Modelling and performance evaluation of chromatographic monosaccharide recovery from concentrated acid lignocellulosic hydrolysates

BACKGROUND: Chromatographic fractionation of concentrated acid lignocellulosic hydrolysates was investigated. The goal was to present a model that can be used in designing and performance evaluation of the fractionation process. Simple models were fitted to the experimental sorption data of the main components of the hydrolysates (sulfuric acid, monosaccharides, and acetic acid) on CS16GC resin. A column model which takes into account resin shrinking was derived. RESULTS: Simulation results were found to be in good agreement with the experimental results. The isotherm models predicted correctly the co‐operative effect of H₂SO₄ on the sorption of the other adsorbates. The effect of column loading on the productivity of the separation process was studied with simulations. With 20 wt% H₂SO₄, the highest productivity was obtained with 11.5 vol% column loading. In addition, a process consisting of concentrated acid lignocellulose hydrolysis, batchwise chromatographic separation, and H₂SO₄ recycling was investigated. With the recycling, the maximum productivity was obtained with 18.2 vol% column loading. CONCLUSIONS: It was demonstrated that the entire reactor‐separation process with internal recycling must be considered when evaluating the performance of the monosaccharide‐acid separation step. Process performance was found to decrease with increasing feed concentration of sulfuric acid. Copyright © 2012 Society of Chemical Industry     

Novel imino diacetamide grafted styrene divinyl benzene resin for separation and recovery of palladium from simulated high level liquid waste

Imino diacetamide styrene divinyl benzene resin was evaluated for separation of palladium from simulated high level liquid waste (HLLW). The kinetics of sorption was found to be fast, and the kinetic data were fitted well to the pseudo-second-order kinetics model. Very high K_d (~10³) were obtained for Pd for feed solutions having acidity from 0.25 M to 4.0 M HNO₃. The loading studies of the resin showed the maximum sorption capacity of 54 mg/g. Back extraction studies showed that sorbed Pd can be effectively back extracted using 0.01 M thiourea in 0.2 M HNO₃. Studies with simulated HLLW showed preferential sorption of Pd over other metal ions.     

Studies on the Sorption of Palladium using Cross‐Linked Poly (4‐Vinylpyridine‐Divinylbenzene) Resins in Nitric Acid Medium

Various cross‐linked (4, 8, and 12%) gel‐type weak‐base poly(4‐vinylpyridine) (PVP) resins were studied for palladium recovery from nitric acid medium. The sorption of palladium was found to decrease with an increase in cross‐linkage of the resin. 8 and 12% PVP resins exhibited maximum D _Pd(II) values at 2–6 M HNO₃, whereas 4% PVP resin showed maximum D _Pd(II) values at lower acidities (0.1 M HNO₃). FT‐IR, SEM, and XPS techniques were used for the characterization of palladium‐loaded resins. Detailed studies were carried out with the resin of modest cross‐linkage i.e., 8% PVP resin. The sorption isotherm studies revealed that the maximum palladium loading approaches the theoretical capacity of the resin, presuming the sorption of palladium as divalent anion at 4 M HNO₃. The pseudo‐second order kinetics model yielded the best fit for the experimental data of sorption kinetics. An increase in temperature accelerates the rate of palladium extraction and also the addition of chloride ions increases the palladium uptake. Column studies were performed using 4 and 8% PVP resins in 2 and 4 M nitric acid concentrations. The loaded palladium could be eluted efficiently with acidic thiourea solution.     

Sorption of N2, CH4 and CO2 in Silicalite-1

An isosteric sorption apparatus has been used to obtain data for the sorption of N₂, CH₄ and CO₂ in Silicalite-1 over the temperature range 0–70°C. Isotherms have also been determined in a high pressure sorption balance at equilibrium pressures up to 20 atm. Isosteric heats of sorption have been calculated from these sorption data. Separation factors calculated from Henry's Law constants determined from the initial slopes of the single-component isotherms have been found to be in good agreement with experimental separation factors. The single-component sorption data have been fitted to various isotherm models and the Ideal Adsorbed Solution theory has been used to predict a binary sorption isotherm from the respective single-component data. The predicted isotherm is in good agreement with the corresponding experimental isotherm.     

Weak Base Anion Exchanger Amberlite FPA51 as Effective Adsorbent for Acid Blue 74 Removal from Aqueous Medium – Kinetic and Equilibrium Studies

In this work, the macroporous anion exchange resin – Amberlite FPA51, is proposed as the effective adsorbent for the removal of Acid Blue 74 from aqueous solutions. The sorption mechanism was investigated under static conditions taking into account the phase contact time, solution pH, initial dye concentration, and temperature. The equilibrium data were fitted to the Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. The maximum monolayer capacity Q ₀ was 123.8 mg/g. The adsorption kinetics was found to follow the pseudo-second order model. The sorption energy was equal to 14.5 kJ/mol and indicated that the adsorption process of the dye may be described via a chemical anion-exchange mechanism.     

Removal of lead(II) from water using activated carbon developed from jujube stones,a low-cost sorbent

The preparation of activated carbon from jujube stones with H₂SO₄ activation and its ability to remove lead from aqueous solutions were reported in this study. The surface structure of the activated carbon was characterized by various physico-chemical methods. Sorption studies were carried out by varying the initial metal ion and the pH: the amount of sorbed Pb(II) ions increased with increasing pH and initial Pb(II) ions concentration. The removal of lead ions was rapid and the kinetic of sorption can be well described by pseudo-second order modelling. The Langmuir model conveniently fits the data of isotherm experiments and the monolayer sorption capacity of Pb(II) ions was determined as 71.43 mg/g at pH 6.0 and 25°C. These results showed that activated carbon prepared from jujube stones could be considered for application as a potential sorbent for the removal of lead from wastewaters.     

Adsorption Characteristics of Benzaldehyde,Sulphanilic acid,and p‐Phenolsulfonate from Water,Acid, or Base Solutions onto Activated Carbon Cloth

Abstract

Adsorption of benzaldehyde (BA), sulphanilic acid (SA), and sodium salt of p‐phenolsulfonic acid (p‐PhS) from water, acid, or base solutions onto activated carbon cloth (ACC) was studied by in‐situ UV‐spectrophotometric method. Kinetics of adsorption was followed over 90 min and the data were fitted to first order rate law. The order of rate of adsorption was found to be BA>SA≈p‐PhS in water, BA>p‐PhS>SA in 1 M H₂SO₄ and BA>SA >> p‐PhS in 0.1 M NaOH. Competitive adsorptions of BA and SA from an equimolar mixture in 1 M H₂SO₄ and of BA and p‐PhS from an equimolar mixture in H₂O were studied for exploring the possibilities of separation of binary mixtures. It was found that p‐PhS was not adsorbed at all from 0.1 M NaOH solution. Adsorption isotherms of BA, SA, and p‐PhS at 30°C were derived and the data were fitted to the Langmuir and Freundlich models. The Freundlich model was found to represent the experimental data better than the Langmuir model.     

Comparison of Cr(VI) Adsorption Using Synthetic Schwertmannite Obtained by Fe3+ Hydrolysis and Fe2+ Oxidation: Kinetics,Isotherms and Adsorption Mechanism

Good sorption properties and simple synthesis route make schwertmannite an increasingly popular adsorbent. In this work, the adsorption properties of synthetic schwertmannite towards Cr(VI) were investigated. This study aimed to compare the properties and sorption performance of adsorbents obtained by two methods: Fe³⁺ hydrolysis (SCH_A) and Fe²⁺ oxidation (SCH_B). To characterise the sorbents before and after Cr(VI) adsorption, specific surface area, particle size distribution, density, and zeta potential were determined. Additionally, optical micrographs, SEM, and FTIR analyses were performed. Adsorption experiments were performed in varying process conditions: pH, adsorbent dosage, contact time, and initial concentration. Adsorption isotherms were fitted by Freundlich, Langmuir, and Temkin models. Pseudo-first-order, pseudo-second-order, intraparticle diffusion, and liquid film diffusion models were used to fit the kinetics data. Linear regression was used to estimate the parameters of isotherm and kinetic models. The maximum adsorption capacity resulting from the fitted Langmuir isotherm is 42.97 and 17.54 mg·g⁻¹ for SCH_A and SCH_B. Results show that the adsorption kinetics follows the pseudo-second-order kinetic model. Both iron-based adsorbents are suitable for removing Cr(VI) ions from aqueous solutions. Characterisation of the adsorbents after adsorption suggests that Cr(VI) adsorption can be mainly attributed to ion exchange with SO₄²⁻ groups.     

Uranium sorption from aqueous solutions using polyacrylamide-based chelating sorbents

ABSTRACT

This article introduces an investigation on the sorption power of two polyacrylamide-based chelating sorbents for uranium ion removal from aqueous solutions. The studied sorption parameters involved pH, contact time, initial uranium concentration, and polymer dosage. The results revealed that a maximum uptake percentage of 65.3 mg/g and 20.1 mg/g for polymers I and II, respectively, could be obtained at pH 4 with 120 min shaking time. Based on isotherm, kinetic, and thermodynamic studies, the sorption process of uranium on the chelating polymers is said to follow Langmuir isotherm model with pseudo second-order mechanism and exothermic nature.     

Biosorptive uranium uptake by a Pseudomonas strain: characterization and equilibrium studies

The biosorptive uranium(VI) uptake capacity of live and lyophilized Pseudomonas cells was characterized in terms of equilibrium metal loading, effect of solution pH and possible interference by selected co‐ions. Uranium binding by the test biomass was rapid, achieving >90% sorption efficiency within 10 min of contact and the equilibrium was attained after 1 h. pH‐dependent uranium sorption was observed for both biomass types with the maximum being at pH 5.0. Metal uptake by live cells was not affected by culture age and the presence of an energy source or metabolic inhibitor. Sorption isotherm studies at a solution pH of either 3.5 or 5.0 indicated efficient and exceptionally high uranium loading by the test biomass, particularly at the higher pH level. At equilibrium, the lyophilized Pseudomonas exhibited a metal loading of 541 ± 34.21 mg g^?1 compared with a lower value by the live organisms (410 ± 25.93 mg g^?1). Experimental sorption data showing conformity to both Freundlich and Langmuir isotherm models indicate monolayered uranium binding by the test biomass. In bimetallic combinations a significant interference in uranium loading was offered by cations such as thorium(IV), iron(II and III), aluminium(III) and copper(II), while the anions tested, except carbonate, were ineffective. Uranium sorption studies in the presence of a range of Fe³⁺ and SO₄^2? concentrations indicate a strong inhibition (80%) by the former at an equimolar ratio while more than 70% adsorption efficiency was retained even at a high sulfate level (30 000 mg dm^?3). Overall data indicate the suitability of the Pseudomonas sp biomass in developing a biosorbent for uranium removal from aqueous waste streams. © 2001 Society of Chemical Industry     

THERMODYNAMIC CONSIDERATIONS ON THE PURIFICATION OF H2SO4 AND HIX PHASES IN THE IODINE-SULFUR HYDROGEN PRODUCTION PROCESS

The reaction equilibrium and phase equilibrium in H₂SO₄ and HIx phases produced by the Bunsen reaction of the iodine-sulfur thermochemical hydrogen production process were examined using a chemical process simulator, ESP, with a thermodynamic database based on the mixed solvent electrolyte model. At temperatures lower than ca. 110°C, the reaction of HI and H₂SO₄ produced elemental sulfur in both phases. At higher temperatures, the reverse Bunsen reaction occurred, and SO₂ was produced in the H₂SO₄ phase. In the HIx phase, conversely, SO₂ formation predominated in a narrow temperature range and H₂S was produced with the increase in temperature. The presence of N₂ gas lowered the temperature of the predominant reaction change. A feed of O₂ for purification was proposed to suppress the consumption of objective components in the H₂SO₄ phase purification, and an O₂ feed to the HIx phase for the suppression of H₂S and S impurities was proposed by the simulation.     

Adsorption of uranium from sulfate leach liquor using rice straw impregnated with chlorophenyl hydrazinyl pyrazoloquinazolinon

The impregnation of rice straw with 2-amino-3-(2-(4-chlorophenyl)hydrazinyl)-8,8-dimethyl-8,9-dihydropyrazolo[1,5-a]quinazolin-6(7H)-one (CPHPQ) has been used for the recovery of uranium from sulfate leach liquor. The uranium adsorption and elution of solvent impregnated mercerized rice straw (SIMRS) were carried out using a batch technique. The uranium adsorption controlling factors include pH, initial uranium concentration, contact time, S/L ratio, and temperature. Thermodynamic characteristics showed that the adsorption process is exothermic with enthalpy change ΔH = ?152.1 kJ/mol. The kinetics data fit well with a pseudo-second-order model. The equilibrium data fit well with the Langmuir isotherm. Uranium cake was obtained from the eluate solution using hydrogen peroxide as UO₄.2H₂O precipitate.     

Water purification of removal aqueous copper (II) by as-grown and modified multi-walled carbon nanotubes

This study compares aqueous copper (II) adsorbed onto as-grown and modified carbon nanotubes (CNTs), using H₂SO₄ and H₂SO₄/KMnO₄ processes. H₂SO₄ and H₂SO₄/KMnO₄ modifications reduced pH_iep and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that some functional groups were formed on modified CNTs. The adsorption capacity of copper (II) onto modified CNTs was greater than that of as-grown CNTs, especially at pH 6. The results demonstrate that the modified processes increased the adsorption capacity because the functional groups were generated on the modified surfaces of the CNTs. Additionally, the adsorption capacity of copper (II) onto as-grown and modified CNTs both increased with temperature, and the results indicated that the Langmuir isotherm fitted the experimental data well. Simulation results indicated that the ΔH⁰ values of as-grown, H₂SO₄-modified CNTs and H₂SO₄/KMnO₄-modified CNTs were 4.83, 14.37 and 29.92 kJ/mol, respectively. Based on ΔH⁰, the adsorption of Cu²⁺ onto H₂SO₄/KMnO₄-modified CNTs is suggested to proceed simultaneously by physisorption and chemisorption but that onto as-grown and H₂SO₄-modified CNTs may proceed only by physisorption.     

Removal of linuron from water by natural and activated bentonite

The sorption of linuron on bentonite desiccated at 110°C untreated, and acid‐treated with H₂SO₄ solutions over a concentration range between 0.25 M and 1.00 M from aqueous solution at 25°C has been studied by using batch experiments. In addition, column experiments were carried out with the bentonite sample treated with the 1.00 M H ₂SO₄ solution [B‐A(1.00)] by using two aqueous solutions of linuron of different concentrations (C=4.97 mg dm⁻³ and C=7.63 mg dm⁻³ ). The experimental data points have been fitted to the Langmuir equation in order to calculate the sorption capacities (X_m) of the samples; X_m values range from 0.02 g kg⁻¹ for the untreated bentonite [B‐N] up to 0.20 g kg⁻¹ for the sample acid‐treated with the 1.00 M H₂ SO₄ solution. The removal efficiency (R ) has also been calculated; R values ranging from 15.86% for the [B‐N] sample up to 41.54% for [B‐A(1.00)]. The batch experiments show that the acid‐treated bentonite is more effective than the natural bentonite in relation to sorption of linuron. The column experiments show that the B‐A(1.00) sample might be reasonably used in removing linuron, the column efficiency increasing from 61.8% for the C=7.63 mg dm⁻³ aqueous solution of linuron up to 77.6% for the C=4.97 mg dm⁻³ one. © 1999 Society of Chemical Industry     

Column Sorption of Citric Acid from Aqueous Solutions Using Tri-n-octylamine-Impregnated Macroporous Resins

Abstract

Column sorption of citric acid from aqueous solutions using tri-n-octylamine (TOA)-impregnated macroporous resins was studied at 298 K. The breakthrough curves were measured as a function of the feed flow rate, citric acid concentration in the feed solution, TOA concentration in the resin phase, and type of resin. It was found that the type of resin played a most important role in determining the saturated capacity under comparable conditions. The desorption of citric acid from loaded resins was also evaluated with various eluants, including HCl, HNO³, H²SO⁴, and Na²CO³     

弱碱性树脂处理β-萘磺酸废水的吸附分离热力学性能

研究了β-萘磺酸废水中β-萘磺酸、H₂SO₄、H₂SO₃ 单组分吸附平衡,并以Langmuir、Freundlich模型对其进行模拟.吸附过程的热力学计算及分析结果表明,吸附过程为放热的化学吸附过程,吸附量顺序为H₂SO₄>NSA>H₂SO₃,推动力大小顺序为H₂SO₄>NSA>H₂SO₃,吸附过程熵增加.以D301R弱碱性树脂为吸附剂,可有效地实现三者的分离.     

Influence of tramadol [2-[(dimethylamino)methyl]-1-(3-methoxyphenyl) cyclohexanol hydrate] on corrosion inhibition of mild steel in acidic media

Tramadol[2-[(dimethylamino)methyl]-1-(3-methoxyphenyl)cyclohexanol hydrate], a drug, was tested as a corrosion inhibitor for mild steel in 0.5 M HCl and 0.25 M H₂SO₄ separately at 300, 310 and 320 K using mass loss and galvanostatic polarization techniques. The percentage protection efficiencies were evaluated at different concentrations of the inhibitor at different temperatures. The protection efficiency increased with increase in inhibitor concentration and decreased with increase in temperature in both the acid solutions. Galvanostatic polarization studies showed that the inhibitor is of mixed type with a slight predominance of cathodic character. The inhibitor was more active in HCl than in H₂SO₄. The maximum protection efficiency approached 82.6% in the presence of 2.16 × 10⁻³ M inhibitor. Some samples of mild steel were examined by scanning electron microscopy. The inhibitor was found to adsorb on the mild steel surface according to the Langmuir adsorption isotherm. The thermodynamic functions of dissolution and adsorption processes were evaluated.     

Factors Affecting on the Sorption/Desorption of Eu (III) using Activated Carbon

Abstract

The sorption and desorption of Eu (III) on H‐APC activated carbon using a batch technique has been studied as a function of carbon type, shaking time, initial pH solution, temperature, particle size of carbon, and concentration of the adsorbent and the adsorbate. The influence of different anions and cations on adsorption has been examined. The experimental data have been analyzed by Langmuir, Freundlich, and Temkin sorption isotherm models and the adsorption data for Eu (III) onto activated carbon were better correlated to the Temkin isotherm and the maximum absorption capacities obtained was 46.5 mg g^?1. Anions of phosphate, carbonate, oxalate, and acetate were found to increase the adsorption of Eu (III), whereas nitrate, chloride and all studied cations, potassium, sodium, calcium, magnesium, and aluminum have a negative effect on the adsorption capacity. More than 99% europium adsorbed on H‐APC eluted with 0.5 M HCl solution. The activated carbon prepared from apricot stone using 70% H₃PO₄ could be considered as an adsorbent that has a commercial potential for Eu (III) treatment.     

Boron removal from aqueous solutions by ion-exchange resin: Batch studies

In this study, boron removal from aqueous solutions was examined using Dowex 2 × 8 anion exchange resin. The sorption behaviour of resin was investigated as a function of pH, contact-time and temperature, initial boron concentration of solution, resin dosage and effect of other ions. The maximum sorption value for boron was observed at pH 9. The percent removal of boron decreased as temperature and initial boron concentration increased. The presence of other ions in solutions affected the sorption of boron significantly. The Langmuir isotherm was used to describe observed sorption phenomena. The maximum sorption capacity of Dowex 2 × 8 was determined as 16.98 mg B/g at pH 9 and 25°C. The quantitative stripping of boron from resin was obtained with 0.5 M H₂SO₄ or 0.5 M HCl solutions at 25°C. A generalised ion exchange kinetic model was applied to fit the kinetic data obtained by using the Dowex 2 × 8 and the rate-determining step is determined as film-intraparticle diffusion.     

KINETICS OF CADMIUM ION SORPTION ON ION EXCHANGE AND CHELATING RESINS

ABSTRACT

Cadmium sorption from aqueous solutions on sulfonic (C-150) and iminodiacetic (S-930) Purolite macroporous resins was investigated. The influence of operating variables such as initial pH, Cd(H) concentration, time and temperature on the equilibrium parameters was measured. The ion preference and sorption ability of resins, i.e. binding constant (b) and saturation capacity {x_m), derived from sorption isotherm, depend on the functional group structure. The Cd(II) uptake is only particle diffusion controlled. The kinetic parameters, i.e. t_1/2 values for 50 % attainment of equilibrium sorption, rate constant (K¯ ) and diffusion coefficient (D¯) are higher on the sulfonic resin. The “moving boundary” particle diffusion model fits the entire ion sorption process on chelating resin, but only the initial sorption on the sulfonic resin, confirming the difference in chemistry between chelation and ion exchange.