CO_(2) mineralization of carbide slag for the production of light calcium carbonates

The production of polyvinyl chloride by calcium carbide method is a typical chemical process with high coal consumption,leading to massive flue gas and carbide slag emissions.Currently,the carbide slag with high CaO content is usually stacked in residue field,easily draining away with the rain and corroding the soil.In this work,we coupled the treatment of flue gas and carbide slag to propose a facile CO_(2)mineralization route to prepare light calcium carbonate.And the route feasibility was comprehensively evaluated via experiments and simulation.Through experimental investigation,the Ca^(2+) leaching and mineralization reaction parameters were determined.Based on the experiment,a process was built and optimized through Aspen Plus,and the energy was integrated to obtain the overall process energy and material consumption.Finally,the net CO_(2)emission reduction rate of the entire process through the life-cycle assessment method was analyzed.Moreover,the relationship between the parameters and the CO_(2)emission life-cycle assessment was established.The final optimization results showed that the mineralization process required 1154.69 kW·h·(t CO_(2))^(-1) of energy(including heat energy of 979.32 kW·h·(t CO_(2))^(-1) and electrical energy of 175.37 kW·h·(t CO_(2))^(-1)),and the net CO_(2)emission reduction rate was 35.8%.The light CaCO_(3)product can be sold as a high value-added product.According to preliminary economic analysis,the profit of mineralizing can reach more than 2,100 CNY·(t CO_(2))^(-1).

Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

Stress sensitivity of permeability in high-permeability sandstone sealed with microbially-induced calcium carbonate precipitation

Microbially induced carbonate precipitation(MICP)catalyzed by S.pasteurii has attracted considerable attention as a bio-cement that can both strengthen and seal geomaterials.We investigate the stress sensitivity of permeability reduction for the initially high-permeability Berea sandstone(initial permeability∼110 mD)under various durations of MICP-grouting treatment.The results indicate that after 2,4,6,8 and 10 cycles of MICP-grouting,the permeabilities decrease incrementally by 87.9%,60.9%,38.8%,17.3%,and then 5.4%compared to the pre-grouting condition.With increasing the duration of MICP-grouting,the sensitivity of permeability to changes in stress gradually decreases and becomes less hysteretic.This stress sensitivity of permeability is well represented by a power-law relationship with the coefficients representing three contrasting phases:an initial slow reduction,followed by a rapid drop,culminating in an asymptotic response.This variation behavior is closely related to the movement and dislocation of the quartz framework,which is controlled by the intergranular bio-cementation strength.Imaging by scanning electron microscopy(SEM)reveals the evolution of the stress sensitivity to permeability associated with the evolving microstructures after MICP-grouting.The initial precipitates of CaCO3 are dispersed on the surfaces of the quartz framework and occupy the pore space,which is initially limited in controlling and reducing the displacement between particles.As the precipitates continuously accumulate,the intergranular slot-shaped pore spaces are initially bonded by bio-CaCO3,with the bonding strength progressively enhanced with the expanding volume of bio-cementation.At this stage,the intergranular movement and dislocation caused by compaction are reduced,and the stress sensitivity of the permeability is significantly reduced.As these slot-shaped pore spaces are progressively filled by the bio-cement,the movement and dislocation caused by compaction become negligible and thus the stress sensitivity of permeability is minimized.

Evolution Mechanism of Calcium Carbonate in Solution

Calcium carbonate was synthesized in a CaCl2/NaCO3 mixed solution by using ethylenediaminetetraacetic acid （EDTA） as an additive. The thermodynamics and kinetics analyses indicate that although the driving force of amorphous calcium carbonate （ACC） precipitation is always less than that of calcite and vaterite precipitation, the nucleation rate of ACC is greater than that of calcite and vaterite at the initial stage of the precipitation reaction. With the increasing incubation time, vaterite and calcite particles nucleate heterogeneously by using the as-formed particles as active sites. Scanning electron microscopy images indicate that the transformation mechanism of ACC and vaterite to calcite is the dissolution-recrystallisation reaction. The presence of EDTA not only improves the stabilities of ACC and vaterite, but also leads to forming enlongated, connected rhombohedral calcite crystals after incubation 7 days in solutions. The ACC and vaterite are stabler in air than in solutions at room temperature, although the dissolution-recrystallisation reaction occurs on the surface.

Surface modification of calcium carbonate:A review of theories,methods and applications

Calcium carbonate,which is widely employed as a filler added into the polymer matrix,has large numbers of applications owing to the excellent properties such as low cost,non-toxicity,high natural reserves and biocompatibility.Nevertheless,in order to obtain the good filling effect,calcium carbonate needs to be surface modified by organic molecules so as to enhance the dispersion and compatibility within the composites.This review paper systematically introduces the theory,methods,and applications progress of calcium carbonate with surface modification.Additionally,the key factors that affect the properties of the composites as well as the current difficulties and challenges are highlighted.The current research progress and potential application prospects of calcium carbonate in the fields of plastics,rubber,paper,medicine and environmental protection are discussed as well.Generally,this review can provide valuable reference for the modification and comprehensive utilization of calcium carbonate.

Preparation of calcium carbonate particles coated with titanium dioxide

The preparation of a new mineral composite material, calcium carbonate particles coated with titanium dioxide, was studied. The mechanism of the preparation process was proposed. The new mineral composite material was made by the mechanoehemieal method under the optimum condition that the mass ratio of calcium carbonate particles to titanium dioxide was 6.5：3.5. The mass ratios of two different types of titanium dioxide （anatase to rutile） and grinding media to grinded materials were 8：2 and 4：1 respectively, and the modified density was 60%. Under this condition, the new material was capable of forming after 120-min modification. The hiding power and oil absorption of this new material were 29.12 g/m^2 and 23.30%, respectively. The results show that the modification is based on surface hydroxylation. After coating with titanium dioxide, the hiding power of calcium carbonate can be improved greatly. The new mineral composite materials can be used as the substitute for titanium dioxide.

Preparation of poly （methyl methacrylate）／nanometer calcium carbonate composite by in-situ emulsion polymerization

Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.

Characterization of calcium deposition induced by Synechocystis sp. PCC6803 in BG11 culture medium

Calcium carbonate （CaCO3） crystals in their preferred orientation were obtained in BG11 culture media inoculated with Synechocystis sp. PCC6803 （inoculated BG11）. In this study, the features of calcium carbonate deposition were investigated. Inoculated BGll in different calcium ion concentrations was used for the experimental group, while the BGll culture medium was used for the control group. The surface morphologies of the calcium carbonate deposits in the experimental and control groups were determined by scanning and transmission electron microscopy. The deposits were analyzed by electronic probe micro-analysis, Fourier transform infrared spectrum, X-ray diffraction, thermal gravimetric analysis and differential scanning calorimetry. The results show that the surfaces of the crystals in the experimental group were hexahedral in a scaly pattern. The particle sizes were micrometer-sized and larger than those in the control group. The deposits of the control group contained calcium （Ca）, carbon （C）, oxygen （O）, phosphorus （P）, iron （Fe）, copper （Cu）, zinc （Zn）, and other elements. The deposits in the experimental group contained Ca, C, and O only. The deposits of both groups contained calcite. The thermal decomposition temperature of the deposits in the control group was lower than those in the experimental group. It showed that the CaCO3 deposits of the experimental group had higher thermal stability than those of the control group. This may be due to the secondary metabolites produced by the algae cells, which affect the carbonate crystal structure and result in a close-packed structure. The algae cells that remained after thermal weight loss were heavier in higher calcium concentrations in BGll culture media. There may be more calcium- containing crystals inside and outside of these cells. These results shall be beneficial for understanding the formation mechanism of carbonate minerals.

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

Experimental study on mitigating wind erosion of calcareous desert sand using spray method for microbially induced calcium carbonate precipitation

Wind erosion is one of the significant natural calamities worldwide, which degrades around one-third of global land. The eroded and suspended soil particles in the environment may cause health hazards, i.e.allergies and respiratory diseases, due to the presence of harmful contaminants, bacteria, and pollens.The present study evaluates the feasibility of microbially induced calcium carbonate precipitation(MICP)technique to mitigate wind-induced erosion of calcareous desert sand(Thar desert of Rajasthan province in India). The temperature during biotreatment was kept at 36℃ to stimulate the average temperature of the Thar desert. The spray method was used for bioaugmentation of Sporosarcina(S.) pasteurii and further treatment using chemical solutions. The chemical solution of 0.25 pore volume was sprayed continuously up to 5 d, 10 d, 15 d, and 20 d, using two different concentration ratios of urea and calcium chloride dihydrate viz 2:1 and 1:1. The biotreated samples were subjected to erosion testing(in the wind tunnel) at different wind speeds of 10 m/s, 20 m/s, and 30 m/s. The unconfined compressive strength of the biocemented crust was measured using a pocket penetrometer. The variation in calcite precipitation and microstructure(including the presence of crystalline minerals) of untreated as well as biotreated sand samples were determined through calcimeter, scanning electron microscope(SEM), and energydispersive X-ray spectroscope(EDX). The results demonstrated that the erosion of untreated sand increases with an increase in wind speeds. When compared to untreated sand, a lower erosion was observed in all biocemented sand samples, irrespective of treatment condition and wind speed. It was observed that the sample treated with 1:1 cementation solution for up to 5 d, was found to effectively resist erosion at a wind speed of 10 m/s. Moreover, a significant erosion resistance was ascertained in15 d and 20 d treated samples at higher wind speeds. The calcite content percentage, thickness of crust,bulk density, and surface strength of biocemented sand were enhanced with the increase in treatment duration. The 1:1 concentration ratio of cementation solution was found effective in improving crust thickness and surface strength as compared to 2:1 concentration ratio of cementation solution. The calcite crystals formation was observed in SEM analysis and calcium peaks were observed in EDX analysis for biotreated sand.

Distribution of Calcium Carbonate in the Process of Concrete Self-healing

The complete deposition distribution process of calcium carbonate is summarized in three directions of cracks. Distribution of calcium carbonate in the self-healing process of microbial concrete is studied in detail, with the help of a variety of analytical techniques. The results show that carbonate deposits along the x-axis direction of the cracks. The farther from the crack surfaces of concrete matrix in x-axis direction, the more the content of the substrate, the less content of calcium carbonate. Gradual accumulation of calcium carbonate along the y-axis direction is like building a house with bricks. Different repair points are gradually connected, and ultimately the whole of cracks are completely filled. In the z-axis direction, calcium deposits on the surface of fracture direction, when the crack is filled on the surface, because the internal crack hypoxia in the depths of cracks hardly produces calcium carbonate.

Mechanism of Calcium Carbonate Scale Deposition under Subcooled Flow Boiling Conditions

Fouling of heat transfer surfaces during subcooled flow boiling is a frequent engineering problem in process industries. It has been generally observed that the deposits in such industrial systems consist mainly of calcium carbonate （CaCO3）, which has inverse solubility characteristics. This investigation focused on the mechanism to control deposition and the morphology of crystalline deposits. A series of experiments were carried out at different surface and bulk temperatures, fluid velocities and salt ion concentrations. It is shown that the deposition rate is controlled by different mechanism in the range of experimental parameters, depending on salt ion concentration. At higher ion concentration, the fouling rate increases linearly with surface temperature and the effect of flow velocity on deposition rate is quite strong, suggesting that mass diffusion controls the fouling process. On the contrary, at lower ion concentration, the fouling rate increases exponentially with surface temperature and is independent of the velocity, illustrating that surface reaction controls the fouling process. By analysis of the morphology of scale, two types of crystal （calcite and aragonite） are formed. The lower the temperature and ion concentration, the longer the induction period and the higher the percentage of calcite nreciDitated.

Formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate by adding CaCO3

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate(VTC)by adding CaCO3 was investigated.Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and Ca CO3 in a reductive atmosphere,where ilmenite is more easily reduced by CO or carbon in the presence of CaCO3.The effects of CaCO3 dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test.Appropriate increase of CaCO3 dosages and reduction temperatures were found to be conducive to the formation of calcium titanate,and the optimum conditions were a CaCO3 dosage of 18 wt%and a reduction temperature of 1400°C.Additionally,scanning electron microscopy–energy dispersive spectrometry(SEM–EDS)analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO3 addition was of higher purity with particle size approximately 50μm.Hence,the separation of calcium titanate and metallic iron will be the focus in the future study.

Characteristics of Soybean Urease Mineralized Calcium Carbonate and Repair of Concrete Surface Damage

The C60 concrete blocks with surface crack damage under high temperature environment were soaked by adding appropriate amount of soybean urease into the CO(NH_(2))_(2)-CaCl_(2) solution,the soybean urease mineralized calcium carbonate were characterized,and the effect of repairing concrete surface crack damage were evaluated by the surface sedimentation of C60 concrete blocks in the study.The experimental results showed that the activity of soybean powder was statistically significant,and its productivity of urease was comparable with that of urease-producing bacteria.After immersion in a soybean solution,a layer of complete and continuous white sediment covered the concrete surface.The cracks on the concrete surface were completely shielded,and the rising temperature on infrared thermal image of the concrete after repair was lower than before.Besides,through analysis by SEM,EDS,and XRD,the products formed after repair were found to be calcite-type CaCO_(3) with high purity,and the crystals exhibited different morphological features.The above results indicate that soybean urease can regulate and induce the formation of calcium carbonate,and the precipitate is innocuous and harmless,suitable for a new type of concrete crack repair material.

Biomediated Precipitation of Calcium Carbonate in a Slightly Acidic Hot Spring,Yunnan Province

A slightly acidic hot spring named ＂Female Tower＂（t=73.5°C, pH=6.64） is located in the Jifei Geothermal Field, Yunnan Province, southwestern China. The precipitates in the hot spring are composed of large amounts of calcite, aragonite and sulfur. Scanning electron microscopy（SEM） analyses reveal that the microbial mats were formed from various coccoid or rod-shaped filamentous microbes. Transmission electron microscopy（TEM） shows that the intracellular sulfur granules are commonly associated with these microbes. A culture-independent molecular phylogenetic analysis demonstrates that the majority of the bacteria in the spring are sulfur-oxidizing bacteria. In the spring water, H2S concentration is up to 60 ppm, while SO4-（2-） concentration is only about 10 ppm. We speculate that H2S might derive from sulfur-oxidizing bacteria in this hot spring water, leading to the intracellular formation of sulfur granules. Meanwhile, this reaction increased the p H in the micronscale microdomains, which fosters the precipitation of calcium carbonate in the microbial mats. The results of this study indicate that the sulfur-oxidizing bacteria might play an important role in calcium carbonate precipitation in slightly acidic hot spring environments.

Effects of Nano Calcium Carbonate on Strength and Microstructure of Corundum-based Castables

The castables specimens were prepared using white fused alumina particle and powder, α-Al2O3 micropowder, hydrated alumina, nano calcium carbonate or calcium aluminate cement as starting materials. Effects of nano calcium carbonate addition on phase compositions, strength and microstructure of corundum based castables were studied. The calcium aluminate cement-containing corundum based castables with the same CaO amount was also tested for comparison. The results show that, when temperature is higher than 900 ℃ , the phase compositions of nano CaCO3-containing mixture and the calcium aluminate cement containing mixture are the same, but the forming mechanism, modality and distribution of new phases in the castables are different. With temperature rising, the hydration cement dehydrates and reacts inside cement forming calcium aluminate until the alumina in cement is not enough for the reaction （ternperature is 91 400 ℃ ） , then reacts with the surrounding alumina forming cluster CA6 in the castables. The change process of nano CaCO3 in corundum based enstables is that nano calcium carbonate decomposes to CaO after firing at 800℃ which reacts with Al2O3 forming amorphous calcium aluminate that causes an in-situ bonding. With temperature rising, the formed calcium aluminate reacts with Al2O3 in matrix and wholly forms tabular CA6 at 1 600 ℃ , which distributes uniformly in the castables. The cold and hot strength of the castables with nano calcium carbonate are obviously higher than those of the castables without nano calcium carbonate, especially at 800 -1 000 ℃ due to smaller size and higher dispersion of the nano calcium carbonate and its different reaction mechanism with Al2O3.

Preparation of CaO-containing carbon pellets from coking coal and calcium oxide:Effects of temperature,pore distribution and carbon structure on compressive strength in pyrolysis furnace

CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350-750℃).The results showed that as the roasting temperature increased,the compressive strength also increased and furthermore,structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures,thus forming high-ordered CC.Notably,the CCCP preheated at 750℃exhibited the highest compressive strength.A positive relationship between the compressive strength and pore-size homogeneity was established.A linear relationship between the com-pressive strength of the CCCP and the average stack height of CC was observed.Additionally,a four-stage caking mechanism was developed.

Regulation of Microstructure of Calcium Carbonate Crystals by Egg White Protein

Crystal growth of calcium carbonate in biological simulation was investigated via egg white protein with different volume fractions,during which calcium carbonate was synthesized by calcium chloride and sodium carbonate.The morphology,thermal properties and microstructure of the calcium carbonate micro-to-nanoscale crystals were characterized by scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,Fourier transform infrared spectroscopy（FTIR）,thermogravimetric analysis（TG） and X-ray diffraction（XRD） analysis.The results show that the volume fraction of egg white protein has great influence on the shape,size and morphology of calcium carbonate crystals.The calcium carbonate crystals were the mixtures of calcite-vaterite-like crystals including spherical and rough surface,which are different from that formed in pure water.With the increase of egg white protein concentration,the diameter of calcium carbonate crystals changed,the amount of formed spherical calcium carbonate particles decreased and that of vaterite increased.These results indicate that the coordination and electrostatic interaction between egg white protein and Ca2＋ significantly affect the calcium carbonate crystalization.

Effects of Copper-Zinc Alloy Doped with Rare Earth Elements on Crystal of Calcium Carbonate

A copper-zinc alloy doped with rare earth elements was prepared and the mechanism was demonstrated in a simulating boiler and circulating cooling water with rigidity 1 mmol·L-1. The polar curve and scale inhibiting ability of the alloy was tested by a corrosion measurement system and a scale inhibition evaluation system, respectively. Scale samples were characterized with SEM and XRD. It is found that the transfer of cations could be promoted by doping with proper rare earth elements, and the corrosion potentials descend by 25～126 mV. The results indicated that the copper-zinc alloy doped with rare earth elements has higher scale inhibiting ability of CaCO3. The growth of calcite was affected by zinc ions dissolved because of primary battery reaction, and the transition of calcium carbonate from aragonite to calcite was hampered resulting in the proportion of aragonite to calcite is changed from 1.7∶1 to 2.7∶1.

Modification of nanometer calcium carbonate for water-borne architectural coatings

A kind of modifier was synthesized to modify the surface of nanometer calcium carbonate （abbreviated as nano-CaCO3）, which is used in architectural coatings. The modification technology of the nano-CaCO3 was studied through orthogonal experimental methods. The factors studied were rotation speed, modifier dosage, emulsification temperature, emulsification time and heat aging time after emulsification. Optimized conditions for modification of the surface were： rotation speed 16000 r/min; modifier dosage 3%; emulsification temperature 75 ℃; emulsification time 60 min and aging time 40 min. The modified nano-CaCO3 was also studied by size-distribution measurements, transmission electron microscopy, infrared spectroscopy and thermal analysis. The results show that the size distribution of the modified nano-CaCO3 is uniform and that there are chemi-sorption and physi-sorption between the nano-CaCO3 and the modifier. Compared to traditional architectural coatings without nano-CaCO3, the nanometer composite coatings are obviously improved in respect to dirt resistance, scrub resistance, thixotropy, water resistance, alkalinity resistance and aging resistance.