Precipitation Of Calcium Sulfate Research Articles

Effect of spacer on mass transfer coefficient and calcium sulfate scaling phenomena in reverse osmosis desalination

Inorganic material (scale) precipitation on reverse osmosis (RO) membranes is a serious issue in plants because performance recovery via cleaning is challenging, and the replacement expenses are enormous. This study investigated the calcium sulfate scaling phenomena on membranes using a flat membrane cell with a spacer to model a spiral wound-type RO element. Subsequently, the mass transfer coefficient of the flat membrane cell with the spacer and the convergent value of permeate flux due to solute precipitation were determined. The dimensionless equation for the mass transfer coefficient of the cell with the spacer could be expressed using the dimensionless equation for the mass transfer coefficient of a flat membrane cell without a spacer. The behavior in permeate flux due to the precipitation of calcium sulfate on the RO membrane of the cell with the spacer was analyzed based on the scaling-based critical flux and scaling index, which discriminate scale precipitation. Finally, scale precipitation experiments were conducted by varying spacers and the operating conditions of pressure, solute concentration, temperature, and Reynolds number; the permeate flux was confirmed to converge to the scaling-based critical flux, and the scaling index could discriminate the operating condition area of scale precipitation.

Homopolymers and copolymers with iminodiacetic acid chelating units for scale inhibition

Novel homopolymer and copolymer scale inhibitors with iminodiacetic acid chelating units were synthesized for inhibiting calcium carbonate and calcium sulfate precipitation. Static scale inhibition tests of SI-1 demonstrated excellent performance, with inhibition performance of 83 % at a concentration of 30 mg/L for CaCO3 and >99 % at a concentration of 8 mg/L for CaSO4. These novel inhibitors surpassed the performance of a commercially available industrial scale inhibitor, 2-phosphonobutane-1,2,4-tricarboxylic acid. The homopolymer significantly altered CaCO3 and CaSO4 crystal structures and reduced crystal size at low concentrations. The primary mechanism of inhibition appears to be a two-fold effect: strong and specific complexation between the iminodiacetic acid chelating units and free Ca2+ ions, coupled with the adsorption of the polymers on the crystal surfaces. These promising scale inhibitors offer a potential replacement for phosphorus-containing compounds currently used in industrial applications.

Fluorescent-tagged antiscalants as a tool of homogeneous membrane scaling mitigation and inhibition mechanism investigation in electrodialysis processing of solutions prone to calcium sulfate precipitation

Fluorescent-tagged antiscalants as a tool of homogeneous membrane scaling mitigation and inhibition mechanism investigation in electrodialysis processing of solutions prone to calcium sulfate precipitation

Study on Mechanical Properties of Sulfate Saline Soil Improved by CLI-Type Polymer Active Agent

Large amounts of soluble salts in a soil enhance the soil sensitivity to changes in its properties induced by changes in environmental conditions, such as easy dissolution in water and easy occurrences of salt heaving in low-temperature environments, which make the soil volume swell rapidly, leading to a series of engineering disasters. Moreover, the growth and development of surface vegetation will be inhibited due to excessive salinity, resulting in a gradual decline in the ecological functionality of the area. A polymer active agent (CLI) was selected for the ecological improvement of sulfuric acid saline soils. Triaxial compression tests and a test on the soluble salt content of the treated soil were carried out to investigate the effects of polymer active agent content and maintenance time on the mechanical properties and soluble salt content of sulfate saline soils. The results showed that the addition of CLI can improve the soil strength by increasing the cohesion of the specimen, and the improvement increases significantly with the content of CLI and the curing age. Meanwhile, the calcium ions in CLI can react with sulfate ions in sulfate-salted soils to produce calcium sulfate precipitation to alleviate soil salinization. The scanning electron microscopy (SEM) images indicated that an appropriate content of CLI (about 8%) can strengthen the soil structure through an excellent chelating ability, enhancing the strength of the soil.

Optimization of salinity and composition of injected low salinity water into sandstone reservoirs with minimum scale deposition

In this study, a mechanistic and comprehensive examination of the impact of the scale formation situation of different diluted seawater levels was conducted to investigate the influence of important factors on the performance and efficiency of low salinity water. To clarify the effective participating mechanisms, scale precipitation by compatibility test, field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopy (EDX) analysis, zeta potentials as surface charge, ion concentration changes, contact angle, pH, CO2 concentration, electrical conductivity, and ionic strength were analyzed. The results showed that increasing the dilution time to the optimal level (10 times-diluted seawater (SW#10D)) could effectively reduce the amount of severe precipitation of calcium carbonate (CaCO3) and calcium sulfate (CaSO4) scales. However, the reduction in CaCO3 scale precipitation (due to mixing different time diluted seawater with formation brine) and its effect on the wettability alteration (due to the change in surface charge of OLSW/oil and sandstone/OLSW) had higher impacts. The zeta potential results have shown that OLSW with optimum salinity, dilution, and ionic composition compared to different low salinity water compositions could change the surface charge of OLSW/oil/rock (− 16.7 mV) and OLSW/rock (− 10.5 mV) interfaces toward an extra negatively charged. FESEM and contact angle findings confirmed zeta potential results, i.e. OLSW was able to make sandstone surface more negative with diluting seawater and wettability changes from oil-wet toward water-wet. As a result, SW#10D was characterized by minimum scaling tendency and scale deposition (60 mg/l), maximum surface charge of OLSW/oil/rock (− 16.7 mV), and the potential of incremental oil recovery due to wettability alteration toward more water-wetness (the oil/rock contact angle ~ 50.13°) compared with other diluted seawater levels.

The Role of Sulfate in Cation Exchange Reactions: Applications to Clay–Brine Interactions on Mars

Phyllosilicates on Mars record a complex history of aqueous activity, including at Gale crater and Meridiani Planum, where stratigraphic differences in clay mineralogy have been recorded in outcrops that also contain calcium sulfate minerals. Thus, characterizing associations between phyllosilicates and calcium sulfates may provide constraints that are useful for constraining the geochemical environments that formed these outcrops. Previous studies have documented calcium sulfate precipitation as a result of clay–salt–atmospheric H2O interactions, but the compositions of brines throughout Mars’ history would have depended on the volume of water available on the Martian surface. Variations in brine composition influence the type and extent of reactions between the brines and the minerals that they come in contact with. To better understand how clay–brine interactions affected near-surface mineral assemblages on Mars, we performed two sets of experiments. The first set of experiments examined the effect of differing total brine concentrations and the second set explored variations in Na+ and SO4 2− concentrations independently. The results of this study show that gypsum readily forms due to cation exchange between montmorillonite and Na2SO4 brines of any concentration, but only near-saturated MgSO4 brines produced gypsum, and these also produced higher quantities of epsomite. Additionally, we found that the amount of gypsum produced from clay–Na2SO4 brine reactions is more strongly influenced by SO4 2− than Na+ or Cl− concentrations. Understanding how rapidly gypsum forms as a product of clay–brine interactions, as well as the influence of SO4 2− on cation exchange, will aid interpretations of sediments and environments that are observed on Mars.

Chemical inhibition of combined gypsum and iron oxides membrane fouling during reverse osmosis desalination process: Prevention and regeneration of membranes

This paper explores the performance of carboxylic acids as environmentally friendly chemical inhibitors and cleaning agents during combined membrane fouling by gypsum and iron oxides. The efficiency of citric acid and two other carboxylic acids was evaluated during combined fouling trials by measuring normalized fluxes drops, using an RO pilot unit. The effect of acid concentration, pH variation and gypsum supersaturation were evaluated. SEM, EDX, X-Ray diffraction and FTIR were used to identify the composition and morphology of fouled membranes. The results indicated that at low pH, citric acid serves to restore the flux drop. This acid serves to orient the crystals towards the hemihydrate form with a flat, thin structure. By increasing the pH, the acid retains its effectiveness and serves to delay the Fe2+ oxidation ions and the precipitation of calcium sulfate for more than 3 h. By comparing them to the citric acid, ascorbic and tartaric acid showed a similar effect at acidic pH. In both cases, normalized fluxes were recovered with the use of 100 ppm of each acid. However, at alkaline pH, citric shows a better performance. The regeneration of RO membranes fouled by iron oxides and gypsum appears to be more effective with citric acid than the other two acids.

Phase changes in cementitious materials exposed to saline solutions

This article summarizes long-term degradation mechanisms of cementitious materials in contact with fresh and saline solutions based on a review of experimental observations in field and laboratory studies. In addition, a simplified thermodynamic modelling approach was used to calculate the effect of the solution composition, ranging from river water to sea water, on the intensity of leaching and the kind and quantity of phases formed at the interface with the environment. This study shows that leaching is the main underlying degradation mechanism for all investigated exposure solutions. The presence of carbonates and sulphates in the solution increases leaching and decalcification of Ca-rich phases leading to the precipitation of calcium carbonate and calcium sulfate, while the presence of chloride has little influence on the intensity of leaching. Carbonates in the interacting solution can suppress ettringite formation. If present, magnesium precipitates as brucite, M-S-H or hydrotalcite-like phase.

Oxidative Decomposition of Silver Telluride (Ag2Te) Using Hypochlorite in Different Acid Environments

ABSTRACT Silver telluride represents one of the most important refractory silver mineral phases and requires the development of alternative processing routes. This work presents a detailed analysis of the effect of sodium and calcium hypochlorite species, HNO3, HCl, H2SO4 and pH on the kinetics and efficiency of silver telluride dissolution. The understanding of the reaction mechanism was complemented with the use of thermodynamic diagrams and characterization of the solid residues by the X-ray diffraction and SEM-EDS techniques. The results revealed that the presence of Ca(ClO)2 and H2SO4 promotes the secondary and massive precipitation of calcium sulfate. A comparison of the oxidative systems containing Ca(ClO)2 and NaClO showed that the solutions containing NaClO are more efficient and selective. The decrease in pH favors the tellurium dissolution due to an increase in the in-situ concentration of chlorine oxidizing species; the silver is transformed into silver chloride solid species on the surface of unreacted silver telluride. Thermodynamic and experimental studies revealed that silver chloride layer and the continuous consumption of hypochlorous acid promote the passivation of the system. The characterization of the solid residues evidenced that the type of acid contained in the systems modifies the morphology of the silver chloride layer. Finally, the surface characterization showed that passivation due to the formation of compact layer of silver chloride can be modified using a hypochlorite system containing nitric acid; this is due to a synergistic effect of nitrate and hypochlorite species on the kinetics of silver telluride dissolution. This effect is also discussed from a mechanistic viewpoint.

Analysis of Calcium Sulfate Scaling Phenomena on Reverse Osmosis Membranes by Scaling-Based Flux Model.

In this study, the behavior of permeate flux decline due to scale precipitation of calcium sulfate on reverse osmosis membranes was investigated. The proposed scaling-based flux model is able to explain that permeate fluxes attributed to three mechanisms of scale precipitation—cake formation, surface blockage, and mixed crystallization—converge to the same newly defined scaling-based critical flux. In addition, a scaling index is defined, which determines whether scale precipitates on the membrane. The experimental results were analyzed based on this index. The mass-transfer coefficients of flat membrane cells used in the experiments were measured and, although the coefficients differed, they could be summarized in the same form as the Leveque equation. Considering the results of the scale precipitation experiments, where the operating conditions of pressure, solute concentration, temperature, and Reynolds number were varied, the convergent values of the permeate fluxes are explained by the scaling-based critical fluxes and the scale precipitation zones by the scaling indexes.

Minimizing calcium lactate precipitation via the addition of gluconate ions for matrix acidizing with lactic acid

Organic acids are commonly used to replace hydrochloric acid (HCl) in high reservoir temperature applications, as they are less corrosive and weaker than HCl. However, organic acids have shown some problems due to acid reaction product solubility. One such organic acid, lactic acid, produces calcium lactate when it reacts with calcite, which has a low solubility in water. However, reaction product solubility can be improved by up to five times when gluconate ions coexist with lactate and calcium ions. The objective of this research is to evaluate lactic and gluconic acid mixtures in term of dissolving calcite, reaction product, corrosion, wettability and generating dominant wormhole.Lactic and gluconic acids were mixed together using deionized water and seawater to conduct calcite solubility tests. Corrosion tests, between 4 and 12 h, were also run under reservoir conditions. A formation response test (FRT) apparatus was used to run different coreflood tests using different combinations of injection rates, total acid concentration, and temperatures. These tests were accompanied with analytical analysis utilizing ICP and IC to measure calcium, iron and sulfate ions in solution.The results showed that mixing lactic and gluconic acids at a 1:1 M ratio provided the optimal results as no precipitation occurred at total acid strengths of 10 wt% and up to 27 wt%. Seawater usage caused calcium sulfate precipitation; therefore, three scale inhibitors were evaluated to determine mitigation rates. Acid-calcite dissolving results were satisfactory when limestone was exposed to a 1:1 and 2:1 M ratio of crushed core-to-acid ratios as at least 50% of the crushed core was dissolved. However, the two-acid mixture showed a corrosion rate that was higher than the acceptable rates and a trace of iron lactate precipitation occurred at 200 and 300 °F. Five gpt from a sulfur-based corrosion inhibitor was enough to mitigate the corrosion rate to allow for 8 h of testing. Coreflood tests showed that the mixture penetrated limestone core with minimal acid pore volume without any face dissolution or salt precipitation on the core faces.This research presents a set of diverse experimental data to confirm that lactic acid accompanied by gluconic acid can penetrate carbonate formation without any by-product precipitation. The two organic acids are less corrosive and less hazardous which can provide a safe operation environment and can decrease replacement and maintenance costs.

Geochemical investigation of electrical conductivity and electrical double layer based wettability alteration during engineered water injection in carbonates

The injection of engineered water to increase the oil recovery from carbonates is increasingly becoming popular due to its reduced environmental impact and low cost of operation. However, the related variation in electric properties of rock and fluid with this technique is still ambiguous and needs thorough investigation. This study explores the variation in electrical conductivity, ion mobility, electrical double layer thickness, and the related oil recovery with the change in water composition from a geochemical perspective. In this study, we implemented an improved wettability alteration model based on the variation in electrical conductivity with a Matlab-IPhreeqc coupled simulator, to model the electrical conductivity, ion mobility, and electrical double layer (EDL) thickness. The variation in concentration of the ionic species obtained from the geochemical model is used to determine the electrical conductivity. This electrical conductivity-based wettability modification is dynamically simulated in the transport model. The model is validated with experimental coreflood data conducted on carbonates by simulating the electrical conductivity measurements reported in the literature. From the findings, it is evident that the formation temperature, sulfate concentration, and dilution of injected seawater has a noticeable effect on electrical conductivity during engineered water injection. It is important to mention that the EDL thickness is the main parameter affected by the change in electrical conductivity. In consequence, it is suggested to inject high-temperature water in carbonate reservoirs because it will increase ion mobility. This increase in ion mobility will enhance the EDL thickness and water film will become stabilized. Moreover, seawater dilution decreases electrical conductivity while spiking of sulfate concentration increases the activity of sulfate ions. However, the concentration of sulfate ions must be controlled as a wettability alteration agent, as it can cause the formation and precipitation of calcium sulfate. Furthermore, the variation in electrical conductivity and EDL thickness caused by the injection of seawater and diluted seawater increased the recovery of oil by approximately 16–21% in the selected case study.

Geochemical modeling of CO2 injection and gypsum precipitation at the Ketzin CO2 storage site

Gypsum crystals are found at the well perforation of observation well Ktzi 202 of the test site for CO2 storage at Ketzin, Germany. XRD analysis confirms pure gypsum. Fluid samples before and after CO2 injection are analyzed. Geochemical modeling is conducted to identify the mechanisms that lead to gypsum formation. The modeling is carried out with PHREEQC and Pitzer database due to the high salinity of up to 5 mol per kg water. Due to their significantly higher reactivity compared to other minerals like silicates, calcite, dolomite, magnesite, gypsum, anhydrite, and halite are considered as primary mineral phases for matching the observed brine compositions in our simulations. Calcite, dolomite, and gypsum are close to saturation before and after CO2 injection. Dolomite shows the highest reactivity and mainly contributes to buffering the brine pH that initially decreased due to CO2 injection. The contribution of calcite to the pH-buffering is only minor. Gypsum and anhydrite are no geochemically active minerals before injection. After CO2 injection, gypsum precipitation may occur by two mechanisms: (i) dissociation of CO2 decreases activity of water and, therefore, increases the saturation of all minerals and (ii) dolomite dissolution due to pH-buffering releases Ca2+ ions into solution and shifts the mass action to gypsum. Gypsum precipitation decreases with increasing temperature but increases with increasing partial CO2 pressure. Our calculations show that calcium sulfate precipitation increases by a factor of 5 to a depth of 2000 m when Ketzin pressure and temperature are extrapolated. In general, gypsum precipitation constitutes a potential clogging hazard during CO2 storage and could negatively impact safe site operation. In the presented Ketzin example, this threat is only minor since the total amount of gypsum precipitation is relatively small.

Effect of sulfate on CO2 binding efficiency of recycled alkaline materials

CO2 mineralization using alkaline waste materials and by-products is a promising technology to reduce CO2 emissions. This work investigates the impact of alkali sulfates on the carbonation process. Detailed investigations of the carbonation reaction show that the sulfates are important phases impacting the mineralization. Alkalis alone accelerate the kinetics and change the morphology of the precipitated phases. Sulfates additionally reduce the amount of CO2 mineralized since a part of calcium precipitates as calcium sulfate. The mutual interaction between alkalis and sulfate ions provides a tool to control the mineralization kinetics and especially the extent of carbonation by preventing calcium sulfate precipitation at surplus of alkalis. Furthermore, sulfate-containing materials, which so far have not been considered as suitable for CO2 mineralization (e.g. gypsum), can now be considered for CO2 sequestration. A modification of the Steinour formula, used for calculations of the carbonation potential, is proposed to account for the observed effects.

CALCIUM SULFATE SCALE IN THE PETROLEUM INDUSTRY

Oilfield scale is defined as the precipitation of hard, adherent deposits of inorganic solid originating from aqueous media. This constitutes sulfate and carbonate of the alkaline earth metals calcium, barium and strontium and complex salts of iron. Generally, the process of the scale deposition occurs when the product solubility of a compound considered is exceeded. The formation of scale, such as calcium sulfate, has long recognised as one of the serious problems in oil and gas production leading to reduced production rates as flow becomes restricted. Calcium sulfate scale found in the oilfield is in the form of gypsum (CaSO4, 2H2,0) which is the most stable form at temperatures of 40 °C or less at atmosphere pressure. Above this temperature, anhydrite (CaSO4,) may be found, although hemihydrate (CaSO. 1/2H,O) may form under certain conditions. The reaction for precipitation of calcium sulfate is as follows: Ca+2 (aq) + so4-2 (aq) = CaSO4 (solid) The solubility of calcium sulfate in distilled water is 2080 mg/l at 25 "C. Calcium sulfate scale arises from several causes, such as temperature, dissolved salts, pressure, and time. The main points of this paper are focused on nomenclature, chemical structure, the occurrence of calcium sulfate scale, example of calcium sulfate scale in the petroleum industry, and calculation of calcium sulfate solubility in brine.

Revisiting the roles of salinity, temperature and water activity in phase selection during calcium sulfate precipitation

Phase selection during precipitation of calcium sulfate is known to be influenced by various parameters. Here we demonstrate that the relative level of supersaturation determines whether more or less hydrated crystalline phases are formed.

Exploiting Confinement to Study the Crystallization Pathway of Calcium Sulfate

AbstractCharacterizing the pathways by which crystals form remains a significant challenge, particularly when multiple pathways operate simultaneously. Here, an imaging‐based strategy is introduced that exploits confinement effects to track the evolution of a population of crystals in 3D and to characterize crystallization pathways. Focusing on calcium sulfate formation in aqueous solution at room temperature, precipitation is carried out within nanoporous media, which ensures that the crystals are fixed in position and develop slowly. The evolution of their size, shape, and polymorph can then be tracked in situ using synchrotron X‐ray computed tomography and diffraction computed tomography without isolating and potentially altering the crystals. The study shows that bassanite (CaSO4 0.5H2O) forms via an amorphous precursor phase and that it exhibits long‐term stability in these nanoscale pores. Further, the thermodynamically stable phase gypsum (CaSO4 2H2O) can precipitate by different pathways according to the local physical environment. Insight into crystallization in nanoconfinement is also gained, and the crystals are seen to grow throughout the nanoporous network without causing structural damage. This work therefore offers a novel strategy for studying crystallization pathways and demonstrates the significant impact of confinement on calcium sulfate precipitation, which is relevant to its formation in many real‐world environments.

Pore structure evolution characteristics of sandstone uranium ore during acid leaching

To better understand the permeability of uranium sandstone, improve the leaching rate of uranium, and explore the change law of pore structure characteristics and blocking mechanism during leaching, we systematically analyzed the microstructure of acid-leaching uranium sandstone. We investigated the variable rules of pore structure characteristics based on nuclear magnetic resonance (NMR). The results showed the following: (1) The uranium concentration change followed the exponential law during uranium deposits acid leaching. After 24 h, the uranium leaching rate reached 50%. The uranium leaching slowed gradually over the next 4 days. (2) Combined with the regularity of porosity variation, Stages I and II included chemical plugging controlled by surface reaction. Stage I was the major completion phase of uranium displacement with saturation precipitation of calcium sulfate. Stage II mainly precipitated iron (III) oxide-hydroxide and aluminum hydroxide. Stage III involved physical clogging controlled by diffusion. (3) In the three stages of leaching, the permeability of the leaching solution changed with the pore structure, which first decreased, then increased, and then decreased.

Sulfate precipitation treatment for NOM-rich ion exchange brines

Ion exchange (IEX) resins can remove natural organic matter (NOM) from drinking water sources. However, the IEX system produces a waste brine rich of sodium, chloride, NOM and sulfate. The treatment of the waste brine aims to recover a clean solution rich of sodium chloride, that can be reused to regenerate IEX resin. Previous research showed that ceramic nanofiltration partially removes NOM from the waste brine, but sulfate removal requires additional treatment. Sulfate removal by chemical precipitation was previously studied either on brines with low NOM concentrations or water with low concentrations of NOM and salts. The current work focussed on sulfate removal from NOM-rich brines by chemical dosing of (1) BaCl2, resulting in precipitation of barite (BaSO4), and (2) CaCl2, Ca(OH)2 and NaAlO2, resulting in precipitation of calcium sulfate and, subsequently, ettringite (Ca6Al2(SO4)3(OH)12). Additionally, the effect of NOM on SO42− removal was studied. Modelling and batch experiments were conducted with IEX and synthetic brines within the typical ion strength range of 0.1 to 1 M. With doses of 2.2 g of BaCl2 per g of initial sulfate, BaSO4 precipitation removed more than 83 percent of sulfate, resulting in final concentrations below 0.4 g/L even in the presence of NOM. However, NOM inhibited the precipitation of calcium sulfate and, subsequently, ettringite. With doses of 1.3 g of CaCl2, 0.5–0.7 g of Ca(OH)2 and 0.4–0.6 g of NaAlO2 per g of initial sulfate, calcium sulfate and ettringite precipitation removed between 8 and 95 percent of sulfate from NOM-rich brines, resulting in final concentrations between 0.8 and 2 g/L. As a reference, NOM-free brines required doses of 1.3 g of CaCl2, 0.2–0.7 g of Ca(OH)2 and 0.1–0.6 g of NaAlO2 per g of initial sulfate for 89 to 99 percent of sulfate removal, resulting in final concentrations of 0.2 g/L. The inhibition might be attributed to covering of crystal sites by NOM molecules, and to NOM coagulation with aluminium.

Enhancing anti-scaling resistances of aromatic polyamide reverse osmosis membranes using a new natural materials inhibitor

The anti-scaling properties of green additive seeds were used as a novel environmentally friendly on the precipitation of calcium sulfate (gypsum) scale on the reverse osmosis (RO) in desalination plants. Initial screening of many additives included: Ginger extract, Pepper extract, Lysine, and Glutamic amino acid have been carried out. The effect of additives was evaluated by measuring calcium ions remained in the solution, and their performance that was comparable with the blank supersaturated calcium sulfate solution. The formation of the gypsum crystals has been verified using XRD and SEM analysis. It can be seen that the degree of inhibition of gypsum scale in the presence of these inhibitors is in the following order: Ginger extract > Pepper extract > Lysine > Glutamic at different concentrations (25,50,100 ppm). A concentration of 100 ppm Ginger extract led to be superior to others with an inhibition 98.80%. The SEM images of the collected precipitates when green inhibitors were added as a scale inhibitor, and were compared with that of the blank solution. The effect of Ginger extract (gypsum) scaling on selected reverse osmosis (RO) membrane surfaces was observed in the extent of surface scale coverage and surface crystal size among the membrane studied.