A Trend to the Production of Calcium Hydroxide and Precipitated Calcium Carbonate with Defined Properties

In this paper, production of precipitated calcium carbonate (PCC) with required particle size and morphological structure, along with its dependence on technological parameters and the properties of Ca(OH)₂, is discussed. The effect of the reaction environment on the kinetics of CaO hydration and the formation of crystals in water suspension was established. A remarkable difference in the system's restoration ability after stirring was observed. The hydration process is initially controlled by a kinetic mechanism, followed by a diffusion‐controlled process. The dissolution speed of lime hydrated to suspension is eight times higher than that of lime hydrated to powder. Particles of hydrated lime appeared in various forms.     

Study on the replacement of the hydrated lime by kaolinitic clay in mortars

ABSTRACT

Mortars are cement-based materials used mainly to coat and settle construction blocks. In addition to cement, their composition usually includes hydrated lime, sand, and water. The hydrated lime is important to improve the mortar workability. However, lime has a high commercial cost, and its production causes emission of CO₂, a major responsible for global warming. Therefore, the purpose of this work was to investigate the possibility of total or partial replacement of hydrated lime in mortars by a kaolinitic clay with ideal plasticity parameters. Clay amounts of 0, 25, 50, 75, and 100?wt-% were used as replacement of hydrated lime in mortars. The results showed that with up to 50?wt-% of hydrated lime replacement, it is perfectly feasible to fulfil with technological parameters of standards.     

Stabilization of PCC dispersions prepared directly in the mother-liquid after synthesis through the carbonation of (hydrated) lime

Various CaCO₃-based products are often used in the form of concentrated aqueous dispersions. This study investigates the stabilization of PCC dispersions prepared directly in the mother-liquid after the carbonation of (hydrated) lime through the adsorption of a commercial sodium polyacrylate dispersant. The results demonstrate that the composition of the mother-liquid, particularly the Ca²⁺ activity, profoundly influences virtually all processes pertinent to dispersion stabilization—from the initial charging of the CaCO₃ surface in base PCC dispersions, to the surface charge regulation and dispersion stabilization efficiency of the polyacrylate dispersing agent. Rising prominence of the counterion condensation effects in Ca²⁺ rich solutions limits the conditions conducive to the surface charge regulation through dispersant adsorption to an optimum pH range of about 8-11. Furthermore, dispersion stability analysis, based on the classical DLVO theory of colloid stability, and corroborated by experimental evidence in the form of particle size distribution analyses, also indicates that optimum stability conditions for such PCC dispersions are established with small dispersant doses (0.25-0.5% per dry weight) in the pH range of about 9-11.     

Decolorization and COD reduction of disperse and reactive dyes wastewater using chemical-coagulation followed by sequential batch reactor (SBR) process

This paper summarizes the results of disperse and reactive dyes wastewater treatment processes aiming at the destruction of the wastewater's color and chemical oxygen demand (COD) reduction by means of coagulation/flocculation (CF) followed by sequential batch reactor (SBR) process. The color removal efficiency of magnesium chloride aided with lime [MgCl₂/CaO] was compared with that of alum [Al₂ (SO₄)₃] and lime [Cao]. The experimental results showed that treatment with lime alone (600 mg/l) at pH value of 11.7 proved to be very effective. Color removal reached 100% and COD was reduced by 50%. Treatment with magnesium chloride aided with lime at pH value of 11 removed color completely and reduced the COD value by 40%. However, lime or lime in combination with magnesium chloride produced high amounts of sludge (1.84 kg/m³ for lime & 1.71 kg/m³ for MgCl₂ aided with lime). Also, the pH of the treated effluent was around 11 and needs correction prior to discharge into sewer network. The use of 200 mg/l alum without pH adjustment removed 78.9% of the color. To improve the effectiveness of alum, the cationic polymer namely cytec was used as a coagulant aid. This significantly increased color removal from 78.9 up to 94% and COD reduction was around 44%. Moreover, sludge production was only 0.36 kg/m³. Chemically pre-treated effluent was subjected to SBR process at an HRT of 5.0 h. Residual COD_total, total biochemical oxygen demand (BOD_{5 total}) and total suspended solids (TSS) in the final effluent were 78 ± 7.7; 28 ± 4.2 and 17 ± 4.2 mg/l, corresponding to the removal efficiency of 68.2; 76.3 and 61.4% respectively. Furthermore, almost complete removal of COD_particulate and BOD_5particulate has been achieved.     

Charged Membrane Ultrafiltration of Multisalt Systems: Application to Acid Mine Waters

Abstract

Ultrafiltration of dissolved and precipitated inorganic salts from synthetic and actual acid mine waters is investigated experimentally in a bench-scale, continuous-flow unit, utilizing negatively charged, noncellulosic membranes. The process is evaluated in terms of the simultaneous achievement of good water flux without membrane fouling and of adequate ultrafiltrate quality at high water recovery for water reuse operation. At a transmembrane pressure of 5.6 X 10⁵ N/m² and a channel Reynolds number of 6,000, the flux drop is less than 30%, even with a concentrated acid mine water containing 16,000 mg/1 total solids and a high CaSO₄ concentration. At 90% ultrafiltrate recovery, depending on the type of noncellulosic membrane utilized, 98% iron removal, 85% aluminum removal, and 50 to 73% calcium and manganese removals can be obtained at an average water flux from 6.4X10^?4 to 13.2X10^?4 cm/sec. The overall ultrafiltrate quality is considerably better than that observed with a lime precipitation process.     

Preparation of environmental-friendly lime paints from hydrated lime and hydrated light burned dolomite

Environment-friendly lime paints were prepared from 38 wt% slurries of hydrated lime (Ca(OH)₂) and hydrated light burned dolomite (Ca(OH)₂·Mg(OH)₂). These materials and the resulting paints?? antibacterial and antimold properties were investigated. The hydrated lime used in this study contained 97 wt% Ca(OH)₂, which implies a 71.85 wt% equivalence of CaO. This 71.85 wt% CaO content was responsible for the antibacterial and anti-mold characteristics. The antibacterial and anti-mold characteristics of the hydrated light burned dolomite were attributed to its 56 wt% CaO and 44 wt% MgO contents. The antibacterial-reducing activities of 38 wt% hydrated lime and hydrated light burned dolomite slurries were found to be 99%. Their anti-mold activities against mixed strains were outstanding. Lime paints produced from the slurries and various additives also showed 99% antibacterial activity and outstanding anti-mold activity. The paints?? low total volatile organic compounds (TVOCs) releases were graded as excellent. Their formaldehyde (HCHO) releases were classed as best through excellent, indicating their suitability as environment-friendly building materials.     

废浆零排放的石灰－烟道气卤水净化新工艺

首先指出了目前石灰-烟道气卤水净化工艺存在将含有大量钙镁泥和轻质碳酸钙（PCC）的“废浆”埋入废井的重大工艺缺陷,然后提出了废浆零排放的石灰-烟道气卤水净化新工艺。该工艺用专业消化机代替乳化桶,实现石灰乳连续生产、石灰渣自动剔除,通过添加聚丙烯酸钠为结晶助剂、静置陈化等手段使氢氧化镁浮于饱和食盐水表面,从而与沉于底部的二水石膏分离,实现了对氢氧化镁、二水石膏、PCC和卤水的几乎全部回收利用。以年产1×106 t精制盐的盐企为例,可回收氢氧化镁4 000 t、回收二水石膏1.39×105 t、回收PCC 2.6×104 t、回收卤水6.25× 105 t,具有显著的经济效益和社会效益。     

Integrated approach of utilizing mill scale waste for titania slag production

ABSTRACT

Titanium-ferromagnetite ore has been considered as an alternate ore for making alloyed pig iron. It is also important for recovery of higher TiO₂ slag and iron as a metal by high temperature process as other chemical methods produce huge amount of oxides of iron as a by-product. In this paper an alternative way of using low-grade Indian ilmenite (< 50% TiO2) with recycling industrial waste mill scale for titania slag recovery as well as alloyed pig iron by arc smelting. The results reveal that mill scale waste for ilmenite processing is gaining iron recovery and TiO2 slag quality at very low energy consumption.     

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.     

Deflocculation and Classification of Electric Arc Furnace Dust in Aqueous Solution

Abstract

Electric arc furnace (EAF) flue dust is generated during EAF steelmaking from iron-containing scrap such as recycled automobile bodies. The relatively high level of Zn (20–30 wt%) in EAF dusts provides a potentially valuable resource, even though the zinc is present as oxide phases such as zincite (ZnO) and zinc ferrite (ZnFe₂O₄). In this work, a method to deflocculate and disperse ZnO and ZnFe₂O₄ particles in aqueous suspension of EAF dust is developed and the efficiency of Zn recovery by the classification method was evaluated. Major findings of this study indicate that citric acid, a tetradendate chelating agent, demonstrates the best liberation and dispersion efficiency for EAF dust. Elutriating at 0.01 cm/min fluid velocity we recover 10 wt% of EAF dust (mostly ZnO particles) at a grad of 70 wt% Zn from a well-liberated and dispersed suspension of EAF dust. About 30 wt% of Zn recovery may be achieved using only simple classification.     

Formation and reactivity of oxides and basic salts. II. Radio-isotope studies of some calcareous materials

Rates of calcium exchange between solid and solution in the ageing of hydrated lime and of calcium carbonate samples have been determined using calcium-45 radio-isotope. After a comparatively rapid calcium uptake of about 1 molecular layer at the hydrated lime surface, the exchange rate diminishes as the ions need to diffuse more deeply into the hydrated lime structure. Results for calcium carbonate samples of widely different specific surfaces are compatible with very slow ageing in water. Rates of gypsum precipitation from radioactive calcium chloride and nitrate solutions have been compared in neutral and acidic media and in the presence of albumen. Lower gypsum saturation ratios are established ultimately in neutral rather than acidic media, particularly in solutions containing no salts other than gypsum. Solid hydrated lime reacts rapidly with dilute sulphuric acid, aluminium and magnesium sulpnates, magnesium chloride or sea-water, releasing calcium ions into solution. The radioactivities of the solutions decrease subsequently as gypsum separates out or calcium ions are adsorbed by the finely-divided magnesium hydroxide precipitated. At higher magnesium salt concentrations, the calcium-45 radioactivity does not initially increase so sharply. This is ascribed to basic salt formation preventing all of the lime from going quickly into solution.     

The effect of high curing temperature on the reaction kinetics in MK/lime and MK-blended cement matrices at 60 °C

It is well known that the pozzolanic reaction between metakaolin (MK) and calcium hydroxide produces CSH, C₂ASH₈ (stratlingite), C₄AH₁₃ and C₃ASH₆ (hydrogarnet). However, the presence or absence of these hydrated phases depends on different parameters, such as curing temperature, matrix used, etc. This paper shows the results of a study in order to know the effect of high curing temperature (60 °C) on the kinetics of the pozzolanic reaction in different matrices. MK/lime (calcium hydroxide) and MK-blended cement matrices were studied in samples stored and cured at 60 °C and up to 123 days of hydration. The nature, sequence and crystallinity of the hydrated phases were analysed using differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques.Results showed that the sequence and formation of the hydrated phases was different in both matrices cured at 60 °C. In an MK/lime matrix, C₂ASH₈, C₄AH₁₃ and C₃ASH₆ were the main hydrated phases; while in an MK-blended cement, stratlingite was the sole hydrated phase issued from pozzolanic reaction. The DTA and XRD data also reveal an important fact: there is no evidence of the presence of hydrogarnet in blended cements.     

Effect of anodic prepolarization on hydrogen entry into iron at cathodic potentials in 0.1 M NaOH without and with EDTA or sodium molybdate

Efficiency of cathodes for water electrolysis decreases after shut-downs due to corrosion at open-circuit potential. In the present work the effect of prepolarization at various potentials on hydrogen entry into iron during cathodic potential sweeps was studied by the measurement of the hydrogen permeation rate (HPR) through a 35-μm thick iron membrane in 0.1 M NaOH without and with EDTA or Na₂MoO₄ at 25 °C. Two types of the enhanced hydrogen entry at low cathodic polarizations were distinguished: one after prepolarization at low cathodic or low anodic potentials, and another after prepolarization at high anodic potentials. It is suggested that both types can be explained by acidification at the metal surface, the former due to anodic oxidation of iron, and the latter due to cathodic reduction of oxide layer (mainly of Fe₃O₄). XPS analysis revealed the presence of hydrated Fe-O species of unidentified valence. EDTA and Na₂MoO₄ increased the efficiency of hydrogen entry (j_H/j_c ratio), and molybdates also strongly increased cathodic currents of HER. Some of the effects of these additives can be explained in terms of their effect on surface layers.     

Reactivity of lime and related oxides. XVII. Sulphating of lime with magnesium and aluminium sulphates

Lime water and solid hydrated lime have been sulphated with magnesium and aluminium sulphate solutions. Changes in phase composition and sulphating rates are followed from pH (glass electrode) and conductivity measurements. The crystallinities of the products have been compared with calcium sulphate dihydrate precipitated directly from solution by double decomposition and subsequently aged. The reactions with the solid hydrated lime are not appreciably impeded by the insoluble products, magnesium and aluminium hydroxides, which are very finely divided. These compounds provide additional surface on which most of the gypsum can form a gel when the gypsum solution saturation ratios have become sufficiently high. The small amounts of gypsum ultimately separating out from the lime water have crystallinity inferior to the larger amounts formed from the solid hydrated lime. Both are still inferior to gypsum from acid-sulphated lime, and are more comparable with gypsums precipitated from calcium nitrate in acidic media containing concentrations (±0.1 %) of albumen, or from calcium chloride in neutral media. Slower gypsum precipitation from calcium chloride with sulphuric acid (as in the manufacture of ‘Pearl hardening’) gives a more consistent degree of crystallinity.     

Effect of precipitated calcium carbonate additions on waterborne paints at different pigment volume concentrations

Titanium dioxide (TiO₂) due to its high refractive index, is widely used in paint industry as a white pigment. In order to reduce this high cost of TiO₂, a part of TiO₂ is generally substituted by some other industrial mineral fillers such as calcite and calcined kaolin; however, this substitution affects the quality of paints in terms of stability, coverage (opacity), brightness (gloss), scrub resistance (film toughness), etc. In the present paper, precipitated calcium carbonate (PCC) was substituted for TiO₂ in paint mixture at three different pigment volume concentrations (PVC). It was observed that substitution of TiO₂ by PCC depends on PVC value at which there is an optimum PCC amount. The quality of paints produced by PCC along with its rheological properties was evaluated based on standard features in both wet and dry paints such as viscosity, density, opacity and gloss values. Addition of PCC increases the opacity to a certain point. Similarly, scrub resistance and viscosity increases with the addition of PCC at all PVCs, however, viscosity is not as much critical for the paint production. On the other hand, there is no any systematic effect of PCC on gloss value of the paint. This study overall demonstrates that PCC can be successfully used to substitute TiO₂ only with a careful adjustment of PVC and other extenders used in the paint formulation.     

Kinetics of the reaction of iron blast furance slag/hydrated lime sorbents with SO2 at low temperatures: effects of sorbent preparation conditions

Sorbents highly reactive towards SO₂ have been prepared from iron blast furnace slag and hydrated lime under different hydration conditions. The reaction of the dry sorbents with SO₂ has been studied under the conditions similar to those in the bag filters in the spray-drying flue gas desulfurization system. The reaction was well described by a modified surface coverage model which assumes the reaction rate being controlled by chemical reaction on sorbent grain surface and takes into account the effect of sorbent Ca molar content and the surface coverage by product. The effects of sorbent preparation conditions on sorbent reactivity were entirely represented by the effects of the initial specific surface area (S_g0) and the Ca molar content (M⁻¹) of sorbent. The initial conversion rate of sorbent increased linearly with increasing S_g0, and the ultimate conversion increased linearly with increasing S_g0M⁻¹. The initial conversion rate and ultimate conversion of sorbent increased significantly with increasing relative humidity of the gas. Temperature and SO₂ concentration had mild effects on the initial conversion rate and negligible effects on the ultimate conversion.     

Better Lime Purification of Raw Sugar Beet Juice by Advanced Fenton Oxidation Process

This work discusses the effects of Fenton oxidation pre-treatment on the lime purification of raw sugar beet juice using iron powder and hydrogen peroxide. During Fenton oxidation, particular attention was paid to the effect of reaction time and dosage of Fenton′s reagent to improve purification indexes of the raw juice throughout the clarification process. The total concentration of lime used for the purification was varied from 4.0 to 16.0 g of CaO/100 mL of juice. The results showed that higher color and total phenolic removal were achieved with an increase in H₂O₂ dosage and reaction time. At an initial pH of less than 6.2 and H₂O₂ concentration of 7000.0 ppm, color removal reached 85% and approximately 81% of total phenolic removal was achieved at a reaction time of 30 min (Treatment 5). It suggests that the quantity of CaO required for the efficient juice purification may be decreased from 16.0 g/100 mL for the control juice to approximately 12.0 g/100 mL for the juice obtained from Treatment 5. Fenton oxidation process improved the quality indexes of the purified juice, and can be combined with a conventional clarification process to achieve juice with high purity and low color.     

Factors affecting the phase and morphology of CaCO3 prepared by a bubbling method

Precipitated calcium carbonate (PCC) was prepared by bubbling a CO₂/N₂ mixed gas into a CaCl₂ solution. The influence of preparation conditions on the phase and morphology of PCC was discussed with the help of XRD and SEM measurements. The results showed that the initial CaCl₂ concentration, flow rate and temperature play an important role on the morphology of PCC. At low initial CaCl₂ concentration or high flow rate, spherical vaterite was preferably formed. Otherwise, the rhombic calcite was ready to form. Temperature is a determining factor on the formation of aragonite. Needle-like aragonite was precipitated at 60 °C. The results also indicated that both the bubbling time and stirring rate have a minor effect on the phase and morphology of PCC.     

Synthesis of magnesium sulfate from seawater using alkaline industrial wastes,sulfuric acid,and organic solvents

ABSTRACT

In this study, we used three processes to synthesize magnesium sulfate from seawater. First, alkaline industrial wastes, cement kiln dust and paper sludge ash, were injected to the seawater to precipitate magnesium in the form of magnesium hydroxide (Mg(OH)₂). Then, magnesium was eluted with a small amount of H₂SO₄ to make a high concentration magnesium solution. Finally, an organic solvent was added to precipitate magnesium sulfate (MgSO₄). Over 90% of magnesium was recovered through the three processes. It is expected that 11.3 kg of magnesium sulfate (based on MgSO₄ · 6H₂O) can be synthesized from 1 ton of seawater.     

Continuous precipitation of calcium sulfate dihydrate from waste sulfuric acid and lime

Precipitation of calcium sulfate dihydrate, gypsum, from (i) a pure sulfuric acid/lime suspension and (ii) a waste sulfuric acid/lime suspension in a continuous pilot plant in the temperature range from 40 °C to 80 °C was studied. It was observed that in the case of waste sulfuric acid with a high content of Mg²⁺ and Fe²⁺ ions, several hours after the beginning of the precipitation, partial dissolution of the product and modification of the crystals from needle‐ and plate‐like to agglomerated structures occurred. It is suggested that the secondary changes occur due to the increased concentration of Mg²⁺ and Fe²⁺ ions in the reactor. Below 60 °C, and above 70 °C plate‐like and needle‐like single crystals respectively were formed. The mean size (d₅₀) of the crystals was found to increase with increasing temperature and decrease with the initial concentration of lime. Gypsum produced between 70 °C and 80 °C is suitable for further processing for construction plaster. In a precipitation process with pure sulfuric acid only single perfect needle‐like crystals occurred. Copyright © 2005 Society of Chemical Industry