Diffusion and reaction mechanism of limestone and quartz in fluxed iron ore pellet roasting process

The increase to the proportion of fluxed pellets in the blast furnace burden is a useful way to reduce the carbon emissions in the ironmaking process.In this study,the interaction between calcium carbonate and iron ore powder and the mineralization mechanism of fluxed iron ore pellet in the roasting process were investigated through diffusion couple experiments.Scanning electron microscopy with energy dispersive spectroscopy was used to study the elements’diffusion and phase transformation during the roasting process.The results indicated that limestone decomposed into calcium oxide,and magnetite was oxidized to hematite at the early stage of preheating.With the increase in roasting temperature,the diffusion rate of Fe and Ca was obviously accelerated,while the diffusion rate of Si was relatively slow.The order of magnitude of interdiffusion coefficient of Fe_(2)O_(3)-CaO diffusion couple was 10^(−10) m^(2)·s^(−1) at a roasting temperature of 1200℃for 9 h.Ca_(2)Fe_(2)O_(5) was the initial product in the Fe_(2)O_(3)-CaO-SiO_(2) diffusion interface,and then Ca_(2)Fe_(2)O_(5) continued to react with Fe_(2)O_(3) to form CaFe_(2)O_(4).With the expansion of the diffusion region,the sillico-ferrite of calcium liquid phase was produced due to the melting of SiO_(2) into CaFe_(2)O_(4),which can strengthen the consolidation of fluxed pellets.Furthermore,andradite would be formed around a small part of quartz particles,which is also conducive to the consolidation of fluxed pellets.In addition,the principle diagram of limestone and quartz diffusion reaction in the process of fluxed pellet roasting was discussed.

Effect of diagenetic variation on the static and dynamic mechanical behavior of coral reef limestone

Coral reef limestone at different depositional depths and facies differ remarkably on the textural and mineralogical characteristics,owing to the complex sedimentary diagenesis.To explore the effects of pore structure and mineral composition associated with diagenetic variation on the mechanical behavior of reef limestone,a series of quasi-static and dynamic compression tests along with microscopic examinations were performed on the reef limestone at shallow and deep burial depths.It is revealed that the shallow reef limestone(SRL)is classified as a porous aragonite-type carbonate rock with high porosity(55.3±3.2)%and pore connectivity.In comparison,the deep reef limestone(DRL)is mainly composed of dense calcite-type calcium carbonate with low porosity(4.9±1.6)%and pore connectivity.The DRL strengthened and stiffened by the tight grain framework consistently displays much higher values of the dynamic compressive strength,elastic modulus,brittleness index,and specific energy absorption than those of the SRL.The gap between two types of limestone further increases with an increase in strain rate.It appears that the failure pattern of SRL is dominated by the inherent defects like weak bonding interfaces and growth lines,revealed by the intricate fracturing network and mixed failure.Likewise,although the preexisting megapores in DRL may affect the crack propagation on pore tips to a certain distance,it hardly alters the axial splitting failure of DRL under impacts.The stress wave propagation and attenuation in SRL is primarily controlled by the reflection and diffusion caused by plenty mesopores,as well as an energy dissipation in layer-wise pore collapse and adjacent grain crushing,while the stress wave in DRL is highly hinged on the insulation and diffraction induced by the isolated megapores.This process is accompanied by the energy dissipation behavior of inelastic deformation resulted from the pore-emanated microcracking.

A machine learning-based strategy for predicting the mechanical strength of coral reef limestone using X-ray computed tomography

Different sedimentary zones in coral reefs lead to significant anisotropy in the pore structure of coral reef limestone(CRL),making it difficult to study mechanical behaviors.With X-ray computed tomography(CT),112 CRL samples were utilized for training the support vector machine(SVM)-,random forest(RF)-,and back propagation neural network(BPNN)-based models,respectively.Simultaneously,the machine learning model was embedded into genetic algorithm(GA)for parameter optimization to effectively predict uniaxial compressive strength(UCS)of CRL.Results indicate that the BPNN model with five hidden layers presents the best training effect in the data set of CRL.The SVM-based model shows a tendency to overfitting in the training set and poor generalization ability in the testing set.The RF-based model is suitable for training CRL samples with large data.Analysis of Pearson correlation coefficient matrix and the percentage increment method of performance metrics shows that the dry density,pore structure,and porosity of CRL are strongly correlated to UCS.However,the P-wave velocity is almost uncorrelated to the UCS,which is significantly distinct from the law for homogenous geomaterials.In addition,the pore tensor proposed in this paper can effectively reflect the pore structure of coral framework limestone(CFL)and coral boulder limestone(CBL),realizing the quantitative characterization of the heterogeneity and anisotropy of pore.The pore tensor provides a feasible idea to establish the relationship between pore structure and mechanical behavior of CRL.

Hydrocarbon generation and organic matter enrichment of limestone in a lacustrine mixed sedimentary environment: A case study of the Jurassic Da'anzhai member in the central Sichuan Basin, SW China

The hydrocarbon generation effectiveness of lacustrine limestone has been gradually proven. The Da'anzhai Member limestone is the most important Jurassic oil-producing layer in the central Sichuan Basin, and the characteristics of limestone organic matter are often overlooked. 175 typical samples of different lithologies from 19 wells were systematically analyzed to determine hydrocarbon generation, controlling factors and formation models by analyses of organic matter, minerals, elements, isotopes and petrography. (1) Lacustrine paleoenvironments can be beneficial for the enrichment of organic matter in limestone. A favorable environment would be a quiet, low-energy zone in a warm and humid climate with an appropriate supply of terrestrial inputs. (2) Lacustrine limestone has a higher organic matter conversion rate, and a lower hydrocarbon generation threshold than argillaceous source rocks, and can be effective source rock. (3) The mud-bearing shell limestone from the forebeach to the lake slope is thick, with a relatively high abundance of organic matter, and its hydrocarbon generation is effective. This study can clarify the effectiveness and enrichment of the limestone organic matters in the study area, and contribute to an understanding of hydrocarbon generation for full-rock system in a lacustrine mixed sedimentary environment.

Effect of High Content Limestone Powder on Microstructure and Mechanical Properties of Cement-based Materials

Compared with the control sample without limestone powder(LP), the mechanical properties of the sample with 30% LP can be significantly improved by using a small amount of water reducer to reduce the water-cement ratio, without significantly affecting the fluidity of the fresh mixture and increasing the economic cost. In addition, compared with the sole addition of limestone powder, dual addition of metakaolin and limestone powder can effectively improve the strengths. The reason of this phenomenon was investigated by means of XRD, TG-DTG, SEM, LF-NMR and isothermal calorimetry, etc. The reactive aluminum-rich phases in metakaolin react with limestone powder in the hydration process, and the formed calcium carboaluminate reduces the porosity and makes the hardened paste denser. The addition of ground granulated blast furnace slag can also improve the strength of the specimen added with limestone powder, whereas, the effect is inferior to that of metakaolin, for the ground granulated blast furnace slag contains less reactive aluminate phases, and accordingly, the amount of calcium carboaluminate generated is lower than that of metakaolin.

The formation of orthogonal joint systems and cuboidal blocks:New insights gained from flat-lying limestone beds in the region of Havre-Saint-Pierre(Quebec,Canada)

Vertical orthogonal joints are a common feature in shallow crustal rocks.There are several competing theories for their formation despite the ubiquity.We examined the exceptional exposures of orthogonal joints in flat-lying Ordovician limestone beds from the Havre-Saint-Pierre Region in Quebec,Canada(north shore of Saint-Lawrence River)to test conceptual models of joint formation in a natural setting.In the region,the spacing of cross-joints is consistently larger than the spacing of systematic joints by a factor of 1.5 approximately.The joint-spacing-to-bed-thickness ratios(s/t)are much larger in these beds(s/t=4.3 for systematic joints,and 6.4 for cross-joints)than those in higher strained strata along the south shore of the Saint-Lawrence River(s/t=1),highlighting the effect of tectonic strain in decreasing fracture spacing and block size.The high values of s/t indicate that cross-joint formation was unlikely caused by a switch from compression to tension once a critical s/t ratio for systematic joints was reached(as hypothesized in previous studies).We proposed a new model for the formation of orthogonal joint systems where the principal stress axes locally switch during the formation of systematic fractures.The presence of ladder-shaped orthogonal joints suggests a state of effective stress withσ_(1)^(∗)≫0>σ_(2)^(∗)>σ_(3)^(∗)and whereσ_(2)^(∗)-σ_(3)^(∗)is within the range of fracture strength variability at the time of fracture.This research provides a new mechanical model for the formation of orthogonal joint systems and cuboidal blocks.

Production of an Eco-Cement by Clinker Substitution by the Mixture of Calcined Clay and Limestone, Songololo (DR Congo)

Ordinary Portland Cement (OPC) is by mass the largest manufactured product on Earth, responsible for approximately 6% - 8% of global anthropogenic carbon dioxide emissions (CO2) and 35% of industrial CO2 emissions. On average 0.8 to 0.9 ton of CO2 is emitted to produce one ton of OPC. In this paper, partial substitution of clinker (30% - 35%) by the calcined clay-limestone mixture was investigated in order to produce an eco-cement (LC3). Analyzes by XRF, XRD and ATG/ATD have characterized different components, determined the calcination temperature and selected the right clay which can act as effective Supplementary Cementitious Material (SCM). Mechanical tests on mortar carried out over a period of 90 days. The WBCSD/WRI “Greenhouse Gas Protocol” methodology then allowed the calculation of CO2 emissions into the atmosphere. Three types of clay are available in the Songololo Region. The kaolinite is the principal clay mineral and its content varies from 27% to 34%. The sum of kaolinite and amorphous phase which enable clay to react with cementitious material ranges from 57% to 60%. The SiO2 content ranges from 33% to 76%, the Alumina content from 12% to 20% so that the ratio Al2O3/SiO2 is on the higher side (0.17 - 0.53). The calcination window is between 750°C and 850°C and the best clay which can act as SCM identified. The clinker’s substitution reduced CO2 emissions from 0.824 ton of CO2 for one ton of OPC to 0.640 ton of CO2 for one ton of LC3, means 22% less emissions. The compressive strengths developed by LC3 vary from 8.91 to 57.6 MPa (Day 1 to Day 90), exceed those of references 32.5 cement and are close to 42.5 cement. In view of the results, LC3 cement can be considered for industrial trials.

Meso-mechanical anisotropy and fracture evolution of reef limestones from the Maldives Islands and the South China Sea

Reef limestone is a biogenic sedimentary rock widely distributed in coral reef areas, acting as an important foundation for coast construction. Due to its special biogenic origin, reef limestone is different from conventional rocks both in terms of rock structure and mechanical properties. In this study, mesoscale uniaxial compression experiments with five different loading directions were conducted on two kinds of reef limestones from the Maldives Islands and the South China Sea, respectively. The real-time high-resolution videos and images of failure processes were recorded simultaneously to investigate the fracture evolution and fracture surface roughness of reef limestones. It demonstrated that the reef limestones belonged to extremely soft to soft rocks, and their uniaxial compressive strength (UCS) values fluctuated with high discreteness. The mesoscale mechanical properties of reef limestones were highly anisotropic and mainly controlled by pore structure. The occurrence of dissolution pores in reef limestone tended to intensify mechanical anisotropy. With the integration of the fracture initiation and propagation features of reef limestones, it is supposed that the intrinsic mechanism of anisotropy was probably attributed to the differences in coral growth direction and dissolution. Furthermore, the quantified fracture surface roughness was revealed to have a good consistency with density and UCS for the reef limestones from the South China Sea. The findings are helpful for providing theoretical and experimental references for engineering construction in coral reef areas.

Geochemistry of the Aptian bituminous limestones in Gümuü?hane area,Eastern Black Sea region:new insight into paleogeography and paleoclimate conditions

Aptian is characterized by widespread deposition of organic-rich sediment.The Aptian bitumen limestone horizon,which is thin decimetre-thick sequences,locally crops out in the Kircaova area,Eastern Black Sea Region(Eastern Pontides).They are well correlated with Aptian bitumen limestone in the other Tethys Reams.They are proposed as episodes of increased organic matter.However,background factors controlling organic matter enrichment are poorly known.In this study,we present new inorganic geochemistry,including trace elements,rare earth elements(REE),redox-sensitive elements(RSE),stable-isotopes(δ~(18)O andδ~(13)C),and total organic carbon(TOC).We integrated new geochemical data with existing stratigraphy,paleontology,and organic chemistry data to provide new insight into the depositional environment and paleoclimate conditions during Aptian.The lacustrine bitumen limestone(LBL)samples have variedδ~(13)C(ave.-1.45‰)andδ~(18)O(ave.-4.50‰).They possess distinct REE patterns,with an average of REE(ave.14.45 ppm)and Y/Ho(ave.35)ratios.In addition,they have variable Nd/YbN(0.28-0.81;ave.0.56)and Ce/Ce*(0.68-0.97;ave.0.86),and relatively high Eu^(*)/Eu(1.23-1.53;ave.1.35).They display seawater signatures with reduced oxygen conditions.The enrichment in RSE(Mo,Cu,Ni,and Zn)and the low Mo/TOC(0.70-3.69;ave.2.41)support a certain degree of water restriction.The high Sr/Ba,Sr/Cu,Ga/Rb,and K/Al records of the LBL facies suggest hot house climatic conditions.The sedimentary environment was probably an isolated basin that is transformed from the marine basin.In addition to depositional conditions,the regional parameters such as the climate,increased run-off period,nutrient levels,alkalinity level,and dominant carbonate producers favored the enrichment in organic matter of LBL facies.Thus,extreme greenhouse palaeoclimate conditions have an important role in organic matter enrichment in the isolated basin.Our results are conformable with the published data from marine,semi-restricted basin,and lacustrine settings in the different parts of the Tethys margin.Thus,this approach provides the first insight into the Aptian greenhouse paleo-climate conditions of the Eastern Black Sea Region,NE Turkey.

Preparation of High Activity Admixture from Steel Slag,Phosphate Slag and Limestone Powder

The problem of low disposal and utilization rate of bulk industrial solid waste needs to be solved.In this paper,a high-activity admixture composed of steel slag-phosphate slag-limestone powder was proposed for most of the solid waste with low activity and a negative impact on concrete workability,combining the characteristics of each solid waste.The paper demonstrates the feasibility and explains the principle of the composite system in terms of water requirement of standard consistency,setting time,workability,and mechanical properties,combined with the composition of the phases,hydration temperature,and microscopic morphology.The results showed that the steel slag:phosphate slag:limestone=5:2:3 gave the highest activity of the composite system,over 92%.Besides,the composite system had no significant effect on water demand and setting time compared to cement,and it could significantly increase the 7 and 28 d activity of the system.The composite system delayed the exothermic hydration of the cement and reduced the exothermic heat but had no effect on the hydration products.Therefore,the research in this paper dramatically improved the solid waste dissipation in concrete,reduced the amount of cement in concrete and positively responded to the national slogan of carbon neutral and peaking.

Lithostratigraphy and Characterisation of Paleocene Limestones for Optimal Exploitation (Senegal, West Africa): Comparative Study of the Bandia and Popenguine Quarries

Limestones of different facies in the Senegal basin are most commonly used as aggregates, regardless of their petrographic properties. These differences may influence their behaviour. The aim of this paper is to study the stratigraphy and characterise the limestones of the Bandia and Popenguine quarries. Sampling and geochemical and geotechnical characterisation were carried out on these limestones. The results show the presence of several very different facies in the Paleocene formation. The geochemical study shows that the Bandia limestones (Bd2) have the highest CaCO3 percentages (98.54%) and the highest SiO2 percentages were recorded in the Popenguine limestones (Pop2). The study also gives MDE values of 22.38 and LA of 22, which are acceptable for use in road construction. It is important to carry out a complete study in order to select the right materials for optimal use.

Study on the Characteristics of Main Vegetation Communities in the Limestone Region of Taihang Mountain

[Objective] The aim was to study the characteristics of main vegetation communities in the limestone region of Taihang Mountain,so as to lay foundation for the further improvement of site conditions and the scientific breeding of vegetation used to restore the mountain field in limestone region.[Method] Based on the investigation of various vegetation communities in controlled test area,forbidden region and barren hillsides in Daqing Mountain basin,Beishui Valley,Mancheng County,Hebei Province,the difference among controlled region,forbidden region and barren hillsides could be found through data analysis and composite score,and the modes of vegetation communities in controlled region and forbidden region were compared to select predominant species of arbor,shrub and grass in limestone region.[Result] Under the similar site conditions,nutrient content and physical properties of soil in controlled region and forbidden region were superior to those of barren hillsides,and persimmon had high nutrient content and better physical properties compared with oriental arborvitae in controlled region;soil water maintenance and litter characters in controlled region and forbidden region improved more obviously than that of barren hillsides,and shrubbery in forbidden region was the most excellent,arborvitae and persimmon in controlled region the second;the biomass and the coverage rate of vegetation communities in controlled region and forbidden region were higher than those of barren hillsides,and those of shrubbery in forbidden region were better than tussock in closing hill,while persimmon was better than arborvitae in controlled region.The predominant species of arbor,shrub and herbage were obtained through composite score.[Conclusion] From the aspects of soil nutrient,physical properties,soil water maintenance,litter characters,vegetation biomass,canopy density and coverage,controlled region and forbidden region were superior to barren hillsides,and the selection of predominant species of arbor,shrub and herbage considered both ecological and economic benefits.

Ordovician limestone aquosity prediction using nonlinear seismic attributes:Case from the Xutuan coal mine

Ordovician limestone water is coal mines. In this paper, we analyze the the main source of water inrush in North China characteristic of three kinds of nonlinear seismic attributes, such as the largest lyapunov exponent,fractal dimension and entropy and introduce their calculation methods. Taking the 81st and 82nd coal districts in the Xutuan coal mine as examples, we extract the three seismic attributes based on the 3D prestack migration seismic data of this area, which can display the Ordovician limestone fracture distribution in the mine. We comprehensively analyzed the three nonlinear seismic attributes and compared the results with transient electromagnetic exploration results and determined the possible Ordovician limestone aquosity distribution. This demonstrated that the nonlinear seismic attributes technology is an effective approach to predict the aquosity of Ordovician limestone.

Model of limestone calcination / sulfation under oxy-fuel fluidized bed combustion

The characteristics of the simultaneous calcination/ sulfation of limestone under oxy-fuel fluidized bed combustion were studied and compared with those of the sulfation of precalcined CaO. During the calcination stage, SO2 can react with product CaO and slow down the CaCO3 decomposition rate by the covering effect of the CaSO4 product. The sulfation rate of simultaneous calcinatiort/sulfation is slower than that of precalcined CaO, but with a long enough sulfation time, the calcium conversion of simultaneous calcination/sulfation is higher than that of the precalcined CaO. A grain-micrograin model is established to describe the simultaneous calcination, sintering and sulfation of limestone. The graln-micrograln model can reflect the true reaction process of the calcination and sulfation of limestone in oxy-fuel fluidized bed combustion.

Time-sensitivity of the Kaiser effect of acoustic emission in limestone and its application to measurements of in-situ stress

Measuring in-situ stress by using the Kaiser effect in rocks has such advantages as timeefficiency, low cost and little limitation, but the precision of the method is dependent on rock properties and delay time of the measurement. In this paper, experiments on the Kaiser effect in limestones were performed, and it was found that the limestones had good ability to retain a memory of their recent stress history and high time-sensitivity. The longer the experiment was delayed from the extraction of the stone, the larger the Felicity ratio was. As the Felicity ratio approached l, significant Kaiser effect was observed. In-situ stress should be determined by the limestone measurements when the delay time was 40-120 days. Finally, the in-situ stress in a limestone formation could be successfully measured in practice.

Computer vision-based limestone rock-type classification using probabilistic neural network

Proper quality planning of limestone raw materials is an essential job of maintaining desired feed in cement plant. Rock-type identification is an integrated part of quality planning for limestone mine. In this paper, a computer vision-based rock-type classification algorithm is proposed for fast and reliable identification without human intervention. A laboratory scale vision-based model was developed using probabilistic neural network（PNN） where color histogram features are used as input. The color image histogram-based features that include weighted mean, skewness and kurtosis features are extracted for all three color space red, green, and blue. A total nine features are used as input for the PNN classification model. The smoothing parameter for PNN model is selected judicially to develop an optimal or close to the optimum classification model. The developed PPN is validated using the test data set and results reveal that the proposed vision-based model can perform satisfactorily for classifying limestone rocktypes. Overall the error of mis-classification is below 6%. When compared with other three classification algorithms, it is observed that the proposed method performs substantially better than all three classification algorithms.

Effect of Limestone Powder on Microstructure of Concrete

The effect of limestone powder on microstructure of concrete was studied by using mercury intrusion porosimetry （MIP）, backscattering scanning electron（BSE）, scanning electron mi- croscopy （SEM） and X-ray diffraction （XRD） techniques. The experimental results show that the compressive strength of concrete containing 100 kg/m3 limestone powder can meet the strength requirement. Limestone powder has not pozzolanic activity; it is still unhydrated at the age of 28 days. But its filling effect can make the paste matrix and the interfacial transition zone between matrix and aggregate denser, which will improve the performance of concrete.

Overburden management in open pits: options and limits in large limestone quarries

The management of overburden is an important task in open pit exploitations. Site topography and morphology as well as geological and geotechnical properties of natural and remoulded materials are the most important factors affecting the disposal phase. Economic and environmental requirements must be followed in order to achieve the best reclamation results, keeping into account site constraints such as slope stability, hauling and dumping issues, and interactions with groundwater. This paper deals with the above mentioned issues, illustrating a rational approach applied on the case of a large limestone quarry where the thickness of the overburden is relevant and the spoil material has to be dumped in a flooded pit. The proposed multidisciplinary approach led to the selection of most suitable methods for excavation, transportation and disposal. The selection was based on a detailed laboratory and site characterisation that defined favorable and adverse factors to be considered during the preliminary study of a large quarrying project.

New Evidence for Hydrothermal Sedimentary Genesis of the Ni-Mo Deposits in Black Rock Series of the Basal Cambrian, Guizhou Province: Discovery of Coarse-Grained Limestones and its Geochemical Characteristics

The molybdenum-nickel deposits in Shuidong District of Nayong County （Guizhou Province, Southwest China） are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich region besides Zunyi District （Guizhou province）. Our systematic study on the Mo-Ni deposits in Tangjiaba of Nayong reveals that layered coarse-grained limestones, spherical beaded limestones concretions are hosted at the lower seam of the Mo-Ni deposits. Its strong negative carbon isotope anomaly （the carbon isotope value of the coarse-grained limestones varies from -2.148‰ to 8.223‰） is similar to that in the modern submarine black smoker chimney. The carbon in the coarse-grained limestones from black rock series of Nayong County might be deep source inorganic carbon. The seams, coarse-grained limestones, ore-bearing coarse-grained limestones and the roof and floor of the deposits are characterized by co-variation on the trace element spider diagram, showing good homology. The extraordinary enrichment of Ag, As and Sb resembles hydrothermal sedimentation. Pro-Earth＇s core elements Se is strongly enriched in Ni-Mo ore-bearing coarse-grained limestones. The ore-bearing rock series has an extremely low Th/U value （0.012-0.19）; in the logU-logTh Cartesian Coordinates, the samples of the roof and floor of the deposits and ore-bearing coarse-grained limestones are found in the East Pacific tise; and the samples of coarse-grained limestones are found between the paleo-hydrothermal dedimentary area and the East Pacific tise. The chondrite-normalized rare earth element patterns of the Ni-Mo deposits show LREE enrichment, Ce negative anomaly, and Eu negative anomaly （which is supposed to be influenced by the deep magmatic processes in an extensional environment） resembles the rare earth element distribution patterns of the fluid and its sediments in modern submarine hydrothermal system. It proves that coarse-grained limestones is characterized by typical hydrothermal limestones, being closely related with the genesis of Mo-Ni deposits in Nayong County, which provides new evidence for hydrothermal sedimentary genesis of Mo-Ni deposit and negative carbon anomaly in the basal Cambrian on a global scale.

Effect of Limestone Powder and Fly Ash on Magnesium Sulfate Resistance of Mortar

The effect of limestone powder and fly ash on magnesium sulfate resistance of mortar was studied by testing on the strength, expansion and hydration products of the specimens stored in MgSO4 solution at certain periods. The experimental results show that the strength of mortar stored in MgSO4 solution increases a little before 28 d, but decreases fast subsequently. The more the contents of limestone powder and fly ash, the less the strength losses. Mortar swells in the MgSO4 solution with the soaking time. And the more the contents of limestone powder and fly ash, the less the expansion rate is. The expansion or strength loss of mortars results from the expansion of gypsum, as well as the loss of Ca（OH）2 and other hydration products of cement. The magnesium sulfate resistance of the mortars containing limestone powder and fly ash is high.