Crystallization Of Calcium Sulfate Dihydrate Research Articles

Effect of trace metals on reactive crystallization of gypsum

AbstractThe effect of Fe2+, Fe3+, and Cr3+ ions on crystallization of calcium sulfate dihydrate (gypsum) produced by the reaction between calcium hydroxide suspension and sulphuric acid solution was investigated at 3.5 pH and 65°C in the absence and presence of 2500 ppm citric acid concentration. Crystal size distributions, filtration rates, and morphology of gypsum were determined and discussed as a function of ion concentration. Average particle size of gypsum was not affected significantly by the presence of Fe2+, Fe3+, and Cr3+ ions individually. Variation of gypsum morphology depending on ion concentration affected the filtration characteristics. The presence of Fe3+ or Cr3+ ions besides 2500 ppm citric acid influenced both average particle size and filtration characteristics. The effect of citric acid on gypsum morphology was suppressed at high Fe3+ and Cr3+ ion concentrations. The change of morphology is related to the complex formation between Fe3+ or Cr3+ ions and citric acid at high ion concentrations. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Dual Roles of Borax in Kinetics of Calcium Sulfate Dihydrate Formation

An additive is not exclusively retardant or promoter for a crystallization system. The kinetic studies of calcium sulfate dihydrate (CSD) crystal growth demonstrated that borax played dual roles in the reaction, which accelerated CSD formations at the low concentration levels but inhibited the crystal growth at the high ones. In situ atomic force microscopy studies revealed that borax modulated the CSD crystallization via two different pathways: promoted the secondary nucleation to increase the step density on the growing crystal faces but simultaneously retarded the spread of these growth steps by the Langmuir adsorption. These two contradictory factors were incorporated in the crystallization, and their balance was regulated by the borax concentration. Both the macroscopic and microscopic experimental data nicely displayed the crystallization model of birth and spread that was able to account for the behaviors of borax in CSD formations.

Influence of citric acid on calcium sulfate dihydrate crystallization in aqueous media

AbstractThe crystallization of Calcium sulfate dihydrate produced by the reaction between pure Ca(OH)2 suspension and H2SO4 solution was investigated at different pH values, temperatures and citric acid concentrations. Crystal size distributions, filtration rates and zeta potentials of gypsum were determined as a function of citric acid concentrations at pH 3.5 and 65°C. The influence of citric acid on the morphology of gypsum was also investigated and discussed. The average particle size of gypsum was reached to maximum in the presence of approximately 2500 ppm citric acid concentration, where the minimum cake resistance and maximum filtration rate were obtained. In the presence of citric acid, various crystal morphologies such as tabular, plate‐like, double‐taper leaf‐like and flower‐like, etc., were obtained. The change of morphology is related to the preferential adsorption of citric acid on different crystallographic faces. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Crystallization of calcium sulfate dihydrate in the presence of some metal ions

Crystallization of calcium sulfate dihydrate (CaSO 4·2H 2O gypsum) in sodium chloride solutions in the presence of some metal ions, and over a range of relative super-saturation has been studied. The addition of metal ions, even at relatively low concentration (10 −6 mol l −1), markedly retard the rate of crystallization of gypsum. Retardation effect was enhanced with increase in the additives contents. Moreover, the effect was enhanced as the relative super-saturation decreases. Influence of mixed additives on the rate of crystallization (Cd 2++Arg, Cd 2++H 3PO 4 and Cd 2++PAA) has also been studied. Direct adsorption experiments of these metal ions on the surface of gypsum crystals have been made for comparison.

Effect of cetyl pyridinium chloride additive on crystallization of gypsum in phosphoric and sulfuric acids medium

AbstractA basic study was carried out to understand effect of Cetyl Pyridinium Cloride (CPC) on calcium sulfate dihydrate (gypsum) crystallization. Induction time was measured under different supersaturation ratios ranging from 1.222 to 1.979. This is the time elapsed between the achievement of supersaturation and the appearance of a solid phase. The results show that, the induction time decreases exponentially with increasing the supersaturation ratio. In addition, the surface energy increases with CPC compared to the baseline (without CPC). Number of molecules required for formation of stable nucleus are calculated to be from 3 to 41 molecules depending on supersaturation ratios and presence of CPC. Interestingly, with addition of the CPC, the mean diameter of the crystals and the median increase. The growth rate was found dependent on the supersaturation with and without CPC. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Effect of citric acid and 1,2-dihydroxybenzene 3,5-disulfonic acid on crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production

The effect of citric acid and 1,2-dihydroxybenzene 3,5-disulfonic acid (DHBDSA), as additives, on the crystallization of gypsum was studied under simulated conditions of the of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 °C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. Addition of citric acid increased the induction time and decreased the growth efficiency while addition of DHBDSA decreased the induction time and increased the growth efficiency compared with in absence of additives. The crystals mean and median diameters were found to decrease in the presence of citric acid and increased in the presence of DHBDSA. The surface energy decreased with citric acid and increased with DHBDSA compared to the baseline (without additives). Interestingly, the majority of the formed crystals are tabular with DHBDSA and needle-like type with citric acid and baseline

Crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production in the presence of aluminum and magnesium ions

The effect of Al 3+ and Mg 2+ ions, as additives, on the crystallization of gypsum was studied under simulated conditions of the phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80°C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. Addition of Al 3+ ions up to 2% decreased the induction time and increased the growth efficiency while addition of Mg 2+ increased the induction time and decreased the growth efficiency compared with in absence of additives. Interestingly, the crystals mean and median diameters were found to increase in the presence of Al 3+ and decrease in the presence of Mg 2+. The surface energy increased with Al 3+ and decreased with Mg 2+ compared to the baseline (without additives). Gypsum morphology changed from needle-like type in absence of additives to thick-rhombic in the presence of Al 3+ ions.

Crystallization of calcium sulfate dihydrate at different supersaturation ratios and different free sulfate concentrations

AbstractFree Sulfate is a major parameter affecting gypsum crystallization during phosphoric acid production. Gypsum crystal size, shape and filtration rate are significantly affected by the concentration of free sulfate. It is, therefore, important to evaluate the effectiveness of different sulfate levels from 1.5% to 3.5% on induction time and gypsum morphology. The crystallization of gypsum was carried out under simulated conditions of phosphoric acid production by the dihydrate process. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 °C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. With increasing free sulfate concentration, the induction time was significantly decreased. Chemical processing of Central and South Florida phosphate concentrates under different concentrations of free sulfate from 1.5% to 5.5% was carried out. The change on crystal size distribution and filtration rate were traced with free sulfate concentrations. The results show that, filtration rate of phosphogypsum was correlated to the mean diameter of crystals. In addition, induction time and co‐crystallized (lattice) P2O5 % in gypsum are decreased with increasing free sulfate content from 1.5% to 3.5%. Morphology of formed gypsum crystals at different sulfate contents and different supersaturation ratios are investigated. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

New hydraulic cements based on α-tricalcium phosphate–calcium sulfate dihydrate mixtures

Calcium sulfate dihydrate (CSD) powder was added to a cement consisting of α-tricalcium phosphate ( α-TCP) and water. The changes of the physico-chemical properties of the cement were investigated as a function of the CSD amount, the phosphate concentration in the mixing solution, and the solution volume. An increase of the phosphate concentration in the mixing liquid and small additions of CSD powder strongly reduced the cement setting time. Simultaneously, the fraction of unreacted α-TCP powder present after 1 day of incubation increased, indicating that α-TCP hydrolysis was inhibited. The effects of the CSD amount and the phosphate concentration were synergetic, i.e. the effect of CSD powder was increased with an increase of the phosphate concentration and vice versa. Interestingly, none of the factors affected the cement diametral tensile strength. The present results were explained based on solubility calculations. The present study shows that the use of CSD crystals in combination with phosphate ions is an easy and interesting way to control the setting time of α-TCP–water mixtures, in particular, because the mechanical properties of the cement are not modified.

Effect of phosphonate additive on crystallization of gypsum in phosphoric and sulfuric acid medium

AbstractUnderstanding the mechanisms of growth and inhibition during crystallization of calcium sulfate is of primary importance for many industrial applications. For instance, inhibition of the crystallization process may be required to prevent scale formation in pipes, boilers, heat exchangers, reactors, reverse osmosis membrane surfaces, cooling water systems, secondary oil recovery utilizing water flooding techniques and desalination evaporators, etc. On the other hand, control growth and morphology of gypsum crystals is desired in achieving higher filtration rate and higher productivity of phosphoric acid from phosphate rocks. In this regard, this basic study is carried out to understand effect of Aminotris (methylenephosphonic acid (ATMP) on calcium sulfate dihydrate (gypsum) crystallization. The time elapsed between the achievement of supersaturation and the appearance of a solid phase (termed as induction time) is measured under different supersaturation ratios ranging from 1.018 to 1.979. The data are used to calculate the surface energy, critical nucleus size, and crystal growth rates of gypsum under different conditions. The results show that, the induction time decreases exponentially with increasing the supersaturation ratio. In addition, the surface energy decreases with ATMP compared to the baseline (without ATMP). Interestingly, with addition of the ATMP, the crystals mean and median diameters are found to decrease. The inhibition efficiency ranges from 16% to 59% depending on supersaturation ratio.

Effect of ferrous and ferric iron impurities on the crystallization of gypsum and sludge formation in wet-process phosphoric acid

The effect of ferrous and ferric iron on the crystallization of calcium sulfate dihydrate, the rate of filtration, and the precipitation of sludge in concentrated acid were investigated. A bench scale unit was used to simulate dihydrate plant conditions. It was found that ferrous iron was oxidized to ferric, and the behavior of the two impurities in the acid was therefore very similar. At low levels of impurities, ferrous and ferric iron improved filtration, but further additions decreased it. Sludge collected from the concentrated acid after five weeks was mainly calcium sulfate hemihydrate and anhydrate. With the addition on 0.5% and 0.75% iron impurities however, the presence of (Fe,Al) 3 KH 14 (PO 4 ) 8 ·4H 2 O was evident in electron micrographs.

Crystallization of Calcium Sulfate Dihydrate from Phosphoric Acid

AbstractKnowledge of the kinetics of calcium sulfate dihydrate crystallization from phosphoric acid solutions is essential for design and operation of the dihydrate process, which is frequently used in fertilizer industries for the production of phosphoric acid A continuous crystallizer was used to investigate the effect of operating parameters on nucleation and growth rates, and ultimately on the crystal size distribution of calcium sulfate dihydrate. It is shown that growth rate increases with the square of supersaturation and that the effect of temperature on the growth rate constant follows an Arrhenius relationship with an activation energy of 65.2 kJ/mol. The predictions of the suggested kinetic models are verified against plant data.

Dissolution of Phosphate Rock by Mixtures of Sulfuric and Phosphoric Acid

AbstractThe dihydrate process for the production of phosphoric acid is increasingly important as the basis for phosphate fertilizer plants. The process involves dissolution of phosphate rock in an aqueous mixture of phosphoric and sulfuric acid and subsequent crystallization of calcium sulfate dihydrate from the product phosphoric acid solution. In this study the mechanisms of dissolution of phosphate rock are studied using reagent grade and plant acids. The effects of various operating parameters such as temperature, particle size and excess sulfuric acid concentration on the rate of dissolution of rock are investigated. The results show that the dissolution of the rock occurs in two stages of different rates. Initially, the dissolution process is fast and is controlled by chemical reaction between rock and acid. In the second stage, when the particles are coated by calcium sulfate dihydrate the dissolution process is slow and controlled by mass transfer of acid through the coating layer.

Effects of Sulfate, Pyrophosphate, and Citrate Ions on the Physicochemical Properties of Cements Made of β‐Tricalcium Phosphate‐Phosphoric Acid‐Water Mixtures

Several additives were selected to increase the setting time of calcium phosphate cements made of β‐tricalcium phosphate (β‐TCP; β‐Ca3(PO4)2)‐phosphoric acid‐water mixtures. The effects of the additives, i.e., sulfate, pyrophosphate, and citrate ions, are presented in this study. The results show that they all increased the setting time of the cement. Their effectiveness at increasing the setting time is in the order pyrophosphate > citrate > sulfate. The effect of sulfate ions on the setting time is increasingly large below a concentration of 0.1M. Above that concentration, calcium sulfate dihydrate (CSD; CaSO4‐2H2O) crystals nucleate and act as nuclei for dicalcium phosphate dihydrate (DCPD; CaHPO4‐2H2O) crystals, which are the normal product of the setting reaction. This decreases the setting time and decreases the DCPD crystal size, resulting in an increase of the tensile strength of the cement.

Adsorption of Some Metal Ions on the Surface of Calcium Sulphate Dihydrate Crystals in Artificial Sea Water

Adsorption of Some Metal Ions on the Surface of Calcium Sulphate Dihydrate Crystals in Artificial Sea Water

The Seeded Growth of Calcium Sulfate Dihydrate Crystals in NaCl Solutions up to 6 m and 90°C

The kinetics of calcium sulfate crystal growth is of importance in various fields, such as geochemistry, desalination technology, petroleum industry, and water and wastewater treatment. The seeded crystal growth rate of calcium sulfate dihydrate was measured as a function of supersaturation in NaCl electrolyte solutions from 0 to 6 m at temperatures of 25, 50, 70, and 90 C. The growth followed a second-order parabolic rate law with activation energies greater than 53 kJ/mol which suggested the surface reaction as the rate-limiting step. It was observed that the rate constant and the activation energy are solution composition dependent. The rate constant increases with NaCl concentration up to 3 molal and then begins to fall slightly. The activation energy dropped from 61 kJ/mol in the pure Ca-SO[sub 4]H[sub 2]O system to 53 kJ/mol in 3.0 m NaCl solutions. The electrolyte effect was similar to the crystal solubility behavior in aqueous electrolyte solutions resulting from the variation of the mean activity coefficient of the crystal with ionic strength. The rate constant is proportional to the crystal solubility and inversely proportional to the edge work or the interfacial tension as expected in the classic BCF model.

Effects of addition of calcium phosphates on the properties of gypsum : Inomata K. (1990) Jap. J. Dent. Mater.9, 121–132

Calcium hydrogen phosphate (CHP), calcium hydrogen phosphate dihydrate (CHPD) and calcium sulfate dihydrate (gypsum) crystals were added to calcium sulfate hemihydrate as gypsum model materials for improvement of the mechanical properties. The compressive and the bending strength of the hardened mixture were improved by the addition of CHPD, while the addition of CHP and gypsum crystals had no effect. The setting time was markedly reduced by the addition of CHPD, but remarkably increased in the case of CHP crystals. On the other hand, the setting expansion was decreased by the addition of CHP and CHPD crystals. Based on the observation of the surface profile of the calcium sulfate hemihydrate set in contact with glass, and scanning electron microscopy (SEM) of the fractured surface of the hardened mixture, the surface roughness was markedly decreased by the addition of CHPD. When the crystals were added to the metastable solution of calcium sulfate supersaturated with respect to gypsum, the presence of gypsum crystals deposited on the CHPD surface was confirmed by atomic absorption analysis, fourier transform infrared spectroscopy. SEM and electron X-ray microanalysis. Therefore, epitaxial growth of gypsum occurred on the CHPD surface and the addition of CHPD improved the mechanical properties of the gypsum materials.

Effects of addition of calcium phosphates on the properties of gypsum

Calcium hydrogen phosphate (CHP), calcium hydrogen phosphate dihydrate (CHPD) and calcium sulfate dihydrate (gypsum) crystals were added to calcium sulfate hemihydrate as gypsum model materials for improvement of the mechanical properties. The compressive and the bending strength of the hardened mixture were improved by the addition of CHPD, while the addition of CHP and gypsum crystals had no effect. The setting time was markedly reduced by the addition of CHPD, but remarkably increased in the case of CHP crystals. On the other hand, the setting expansion was decreased by the addition of CHP and CHPD crystals. Based on the observation of the surface profile of the calcium sulfate hemihydrate set in contact with glass, and scanning electron microscopy (SEM) of the fractured surface of the hardened mixture, the surface roughness was markedly decreased by the addition of CHPD. When the crystals were added to the metastable solution of calcium sulfate supersaturated with respect to gypsum, the presence of gypsum crystals deposited on the CHPD surface was confirmed by atomic absorption analysis, fourier transform infrared spectroscopy. SEM and electron X-ray microanalysis. Therefore, epitaxial growth of gypsum occurred on the CHPD surface and the addition of CHPD improved the mechanical properties of the gypsum materials.

Microhardness studies on calcium sulphate dihydrate crystals grown in silica gel in the presence and absence of barium chloride as additive

Microhardness studies on calcium sulphate dihydrate crystals grown in silica gel in the presence and absence of barium chloride as additive

Microtopographical and Raman spectral studies on calcium sulphate dihydrate (gypsum) crystals grown in silica gel in the presence and absence of barium chloride as additive

A procedure for the growth of calcium sulphate dihydrate (gypsum) crystals, CaSO4 · 2H2O, by a gel technique in the presence of barium chloride as an additive as well as without the additive, is described. Optimum conditions for the growth of good quality crystals are worked out. Needle-shaped crystals with well-defined prism faces are obtained. Microtopographical studies of the crystals are carried out. The observed surface structures on the prism faces of the crystals include vertical striations and parallelogram-shaped, oriented growth hillocks. Etch patterns on these faces are described and discussed. Reciprocity of the growth and etch mechanisms is established. Laser Raman spectral studies of these crystals are also made. Splitting of the non-degenerate fundamental is observed in the spectrum of the crystals grown in the presence of the additive. The present studies indicate that the additive used enhances the quality of the crystals.