mix containing ceramic waste as an alternative raw material were characterized in the present study. Their hydration, physical–chemical properties and leaching behaviour in different acid media were also explored. The findings showed that both the clinker and the cement met all the requirements set out in European standards EN 197-1 [1], although they had higher ZnO, ZrO₂, and B₂O₃ contents than an industrially produced reference product.According to the hydration studies, initial hydration was somewhat retarded in the new cement, which exhibited longer initial and final setting times and lower 2-day mechanical strength. The SEM/BSE/EDS microstructural study showed, however, that morphologically and compositionally, the hydration products formed were comparable to unadditioned Portland cement paste products. While low concentrations of Zn and B were observed to leach in acid media, the biotoxicity trials conducted confirmed that these concentrations were not toxic. Zr was retained in the cement pastes.     

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.     

Concretes made of efficient multi-composite cements with slag and limestone

The present paper deals with the performance of concretes made of multi-composite cements with granulated blast furnace slag (GBFS) and limestone (LL) contents beyond the limits of current EN 197-1. The combined application of ground limestone (up to 50%) and GBFS in multi-composite cements can enable a significant reduction in the Portland cement clinker content of cements for the same concrete strength and durability. The lower the w/c-ratio the higher is the potential for the efficient use of Portland cement clinker together with limestone and slag.A comprehensive experimental study was conducted to analyze the mechanical properties and durability of concrete made of multi-composite cements at both laboratory and plant scale. The efficient use of Portland cement clinker together with GBFS and limestone is analyzed for different cement compositions and w/c-ratios. An approach for the optimization of the slag efficiency is proposed. It was concluded that the efficiency of GBFS increases significantly with decreasing w/c-ratio and slag content.Due to the limited availability of slag, the slag content was limited to 30 wt.-% for multi-composite plant cements. The performance of concretes made of such cements containing 50%, 35% and 20% clinker and 20%, 35% and 50% limestone respectively were experimentally analyzed. The results revealed that concrete made of cement with 50 wt.-% clinker, 30 wt.-% GGBFS and 20 wt.-% limestone and a w/c-ratio of 0.50 could exhibit comparable hardened properties compared to reference concrete made of slag cement CEM III/A 42.5 N (with 50 wt.-% slag) with the same w/c-ratio. Concrete made of cements with clinker content of 35 wt.-% and a reduced w/c-ratio of 0.40 could result in a performance similar to the reference concrete made of CEM III/A 42.5 N. Further reduction of clinker content to 20 wt.-% was possible only at a low w/c-ratio of 0.35. Life cycle assessment (LCA) analysis revealed that the application of such multi-composite cements can lead to a concrete with a remarkable lower global warming potential up to about 35% compared to the concrete made of German average cement with a similar performance.     

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.     

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.     

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 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.     

Micro-structural development of gap-graded blended cement pastes containing a high amount of supplementary cementitious materials

To clarify the strength improvement mechanism of gap-graded blended cements with a high amount of supplementary cementitious materials, phase composition of hardened gap-graded blended cement pastes was quantified, and compared with those of Portland cement paste and reference blended cement (prepared by co-grinding) paste. The results show that the gap-graded blended cement pastes containing only 25% cement clinker by mass have comparable amount of gel products and porosity with Portland cement paste at all tested ages. For gap-graded blended cement pastes, about 40% of the total gel products can be attributed to the hydration of fine blast furnace slag, and the main un-hydrated component is coarse fly ash, corresponding to un-hydrated cement clinker in Portland cement paste. Further, pore size refinement is much more pronounced in gap-graded blended cement pastes, attributing to high initial packing density of cement paste (grain size refinement) and significant hydration of BFS.     

Dredged sediments used as novel supply of raw material to produce Portland cement clinker

The maintenance of waterways generates large amounts of dredged sediments that are an environmental issue. This paper focuses on the use of fluvial sediment to replace a portion of the raw materials of Portland cement clinker, which would otherwise come from natural resources. The mineralogy of the synthetic cement was characterised using X-ray diffraction and scanning electron microscopy and its reactivity was followed by isothermal calorimetry. Comparisons were made to a commercial ordinary Portland cement (CEM I 52.5). Compressive strength measurements were conducted on cement pastes at 1, 2, 4, 7, 14, 28 and 56 days to study strength development. The results showed that Portland cement clinker can be successfully synthesised by using up to 39% sediment. The compressive strengths developed by the cement made from sediment were equivalent to those obtained with the reference at early ages and 20% higher at long term.     

An investigation on the recycling of hydrated cement from concrete demolition waste

Construction and demolition waste (CDW) recycling is generally limited to the use of the coarser fraction as aggregate for new concrete. The recovery of fine aggregates requires a cleaning by removing the hydrated cement waste (HCW). In this paper, the possibility to use HCW extracted from CDW as alternative component for the production of new clinker is explored.A pure HCW sample was prepared and used in partial replacement of natural materials in raw admixtures for new clinker production. At a replacement degree of 30%, a new Portland clinker containing almost 50% of C₃S could be produced with a huge spare in the release of CO₂ (about 1/3 less). At higher HCW dosage a non-Portland clinker containing almost 80% of C₂S has been obtained: its use as supplementary cementing material in blended cements revealed satisfying long term performances.     

Effect of PCs superplasticizers on the rheological properties and hydration process of slag-blended cement pastes

The effect of polycarboxylate (PC) superplasticizers with different structure on the rheological properties and hydration process of slag-blended cement pastes with a slag content between 0 and 75% has been studied. Fluidizing properties of PCs admixtures are significantly higher in slag-blended cement with respect to non-blended Portland cement. Also, it has been observed that the rise of the fluidity induced by the PCs on the cement pastes increases with the slag content. This effect is mainly attributed to a decrease in the amount of C₃A available to adsorb and consume admixture to form an organo-mineral phase. Consequently, the PC admixtures are absorbed onto the silicate phases of the clinker and onto the slag particles, inducing a repulsion and the concomitant reduction in yield stress despite a reduction in the zeta potential. The rheological results allow us to conclude that the highest increase of the fluidity is caused by the admixtures with highest molecular weight due to the higher steric repulsion induced. As a consequence of the adsorption of the PCs, a delay of the hydration process of the pastes has been observed.