Crystallization of Nano‐Calcium Carbonate: The Influence of Process Parameters

Precipitated calcium carbonate was synthesized by carbonation of calcium hydroxide in the presence and absence of ultrasound (conventional stirring) at atmospheric as well as at elevated pressures and different initial concentrations of Ca(OH)₂. Spherical morphology of the formed calcite was favored at high Ca(OH)₂ concentrations and low CO₂ pressures. The presence of ultrasound did not show any influence on the reaction rate in case of efficient mixing. A small increase of the reaction rate was observed at lower CO₂ pressures. Elevated pressures in combination with ultrasound did not lead to notable changes of reaction rate or particle morphology.     

A theory of the formation of magnesium scales in sea water distillation plants,and means for their prevention

Some additives, which retard the formation of alkaline scale from sea water at temperatures up to 230°F, delay the precipitation of calcium carbonate but have no effect on the precipitation of magnesium hydroxide.Boiling aqueous solutions containing magnesium and bicarbonate ions or calcium/magnesium and bicarbonate ions produce an initial deposit of hydromagnesite (3MgCO₃·Mg(OH)₂·3H₂O) which converts on further heating to magnesium hydroxide. It is proposed that additives, to control magnesium scale formation, have to affect this intermediate.Crystals of calcite and hydromagnesite, produced in the presence of an additive which is effective in preventing alkaline scale formation, show marked distortion, tending to make the crystals larger and less regular in shape.     

Effects of humidity on calcite block fabrication using calcium hydroxide compact

Calcite has attracted attention as an artificial bone replacement material and as a precursor for the fabrication of carbonate apatite, which is also an artificial bone replacement material. In this study, the effect of humidity on calcite block fabrication was investigated using calcium hydroxide (Ca(OH)₂) compact. Ca(OH)₂ compact and Ca(OH)₂ paste compact were exposed to CO₂ at room temperature under 0%, 50%, and 100% humidity for two weeks. No carbonation was observed when Ca(OH)₂ compact was exposed to CO₂ under 0% humidity. In contrast, Ca(OH)₂ compact transformed into pure calcite under 100% humidity. Forty percent of the Ca(OH)₂ compact transformed into calcite under 50% humidity, while 30% of the Ca(OH)₂ paste compact transformed into calcite. Interestingly, the diametral tensile strength of the Ca(OH)₂ paste compact was four times higher than that of the Ca(OH)₂ compact when both were exposed to CO₂ under 100% humidity, despite the paste compact׳s lower conversion into apatite. After exposure to CO₂, SEM observations revealed that in the case of the paste compact, the Ca(OH)₂ powder was bridged with a precipitate, whereas in the case of Ca(OH)₂ compact, no precipitate was found. Results obtained in this study demonstrated that carbonation of the Ca(OH)₂ compact at room temperature was the result of a dissolution–precipitation reaction. Ca(OH)₂ powder was dissolved into water to supply the Ca²⁺, and CO₃²⁻ was supplied for the calcite precipitation from the interaction of CO₂ and water. Excess humidity from the paste compact was the key to the precipitation of the calcite bridge. The presence of the calcite bridge resulted in a higher mechanical strength for the calcite block.     

Tensile properties of polypropylene flame-retardant composites

The polypropylene (PP) flame-retardant composites filled with aluminum hydroxide (Al(OH)₃), magnesium hydroxide (Mg(OH)₂), zinc borate (ZB), nanometer calcium carbonate (nano-CaCO₃), and polyolefin elastomer (POE) were prepared using a twin-screw extruder, and the tensile properties were measured at room temperature by means of an electronic universal test machine (Model CMT4104) in this paper, to identify the influence of the flame-retardant content on the tensile properties. The results showed that the tensile strength decreased roughly nonlinearly while the tensile elongation at break decreased nonlinearly with increasing the flame-retardant weight fraction. The Young’s modulus and the tensile fracture strength increased nonlinearly with an addition of the flame-retardant weight fraction. The tensile ductility of PP/Al(OH)₃/Mg(OH)₂/ZB/Nano-CaCO₃/POE composite was the best in the three kinds of the composite systems. Moreover, good agreement was showed between the predictions and the measurements of the tensile strength.     

Rapid Carbonation for Calcite from a Solid-Liquid-Gas System with an Imidazolium-Based Ionic Liquid

Aqueous carbonation of Ca(OH)₂ is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO₂ in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO₂ with Ca(OH)₂. The use of the IL increased the solubility of CO₂ in the aqueous environment and enhanced the transport of the reactive species (Ca²⁺ and CO₃²⁻) and products. The presence of the IL also avoided the formation of the CaCO₃ protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time.     

Synthesis of pure aragonite by sonochemical mineral carbonation

The objective of this work was to promote the formation of the aragonite polymorph of calcium carbonate, which has some valuable applications in industry, via the mineral carbonation route. The combination of ultrasound with magnesium ions promoted the formation of pure aragonite crystals at optimum conditions. It was possible to synthesize high purity aragonite precipitates at temperatures ranging from 24 °C to 70 °C, with the resulting powders possessing varying particle size distributions (from sub-micron up to 20 μm) and crystal morphologies (from acicular needles to novel hubbard squash-like particles). Several process parameters were found to influence the produced calcium carbonate polymorph ratios (aragonite over calcite). Higher values of magnesium-to-calcium ratio, intermediate ultrasound amplitude (60%), continuous ultrasound application (100% cycle), introduction of ultrasound pre-breakage, lowering of the CO₂ flow rate, and increase in the relative concentration (g/L Ca(OH)₂), all promoted aragonite formation. A potential route for industrial production of this material has been identified via a fed-batch process, which effectively reutilizes magnesium chloride while maintaining high aragonite yield. The results presented herein are significantly superior to aragonite formation using only single promoting techniques, typically found in literature, and go beyond by focusing on pure (>99%) aragonite formation.     

Propylene polymerization by using TiCl4 catalyst supported on solvent‐activated Mg(OEt)2

Solvent activation of Mg(OEt)₂ in ethanol with carbon dioxide was carried out in a 1‐L three‐neck flask under nitrogen atmosphere, to investigate structural changes of Mg(OEt)₂ support. During activation of Mg(OEt)₂ by ethanol and CO₂, a suspension mixture was converted to a clear solution and CO₂ was inserted into the Mg? O bond of Mg(OEt)₂, to form magnesium ethyl carbonate. The solid supports were obtained from the removal of solvents by heating, during which CO₂ split off from the magnesium ethyl carbonate between 100 and 150°C. The structural changes of the obtained supports and the corresponding catalysts were checked by IR and TGA. The polymerization behavior of propylene with the catalyst and morphology of the obtained polymer were also examined. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 460–467, 2001     

Experimental design approach to calcium carbonate precipitation in a semicontinuous process

The production of precipitated calcium carbonate, PCC, by a semicontinuous process of slaked lime carbonation was performed in a bench-scale chemical reactor, fully controlled by means of custom built electronics and software for the personal computer. Calcite crystals, with different characteristic morphologies (rhombohedral, truncated prismatic, scalenohedral, spheroidal or chain-like agglomerates) were produced by varying a range of process parameters, like temperature, supersaturation, gas mixture flow rate, stirring rate and mass concentration of Ca(OH)₂ suspension. In order to identify the effects of the chosen process parameters on the PCC morphology and on the related specific surface area, as well as on the extent of CO₂ conversion, an empirical approach based on the experimental design techniques was employed. A multiple correlation analysis of the obtained data suggests that temperature and conductivity significantly influence the PCC morphology, while CO₂ conversion is principally influenced by stirring rate, conductivity and gas mixture flow rate.     

Immobilization of metal-containing waste in alkali-activated lime-RHA cementitious matrices

This research investigated the immobilization potential of alkali-activated lime-rice husk ash (RHA) for synthetic Cr(OH)₃, Fe(OH)₃, Zn(OH)₂ and zinc cyanide plating sludge. The binder consists of hydrated lime and RHA at a weight ratio of 45:55. Waterglass (Na₂SiO₃) with SiO₂/Na₂O ≈ 3 and anhydrous sodium carbonate (Na₂CO₃) were used as alkali activator between 0 and 8 wt.% of the binder. Results showed that Zn(OH)₂ addition causes a considerable strength development in control and sodium silicate-activated samples but only after 14 days. Similar observations were found for the sample loaded with 10 wt.% plating sludge but this only occurred after 28 days. A possible explanation for these phenomena is that the initial formation of calcium zincate, which has a set retarding effect, inhibits early strength development. At later ages, calcium zincate dissolves and Zn is taken up in the formation of C-S-Z-H solid solutions leading to strength development. These phenomena were not observed from the sodium carbonate-activated lime-RHA matrices. In these, it is believed that zinc/calcium carbonates readily form inhibiting calcium zincate and C-S-Z-H formation. Despite this, carbonate-containing mixes with up to 30 wt.% plating sludge gave a 14-day strength and Cr concentration in TCLP leachate that meet the regulatory limit for landfilling.     

Effect of cation exchange on the distribution and movement of cations in soils with variable charge. I. Effect of lime on potassium and magnesium exchange equilibria

The influence of Ca(OH)₂ on K and Mg exchange equilibria in three New Zealand soils was studied. Calcium hydroxide was mixed with each soil to raise the pH to about 6 or 7. For each Ca(OH)₂ treatment, K and Mg exchange isotherms were determined, from which the equilibrium activity ratios were derived. Exchange coefficients and solution activity ratios were calculated according to the Gapon convention.The addition of Ca(OH)₂ produced varying effects in the Gapon exchange coefficient for both K and Mg. The magnitude and direction of change in the exchange coefficient were related to the cation initially dominating the exchange sites, rate of Ca(OH)₂ addition, soil colloids contributing to the CEC and specific interactions of Ca with these soil colloids.Addition of Ca(OH)₂ reduced the equilibrium activity ratio of all soils. Changes in the bonding strength of K and Mg with increasing CEC were suggested as a possible mechanism for this decrease.     

Formation of organic-inorganic composite materials based on cellulose <Emphasis Type="Italic">Acetobacter xylinum</Emphasis> and calcium phosphates for medical applications

The formation of composites based on the cellulose Acetobacter xylinum and calcium phosphates has been investigated using X-ray diffraction, electron diffraction, electron microscopy, energy-dispersive analysis, and differential scanning calorimetry. It has been demonstrated that the planar morphology of calcium phosphate nanoparticles capable of interacting with nanofibrils of the cellulose matrix is an important factor providing interfacial contacts in the formation of organic-inorganic composite materials. It has been established that magnesium-containing calcium phosphates represent two-phase systems consisting of calcium magnesium phosphate Ca_2.6Mg_0.4(PO₄)₂ (whitlockite) and hydroxyapatite Ca₅(PO₄)₃(OH). The biocompatibility of the composite materials based on two-phase calcium phosphate systems and the temperature range of their stability (∼20–250°C) determined by the thermal stability of the organic component have been investigated.     

Preparation of nanoparticles with a semi-batch gas-liquid membrane contactor

Nanosized calcium carbonate particles were prepared with a semi-batch gas-liquid membrane contactor. A mathematical model of the semi-batch operated contactor was given, and the effects of Ca(OH)₂ concentration, CO₂ partial pressure and additives on the absorption rate were estimated theoretically. The predicted data were consistent with the experimental results. The Ca(OH)₂ concentration and CO₂ pressure have no apparent effects on the particles. In the presence of PVP and PEG, the particles are well-dispersed and the size is effectively reduced. After reaction, the membranes were washed with dilute hydrochloric acid and the membranes can be reused for at least 9 times without apparent performance deterioration.     

Use of gypsum/brucite mixed precipitate instead of gypsum in Portland cement

The possibility of replacing the natural gypsum used in cement production by a chemical precipitate consisting of gypsum (CaSO₄ ·2H₂O) and brucite (Mg(OH)₂), was investigated. This precipitate is a by‐product of a new hydrometallurgical process, which was developed in order to treat economically low‐grade nickel oxide ores. More specifically, it is obtained by hydrolytic precipitation of magnesium at temperatures not exceeding 80 °C, from sulfate solutions which result from heap leaching of nickel oxide ores with dilute sulfuric acid at ambient temperature, using calcium hydroxide as a neutralizing agent. The mixture generally consists of 20–30% non‐fibrous magnesium hydroxide, 60–75% gypsum and any excess of calcium hydroxide, depending on the precipitation conditions. In the present work, a mixture was produced by hydrolytic precipitation at 25 °C, using 1.1 times the stoichiometric quantity of Ca(OH)₂ required to precipitate all of the magnesium. The possibility of using the above precipitate as a substitute for gypsum in cement was examined by testing four different cement mixtures, one reference sample, containing 4.5% gypsum and 0.5% anhydrite ((PC)_Ref) and another three with 4.1%, 5.2% and 6.3% of gypsum/brucite mixed precipitate ((PC)_B/G), in the place of gypsum. All samples were tested by determining the grindability, setting time, expansion and compressive strength. The results of the physico‐mechanical tests showed that the replacement of natural gypsum by the above precipitate did not affect negatively the quality of the produced cements. Copyright © 2005 Society of Chemical Industry     

Indirect mineral carbonation of titanium-bearing blast furnace slag coupled with recovery of TiO2 and Al2O3

Large quantities of CO_2 and blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial CO_2 emission reduction and comprehensive utilization of the solid waste.This paper describes a novel route for indirect mineral carbonation of titanium-bearing blast furnace(TBBF) slag,in which the TBBF slag is roasted with recyclable(NH_4)_2SO_4(AS) at low temperatures and converted into the sulphates of various valuable metals, including calcium, magnesium, aluminium and titanium. High value added Ti-and Al-rich products can be obtained through stepwise precipitation of the leaching solution from the roasted slag. The NH_3 produced during the roasting is used to capture CO_2 from flue gases. The NH_4HCO_3 and(NH_4)_2CO_3 thus obtained are used to carbonate the CaSO_4-containing leaching residue and MgSO_4-rich leaching solution, respectively. In this study, the process parameters and efficiency for the roasting, carbonation and Ti and Al recovery were investigated in detail. The results showed that the sulfation ratios of calcium,magnesium, titanium and aluminium reached 92.6%, 87% and 84.4%, respectively, after roasting at an AS-to-TBBF slag mass ratio of 2:1 and 350 °C for 2 h. The leaching solution was subjected to hydrolysis at 102 °C for 4 h with a Ti hydrolysis ratio of 95.7% and the purity of TiO_2 in the calcined hydrolysate reached 98 wt%.99.7% of aluminium in the Ti-depleted leaching solution was precipitated by using NH_3. The carbonation products of Ca and Mg were CaCO_3 and(NH_4)_2 Mg(CO_3)_2·4H_2O, respectively. The latter can be decomposed into MgCO_3 at 100–200 °C with simultaneous recovery of the NH_3 for reuse. In this process, approximately 82.1% of Ca and 84.2%of Mg in the TBBF slag were transformed into stable carbonates and the total CO_2 sequestration capacity per ton of TBBF slag reached up to 239.7 kg. The TiO_2 obtained can be used directly as an end product, while the Al-rich precipitate and the two carbonation products can act, respectively, as raw materials for electrolytic aluminium,cement and light magnesium carbonate production for the replacement of natural resources.     

A breakthrough technique for the preparation of high-yield precipitated calcium carbonate

Precipitated calcium carbonate (PCC) is conventionally produced through the gas-solid-liquid carbonation route, which consists on bubbling gaseous CO₂ through a concentrated calcium hydroxide (Ca(OH)₂) slurry. However, atmospheric carbonation processes are slow and have low carbonation efficiency. A novel technology based on the combination of supercritical carbon dioxide (scCO₂) and ultrasonic agitation is described here for the preparation of high-yield PCC. The combination of both techniques has demonstrated to produce outstanding improvement for the conversion of Ca(OH)₂ to the stable calcite polymorph of calcium carbonate (CaCO₃). These experiments were carried out at 313 K and 13 MPa using a high-pressure reactor immersed in an ultrasounds cleaner bath. The process kinetics and the characteristics of the precipitated particles using ultrasonic agitation were compared with those obtained under similar experimental conditions using mechanical stirring and non-agitated systems. The crystal characteristics of the samples obtained using the three different agitation techniques were characterized by X-ray diffraction and scanning electron microscopy.     

Mechanical properties of Mg(OH)2/polypropylene composites modified by functionalized polypropylene

Modified Mg(OH)₂/polypropylene (PP) composites were prepared by the addition of functionalized polypropylene (FPP); and acrylic acid (AA) and by the formation of in situ FPP. The effects of the addition of FPP and AA and the formation of in situ FPP on the mechanical properties of Mg(OH)₂/PP composites were investigated. Experimental results indicated that the addition of Mg(OH)₂ markedly reduced the mechanical properties of PP. The extent of reduction in notch impact strength of PP was higher than that in flexural strength and tensile strength. However, tensile modulus and flexural modulus increased with increased Mg(OH)₂ content. The addition of FPP facilitated the improvement in the flexural strength and tensile strength of Mg(OH)₂/PP composites. The higher the Mg(OH)₂ content was, the more significant the effect of FPP was. The incorporation of AA resulted in further increased mechanical properties, in particular the flexural strength, tensile strength, and notch impact strength of Mg(OH)₂/PP composites containing high levels of Mg(OH)₂. It not only improved mechanical properties but also increased the flame retardance of Mg(OH)₂/PP composites. Although the mechanical properties of composites modified by the formation of in situ FPP were lower than those of composites modified by only the addition of AA in the absence of diamylperoxide, the mechanical properties did not decline with increased Mg(OH)₂ content. Moreover, the mechanical properties increased with increasing AA content. The addition of an oxidation resistant did not influence the mechanical properties of the modified Mg(OH)₂/PP composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2139–2147, 2003     

Control of corrosive water in advanced water treatment plant by manipulating calcium carbonate precipitation potential

The corrosion of metal pipes in water distribution networks is a complex electrochemical and physicochemical phenomenon between a metal surface and corrosive water. The level of corrosion in water distribution systems was controlled by manipulating the calcium carbonate precipitation potential (CCPP) concentration, and the corrosive water quality was controlled in two steps within the advanced water treatment plant (AWTP) constructed at the Institute of Water Quality Research (IWQR), Busan Metropolitan City, Korea. The 1 ^st control step was located before a coagulation process included on a rapid mixer, and the 2 ^nd control step was located after a biological activated carbon (BAC) process. The capacity of the AWTP in IWQR was 80 m³/day. The CCPP concentration was controlled from the calcium hardness, alkalinity, and pH by adding calcium hydroxide (Ca(OH)₂), sodium carbonate (Na₂CO₃), and carbon dioxide (CO₂) in the above two steps. A CCPP control system was installed and operated according to the developed algorithm to maintain a CCPP range of 0–4 mg/L. The CCPP range was reasonably controlled to induce the formation of a CaCO₃ film on the surface of the simulated water distribution system (SWDS). From the result of the corrosive water control, the CCPP formed greater than 0.0 mg/L. The crystalloid structure of the scale produced by CCPP control in the inner surface of pipe was zinc carbonate hydroxide hydrate (Zn₄CO₃(OH)₆·H₂O).     

Influence of precursors of Li2O and MgO on surface and catalytic properties of Li‐promoted MgO in oxidative coupling of methane

The influence of the catalyst precursors (for Li₂O and MgO) used in the preparation of Li‐doped MgO (Li/Mg = 0.1) on its surface properties (viz basicity, CO₂ content and surface area) and activity/selectivity in the oxidative coupling of methane (OCM) process at 650–750 °C (CH₄/O₂ feed ratio = 3.0–8.0 and space velocity = 5140–20550 cm³ g⁻¹ h⁻¹) has been investigated. The surface and catalytic properties are found to be strongly affected by the precursor for Li₂O (viz lithium nitrate, lithium ethanoate and lithium carbonate) and MgO (viz magnesium nitrate, magnesium hydroxide prepared by different methods, magnesium carbonate, magnesium oxide and magnesium ethanoate). Among the Li–MgO (Li/MgO = 0.1) catalysts, the Li–MgO catalyst prepared using lithium carbonate and magnesium hydroxide (prepared by the precipitation from magnesium sulfate by ammonia solution) and lithium ethanoate and magnesium acetate shows high surface area and basicity, respectively. The catalysts prepared using lithium ethanoate and magnesium ethanoate, and lithium nitrate and magnesium nitrate have very high and almost no CO₂ contents, respectively. The catalysts prepared using lithium ethanoate or carbonate as precursor for Li₂O, and magnesium carbonate or ethanoate, as precursor for MgO, showed a good and comparable performance in the OCM process. The performance of the other catalysts was inferior. No direct relationship between the basicity of Li‐doped MgO or surface area and its catalytic activity/selectivity in the OCM process was, however, observed. © 2000 Society of Chemical Industry     

Improving the Yield of Sonochemical Precipitated Aragonite Synthesis by Scaling up Intensified Conditions

Precipitated aragonite can be synthesized at relatively low temperatures by combining the application of low-frequency sonication with the use of magnesium chloride additive, as demonstrated by our prior study. In the present study, new process conditions were found that promote aragonite formation while accelerating and increasing the reaction yield. It was found that Mg-to-Ca molar ratio of 3:1, together with higher slurry concentration (74 g/L Ca(OH)₂) and higher power-to-volume ratio (800 W/L gross, achieved by reducing slurry volume), promoted the aragonite formation while working at a higher CO₂ flow rate (2.0 NL/min), and consequently higher precipitated calcium carbonate production rate (1 g/(L · min) CaCO₃). The yield was thus improved while conserving the desired product properties as follows: high polymorph purity (95.7 wt%), small and narrow particle size distribution (D[3,2] = 0.74 µm), and unique shape (hubbard squash-like).