Ammonia Removal from Aqueous Solutions by Iranian Natural Zeolite

Abstract

The capability of Iranian natural clinoptilolite for ammonia removal from aqueous solutions has been thoroughly studied. Both batch and continuous (column) experiments were carried out. The viability of this natural zeolite in reducing the leakage of ammonia to the environment through waste water streams was a main focus of this research. Through the batch experiments, the effect of process variables such as the size of zeolite particles, pH, and ammonia concentration of the feed solution on the kinetics of ammonia uptake were investigated. Ammonia removal occurred rapidly and within the first 15 minutes of contact time, a major part of ammonia was removed from the solution. An adsorption capacity about 17.8 mg NH₄ ⁺/g zeolite at feed ammonia concentration of 50 mg/L was obtained and the optimum range for pH was achieved about 5.5–7.6. The adsorption capacity of clinoptilolite in the continuous mode was about 15.16 and 15.36 mg NH₄ ⁺/g zeolite for the original and regenerated types of clinoptilolite, respectively, where feed ammonium concentration was 50 mg/L. Increasing the feed ammonium concentration to 100 mg/L did not reduce the capability of the column for its ammonium removal and up to a bed volume (BV) of 85, there was only less than 1 mg/L ammonium in the column outlet. Presence of cations such as Ca²⁺, Mg²⁺ and Na⁺ in the feed solution reduced the clinoptilolite adsorption capacity to about 11.68 mg NH₄ ⁺/g zeolite. Regeneration experiments were carried out using concentrated sodium chloride solutions, as well as tap water. Where tap water was used as the regenerant, gradual release of ammonium from exhausted clinoptilolite was observed.     

Ion exchange properties of NASICON-type ceramics—Application to ion selective electrodes

The ion-exchange properties of NASICON type ceramics of composition Na₃Zr₂Si₂PO₁₂ were investigated in aqueous solutions of NaCl, LiCl and KCl. The solution analysis shows that the [Zr₂Si₂PO₁₂] framework strongly prefers Na⁺ ion relative to K⁺ and Li⁺. The exchange current density of the alkali-cations at the NASICON/solution interface determined by impedance measurements varies in the order Na⁺>Li⁺>K⁺. These results agree well with the selectivity coefficients of Na⁺ ion selective electrodes based on NASICON. The interference process to alkali-cations in the NASICON based electrode was shown to result from an ionic exchange. The selectivity was suggested to be governed by the mobility of the cation inside the NASICON framework.     

Hydrothermal modification of natural zeolites to improve uptake of ammonium ions

The modification of natural zeolites was carried out under hydrothermal conditions to improve the effectiveness of the uptake of ammonium ions. Natural zeolites originating in Japan, such as mordenite and clinoptilolite with quartz, feldspar and a trace of layered silicate, were treated with 0.1, 0.3, 1.0 and 3.0 M NaOH solutions at temperatures from 25 to 150 °C under autogenous pressure for 7 days. After the hydrothermal treatment, the transformation of the zeolites to phillipsite, hydroxyl‐sodalite and analcime was observed, depending on the temperature and NaOH concentration. The amounts of ammonium ions taken up into the hydrothermally‐treated zeolites were compared with those of the starting materials. The treated products, containing mainly phillipsite, took up twice the amount of ammonium ions as the starting materials. The maximum uptake of ammonium ions was 1.92 mmol g^?1. The number of ammonium ions taken up into phillipsite was equal to the number of Na⁺ ions released from phillipsite. These results indicate that the uptake of ammonium ions proceeds by an ion‐exchange mechanism with Na⁺ ions. Copyright © 2005 Society of Chemical Industry     

An assessment of the effectiveness of natural zeolites for removal of ammonium and zinc from their dilute solutions

The adsorption of NH₄⁺ and Zn²⁺ by four Korean zeolite samples which contained clinoptilolite, mordenite or both was measured by adding solutions containing NH₄⁺, Zn²⁺, or both, each at a concentration ranging from 1 to 7 meq./l. Both single and successive equilibrations of the sample with the solution showed that clinoptilolite and mordenite have a certain number of NH₄⁺-selective exchange sites but not Zn²⁺-selective exchange sites. The successive equilibrations were useful to assess the effectiveness of zeolite for removal of NH₄⁺ and Zn²⁺. Mordenite and clinoptilolite would adsorb NH₄⁺ corresponding to 40–45% and 30% of its cation exchange capacity (CEC), respectively, from the solution containing both NH₄⁺ and Zn²⁺ each at 3 meq./l. The corresponding adsorption of Zn²⁺ would be 5–10% of the CEC of each mineral.     

Synthesis, Characterization and Properties of New Lauryl Amidopropyl Trimethyl Ammoniums

A new lauryl amidopropyl trimethyl ammonium methyl carbonate with the formula CH₃(CH₂)₁₀CONH(CH₂)₃N⁺(CH₃)₃CH₃CO₃ ^? was synthesized via a high pressure process with tertiary amines and dimethyl carbonate, and its chemical structure was confirmed using ¹H-NMR spectra, mass spectral fragmentation, and FTIR spectroscopic analysis. In addition, several quaternary ammonium salts with new counterions X^? (X^?=HCO₃ ^?, HCOO^?, CH₃COO^?, CH₃CH(OH)COO^?) were also synthesized by the ion exchange reaction of methyl carbonate quaternary ammoniums with corresponding acids. The surface activities of these compounds were measured, including surface tension (??), critical micelle concentration and minimum surface area (A _min) at 25?°C. Adsorption and micellization free energies of these quaternary ammonium salts in their solutions showed a good tendency towards adsorption at interfaces. The antimicrobial activities are reported for the first time against representative bacteria and fungi for lauryl amidopropyl trimethyl ammoniums. It was found that the antimicrobial potency was Gram-positive bacteria?>?fungi?>?Gram-negative bacteria.     

A generalized model for the measurement of effective diffusion coefficients of heterovalent ions in ion exchangers by the zero-length column method

A generalized theoretical model for the measurement of effective diffusion coefficients of heterovalent ions in ion exchange resins by the zero-length column method was developed. The model included the resistance to mass transfer both in the particle and in the film and described ion fluxes with Nernst-Planck equations. Equilibria were described using a model based on the mass action law. The values of intraparticle diffusivity of Cu²⁺, Cd²⁺, Zn²⁺, and H⁺ on commercial Amberlite IR-120 were obtained by non-linear regression, these values agree fairly well with data reported previously in literature. The following trend was observed: D_Cu>D_Zn>D_Cd.     

ION EXCHANGE PROPERTIES OF THE SODIUM PHLOGOPITE AND BIOTITE

ABSTRACT

The ion exchange behavior of three sodium micas (phlogopite, Ward's Sci.; phlogopite, Suzorite Inc., biotite, Ward's Sci.) towards Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺. Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ Hg²⁺, Co²⁺, Cu²⁺ Cd²⁺ and Zn²⁺ ions has been studied. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and concentration equilibrium constants as a function of metal loading and temperature were analyzed. Sodium micas exhibit high affinity for heavy alkali metals with the selectivity order Rb⁺ > Cs⁺ > K⁺. By studying the cesium uptake in the presence of NaNO₃, CaCl₂, NaOH, NaOH+KOH, HNO₃ electrolytes (in the range of 0.01–6 M) it was found that sodium micas could remove cesium efficiently in neutral and alkaline media, which make them promising for certain types of nuclear waste treatment.     

Effect of chemically modified clinoptilolite on the thermal,morphological, and gas separation properties of mixed matrix membranes

Mixed matrix membranes (MMM) based on polysulfone and chemically modified clinoptilolite were prepared. Clinoptilolite enriched with Ca²⁺, K⁺, and Na⁺ by ion exchange at two test temperatures was prepared. Chemical composition was monitored by energy dispersive X‐ray spectroscopy. X‐ray diffraction, thermogravimetric analysis, and N₂ adsorption–desorption isotherms were also performed. Thermal and morphological properties of MMM were evaluated. CH₄/CO₂ gas mixture permeability tests at different upstream pressure were carried out. Type of exchanged cation in modified clinoptilolite affected the CO₂ permeability. An improvement on the CO₂/CH₄ selectivity values in the MMM compared to the polymeric membrane was appreciated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45659.     

Interactions of Some Hofmeister Cations with Sodium Dodecyl Sulfate in Aqueous Solution

In this work, we have investigated the influence of some alkali metal ions on the Krafft temperature (T_K) and critical micelle concentration (CMC) of a classical ionic surfactant, sodium dodecyl sulfate (SDS), over a wide range of temperature. The alkali metal cations such as Li⁺, Na⁺, Cs⁺, and K⁺ are found to affect the solubility and hence the T_K of the surfactant. It was observed that kosmotropic Li⁺ lowers the T_K of the surfactant. Due to the common ion effect, the solubility of SDS decreases in the presence of Na⁺, resulting in an increase in the T_K. On the other hand, chaotropic K⁺ and Cs⁺, capable of forming contact ion pairs with the chaotropic dodecyl sulfate ion, lower the solubility and hence elevate the T_K. In terms of decreasing the T_K, the ions follow the trend: Li⁺ > Na⁺ > Cs⁺ > K⁺ except for 0.0025 M CsCl. The added cations screen the charge of the micelle surface and facilitate closer packing of the surfactant with a consequent decrease in the CMC. In terms of the effectiveness in lowering the CMC, the ions follow the order: Cs⁺ > K⁺ > Na⁺ > Li⁺. In the presence of added electrolytes, the γ_CMC values are found to be lower than the corresponding values in pure water. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy changes) of micellization were calculated to gain insights into the mechanism of the process.     

SEPARATION OF COBALT(II) AND NICKEL(II) IONS FROM ACID AQUEOUS SOLUTIONS BY Co IT ION-EXCHANGE INTO γ-TITANIUM PHOSPHATE

ABSTRACT

The Co²⁺-2H⁺, Ni²⁺-2H⁺, and Co²⁺-Ni²⁺-2H⁺ ion exchange processes into γ-Ti(H₂PO₄)(PO₄)2H₂O were studied. Exchange isothenns and titration curves were obtained. Monometallic half ion exchange phases were formed by using MC₂+HCl (M=Co,Ni) solutions. Equilibrium constants, free energy, enthalpy, and entropy of the Co²⁺-2H²⁺ ion exchange reaction were determined. In (Co,Ni)Cl₂ solutions, bimetallic a half ion exchange substitution solid solution is detected. Equilibrium constant of the Co²⁺-Ni²⁺ substitution process in the γ-Ti(Co_xNi_0.5?x.HPO₄)(PO₄)nH₂O phase at 85°C was determined. In (Co,Ni)Cl₂+HCl solutions, total separation of Co²⁺ and Ni²⁺ is obtained.     

Removal of Heavy Metals and Other Cations from Wastewater Using Zeolites

Abstract

Zeolites from abundant natural deposits were investigated by the Bureau of Mines for efficiently cleaning up mining industry wastewaters. Twenty-two zeolites were analyzed by X-ray diffraction and inductively coupled plasma analysis (ICP). These included clinoptilolite, mordenite, chabazite, erionite, and phillipsite. The zeolites were primarily in the sodium or calcium form, but potassium and magnesium counter ions were also present. Bulk densities of a sized fraction (minus 40, plus 65 mesh) varied from 0.48 to 0.93 g/cc. Heavy metal ion exchange loading values on two clinoptilolites ranged from 1.6 meq/g for lead to 0 meq/g for mercury in single ion tests. The selectivity series was determined to be Pb>Cd>Cs>Cu(II)>Co(II)>Cr(III)>Zn>Ni(II)>Hg(II). Sodium was the most effective exchangeable ion for ion exchange of heavy metals. Wastewater from an abandoned copper mine in Nevada was used to test the effectiveness of clinoptilolite for treating a multiion wastewater. Aluminum, Fe(III), Cu(II), and Zn in the copper mine wastewater were removed to below drinking water standards, but Mn(II) and Ni(II) were not. Calcium and NH₄ were absorbed preferentially to all heavy metal cations except Pb. Adsorbed heavy metals were eluted from zeolites with 3-pct NaCl solution. Heavy metals were concentrated in the eluates up to 30-fold relative to the waste solution. Anions were not adsorbed by the zeolites.     

Clinoptilolites for nitrogen/methane separation

Clinoptilolites, naturally occurring zeolites, currently used by nuclear industry for ion exchange and drying, were evaluated for the nitrogen/methane separation. Ion exchange of purified clinoptilolite was carried out individually with the cations Na⁺, Mg²⁺, Ca²⁺, K⁺ and H⁺, and the adsorption isotherms and diffusion rates were measured. Purified and Mg-clinoptilolite show potential for nitrogen/methane separation and high-pressure adsorption isotherms were measured in a differential absorption bed. Pressure swing adsorption simulations were performed for purified clinoptilolite, Mg-clinoptilolite and the commercial sorbent ETS-4. Purified clinoptilolite shows slightly higher recovery and lower productivity than ETS-4 for similar product purity (∼95%). Mixed ion-exchanged clinoptilolites of Mg/Ca cations, K/Na cations and Mg/Na cations were also prepared and studied for the nitrogen/methane separation. Mg/Na (50/50) mixed ion-exchanged clinoptilolite exhibits very good equilibrium and kinetic selectivity in the low-pressure range, better than purified clinoptilolite. Mixed-exchange clinoptilolites were also found to show a wide range of adsorption characteristics with varying ratios of cation exchange, thereby making them suitable for further improvements in nitrogen/methane separation.     

Magnesiothermal synthesis of nanostructured SiC from natural zeolite (clinoptilolite) and mesoporous carbon CMK-1

Magnesiothermal synthesis of nanosized SiC has been successfully achieved from a mixture of the natural zeolite clinoptilolite and a high-surface area mesoporous carbon CMK-1, synthesized by impregnating a mesoporous silica template MCM-48 with sucrose, followed by carbonization in argon and removal of the silica template. Magnesium powder was used to initiate the self-combustion reaction. Removal of the alkaline and alkaline earth exchangeable cations from the clinoptilolite by ion exchange with NH₄⁺ was essential for a good yield of product, which is also dependent on the use of excess of carbon. TEM confirmed the nanostructure and size of the 15–25 nm SiC product crystallites.     

Rapid Separation of Tl+ and Pb2+ from Various Binary Cation Mixtures Using Dicyclohexano-18-crown-6 Incorporated into Emulsion Membranes

Abstract

Relative transport rates of metal cation nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, Tl⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺) in a water-toluene-water emulsion membrane system were measured. The toluene component contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6. The aqueous receiving phase contained Li₄P2O₇. When each metal cation was individually present in the aqueous source phase, metal extraction was complete within 10 min with the order of extraction being Tl⁺ > Cs⁺ > Ag⁺ > Rb⁺ > K⁺ ≥m Na⁺ and Pb⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ for uni-and bivalent cations, respectively. Significant extraction was found for all cations except Na⁺, K⁺, and Ba²⁺. Some metal ions were concentrated nearly 10-fold in a 10-min period. Relative transport rates were determined when binary cation mixtures of either Tl⁺ or Pb²⁺ were present at equal concentrations with each of the remaining metal ions in the source phase. Tl⁺, when present with either Na⁺, Cs⁺, or Rb⁺, was selectively extracted from the source phase. Complete and nearly exclusive extraction of Pb²⁺ was observed in the presence of all cations including Tl⁺. The enrichment ratios of Pb²⁺ in the binary mixtures were approximately 10 while those of the second cation were less than 0.5 except for Sr²⁺ which was 0.86. Corresponding separation factors for Pb²⁺ ranged from 1000 to > 6000.     

EQUILIBRIUM OF METALS WITH IMINODIACETIC RESIN IN BINARY AND TERNARY SYSTEMS

ABSTRACT

Experiments of binary and ternary ion exchange equilibrium of heavy metals and sodium were carried out in a complexing iminodiacetic resin Lewatit TP 207. First, binary equilibrium data were obtained at different temperatures and ionic strength and fixed to models considering two different ion exchange stoichiometrics. For ternary equilibrium data, two distinct simple models were applied. One to be applied to systems showing very different selectivity for the metals (for instance, Cu²⁺/Co²⁺/Na⁺) and the other for systems with similar selectivity for the metals (such as Zn²⁺/Co²⁺/Na⁺). The ternary equilibrium data obtained is presented in this work and fitted using the two above mentioned models. These models allow us to obtain the equilibrium parameters for binary and ternary system to be used in the design of equipment using this iminodiacetic resin.     

Chemical Modification Effect on the Sorption Capacities of Natural Clinoptilolite

This work determines the effect of chemical modification on the sorption capacity of natural Turkish zeolite, clinoptilolite, for its potential application as a sorbent. Pore size distribution and surface area are critical for assessing the suitability of the zeolite for sorbent application. Because natural clinoptilolite has small pore sizes and low surface area compared to synthetic zeolites, modification studies have been performed to improve the sorption capacity. The conversion of natural clinoptilolite to the hydrogen form has been carried out by two different ion exchange procedures, namely ammonium exchange followed by calcination and direct treatment with HCl. The natural and modified clinoptilolite samples were characterized by XRD, ²⁷Al MAS NMR and BET methods.     

ION-EXCHANGE EQUILIBRIUM OF THE Cu2+/H+, Zn2+/H+ AND Pb2+/H+ IONS ON HYDRATED FERRIC OXIDE

ABSTRACT

The ion exchange of trace amounts of Cu²⁺, Zn²⁺ and Pb²⁺ with the hydrogen-form of hydrated ferric oxide as a function of nitric acid concentration has been studied at 25, 30,35 and 60^°C. Ion exchange of these cations increases with increasing temperature in the investigated temperature range. From these results, equilibrium constants for the Cu²⁺/H⁺, Zn²⁺/H⁺ and Pb²⁺/H⁺ ion exchange on hydrated ferric oxide and thermodynamic quantities for these reactions were calculated, and some predictions made for the exchange process taking place in this material. The selectivity series is Zn²⁺ > Cu²⁺ > Pb²⁺.     

Ion exchange properties of sulfonated polycarbonate and polyimide track etch membranes

Heterogeneous sulfonation was successfully utilized to convert the surfaces of PC and PI track etched membranes with 20 nm pores into ion exchange membranes. Short sulfonation times of 1-5 min using gaseous sulfuric trioxide were sufficient to achieve good coverage of ion exchange sites on the membrane surface yet minimal structural damage to the bulk material. Consequently, the ion exchange capacities were relatively low, up to 0.015 meq/g, compared to literature. Electroselectivity typical of ion exchange materials was observed for these membranes and metal uptake of higher valences was preferred Eu³⁺ > Co²⁺ > Cs⁺. Clear differences in metal uptake properties were measured between the sulfonated PC and PI membranes with different ions. As a consequence of relatively high metal uptake and certain experiment set up also Donnan exclusion was determined to play a role in the overall ion exchange process.     

Removal of Cs1+, Sr2+ and Co2+ from aqueous solutions by adsorption on natural clinoptilolite

The adsorption properties of local clinoptilolite (Serbia) towards Cs⁺, Co²⁺, and Sr²⁺ were investigated by batch equilibration technique. The influence of equilibration time, initial metal cation concentration, solution pH and presence of EDTA on these properties was studied and discussed. Kinetic data were found to be well fitted with pseudo-second order kinetic model. Cs⁺ is preferably adsorbed by the natural clinoptilolite, followed by Sr²⁺ and Co²⁺. The Langmuir adsorption isotherm was used to determine the adsorption capacities from both single and mixed metal solutions. At pH range of 3–12 the adsorption of Cs⁺ remains almost constant, while at low pH (2–3) the adsorption is lesser. At initial pH range of 2–10 adsorption of Sr²⁺ remains approximately stable, whereas at initial pH > 10 adsorption increases significantly. The adsorption of Co²⁺ is low at low pH but increased remarkably with increasing pH and precipitated at pH > 8. Cs⁺ adsorption on the clinoptilolite was not affected by the presence of EDTA, while the presence of EDTA hinders the adsorption of Co²⁺ and Sr²⁺ on clinoptilolite.     

Mechanism of the Adsorption of Ammonium Ions from Aqueous Solution by a Chinese Natural Zeolite

Abstract

The adsorption of ammonium ions onto a Chinese natural zeolite in an agitated batch adsorber was studied. A trial‐and‐error non‐linear method was developed to examine two widely used isotherms, the Langmuir and Freundlich. The data gained from the adsorption system fitted the Freundlich isotherm better. An ion exchange model, describing the relationship among the total metal ions in the solution, NH₄ ⁺ removed from the solution, and ions initially released from the zeolite, was developed for the adsorption system. In addition, a parameter of the ion exchange potential was defined to describe the adsorption mechanism. Ion exchange was the main mechanism that accounted for the adsorption of ammonium ions onto the Chinese natural zeolite.