EXTRACTION OF CADMIUM FROM PHOSPHORIC ACID WITH DIORGANYLDITHIOPHOSPHINIC ACIDS. Part I: Equilibrium Data.

Liquid-liquid extraction of cadmium ions from 55-65 w% “black” phosphoric acid from a Nissan H process with diphenyldithio-phosphinic acid (DPP) or dicyclohexyldithiophosphinic acid (DCP) dissolved in an alkane (C₁₂ or C₁₆) at 90°C was investigated. The cadmium concentration could be reduced from 25 ppm to below 2 ppm at a ligand/(Cd+Cu) ratio of 6 (mol/mol). Cd and Cu were removed with a high selectivity. At lower ligand/(Cd+Cu) ratios Cu is removed more selectively than Cd. DPP forms precipitates with Cd, Ni, Zn and Cu, whereas the Cd and Zn complexes of DCP are soluble in the organic phase.

For DCP the equilibrium constant K_e =[CdL₂] / ( [Cd] [L¯]²) in 55 w% c.p. H₃Po₄ (90°C) has a value of 5?10⁵l²/mol². K_e decreases slightly with decreasing % H₃PO₄ A fast decomposition of DPP was observed in “black” phosphoric acid at 90°C.     

EXTRACTION OF CADMIUM FBOM PHOSPHORIC ACID WITH DIORGANYLDITHIOPHOSPHINIC ACIDS. Part II: Rate of Extraction and Decomposition.

Liquid-liquid extraction of cadmium ions from 55-65 w% “black” phosphoric acid from a Nissan H process with diphenyldithio-phosphinic acid (DPP) or dicyclohexyldithiophosphinic acid (DCP)dissolved in an alkane(c₁₂or c₁₆) at 90°C was investigated.The rate of extraction of Cd from chemically pure phosphoric acid (55 w% H₃Po₄,90°C) is mainly determined by film diffusion of cadmium ions in the phosphoric acid phase to the interface. In the extraction from “black” acid, mass transfer in the organic phase or chemical reaction (ligand exchange) is probably the rate limiting step. An apparent mass-transfer coefficient (based on -5 [Cd] in the phosphoric acid phase) of about 1.6?10^?5 m/s was obtained for the extraction from “black” acid.

A fast decompositon of DPP was observed and in a batch experiment the Cd concentration was already more than 50% of the initial value after 6 hours. This phenomenon is probably caused by the formation of solid complexes with Cu, Cd and Zn, which are dispersed in the phosphoric acid phase and then oxidized. The decomposition of DCP proceeded much slower and after 30 hours the Cd concentration was still below 50% of the initial value. Cu formed a solid complex with DCP, whereas t.he Cd and Zn complexes were soluble in the organic phase. A surface decomposition rate constant of the free ligand in the organic phase of 4?10^?8m/s was obtained.     

Selectivity and competitive mechanism of cation exchange resin for Fe,Mg, and Al ions in phosphoric acid

The presence of iron, magnesium, and aluminum elements as the primary impurities in wet-process phosphoric acid (WPA) adversely affects the industrial phosphoric acid and subsequent phosphorus chemical products. This study aims to investigate the selectivity and competition mechanism of Sinco-430 cation exchange resin for Fe, Mg, and Al ions in phosphoric acid solution. By studying the effects of different process conditions on the removal efficiency, the suitable conditions for the static removal of metal ions from Fe-Mg, Al-Mg, and Fe-Al binary systems were determined: solid–liquid mass ratio (S/L) of 0.3, phosphoric acid concentration of 27.61 wt.%, system temperature of 50°C, and rotational speeds of 200, 400, and 200 rpm, respectively. By calculating the selectivity coefficients of the resin for metal ions under different experimental conditions and mutual replacement experiments, the semi-empirical formulas for the selectivity coefficients were derived and order of selectivity was determined as follows: Mg²⁺ > Fe²⁺ > Al³⁺. Visual MINTEQ 3.1 software and density functional theory (DFT) calculations demonstrated that at low pH, the main forms of Fe, Mg, and Al present in phosphoric acid were FeH₂PO₄⁺, Mg²⁺, and AlH₂PO₄²⁺, respectively. This finding explained the differences in selectivity of the resin for Fe, Mg, and Al. The dynamic removal of metal ions from phosphoric acid was investigated. The order of metal ion selectivity of the resin by the dynamic method is the same as that of the static method, and the dynamic exchange behaviour was most consistent with the Yan model.     

Adsorption and inhibitive action of hexadecylpyridinium bromide on steel in phosphoric acid produced by dihydrate wet method process

The adsorption and inhibitive action of hexadecylpyridinium bromide (HDPB) on the corrosion of cold rolled steel (CRS) in phosphoric acid produced by dihydrate wet method process (7.0 M H₃PO₄) was studied by weight loss, open circuit potential (OCP), potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM), and atomic force microscopy (AFM) methods. The results show that HDPB is a good inhibitor in 7.0 M H₃PO₄, and its maximum inhibition efficiency (IE) is higher than 90% at little concentrations. The adsorption of HDPB obeys Langmuir adsorption isotherm equation. Thermodynamic parameters (adsorption enthalpy ∆H ⁰, adsorption free energy ∆G ⁰, and adsorption entropy ∆S ⁰) were calculated and discussed. Polarization curves show that HDPB acts as a mixed-type inhibitor in phosphoric acid. EIS shows that charge-transfer resistance increases with the inhibitor concentration, confirming adsorption process mechanism. The inhibition action of HDPB could also be evidenced by SEM and AFM images. A probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

Determination of Diffusivity From Steady‐state Mass Transfer Measurements in a Continuous Dialyzer Under Conditions of Non‐zero Solution Flux Through a Membrane

The transport of selected inorganic acids (HCl, H₃PO₄) through an anion‐exchange membrane, Neosepta‐AFN, was investigated in a two‐compartment counter‐current continuous dialyzer with single passes at steady state. The basic data obtained were completed by the measurement of sorption isotherms. The mass transfer rate of the individual acids was quantified by the diffusivity of acid in the membrane, which was determined from the acid concentrations in the streams entering and leaving the dialyzer. For this purpose, two ordinary differential equations describing the steady‐state concentration profiles of acid in both the compartments of the dialyzer were numerically solved in connection with an optimizing procedure. In the mathematical model used, the mass transfer resistances in the liquid films on both sides of the membrane and the flux of solution through the membrane were taken into account. All the experiments, carried out at a constant temperature of 25 °C with subsequent data treatment, revealed that the diffusivity of hydrochloric acid is about one order of magnitude higher than that of phosphoric acid. Moreover, regarding the dependence of the diffusivity of hydrochloric acid upon its concentration in the membrane, a maximum at an acid concentration of 0.622 kmol/m³ can be identified, while the diffusivity of phosphoric acid remains practically constant.     

Characterization and application of activated carbon produced by H3PO4 and water vapor activation

Activated carbons have been prepared from woody biomass birch by using various activation procedures: a) treatment with phosphoric acid and pyrolysis at 600 °C in inert atmosphere, b) the same as in (a) followed by steam activation at the same temperature and c) treatment with phosphoric acid and direct pyrolysis in a stream of water vapor at 700 °C. The surface area and the porosity of the activated carbons were strongly dependent on the treatment after impregnation with H₃PO₄ (pyrolysis in inert atmosphere, steam pyrolysis or combination of both).Activated carbon, prepared by impregnation with phosphoric acid followed by steam pyrolysis (steam activation) had highly developed porous structure and the largest surface area among all prepared carbons (iodine number 1280 mg/g and BET surface area 1360 m²/g). The adsorption capacity of this sample for Hg(II) from aqueous solution was studied in varying treatment conditions: contact time, metal ion concentration and pH. The adsorption followed Langmuir isotherms and the adsorption capacity for Hg(II) at 293 K was 160 mg/g.     

Etude du mecanisme et de la cinetique de la reduction des ions uranyles dans des solutions d'acide phosphorique

The electrochemical reduction of uranyl ions in 0,1-9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometriy and potentiostatic coulometry.In concentrated phosphoric acid solutions (H₃PO₄ < 1 M), an adsorption pre-wave appears in addition to the main wave of diffusion. The electrochemical reaction involves a single electron. Kinetic usually corresponds to a quasi-reversible system, but it evolves according to the variation of U(VI) and H₃PO₄ concentrations. So, when the concentration of U(VI) increases and/or that of H₃PO₄ reduces, the system becomes reversible.     

Adsorption Characteristics of Microporous Carbons from Apricot Stones Activated by Phosphoric Acid

Crushed apricot stone shells were impregnated with varying H₃PO₄ acid concentrations (20–50 wt%), followed by carbonisation at 573–773 K. The products were characterised by nitrogen gas adsorption. Analysis of the nitrogen isotherms by the DR and α_s methods proved that most of the obtained carbons are highly microporous, with high surface areas (⩾1000 m² g^-1) and very low mesoporosity. Increasing acid concentration, at 573 and 673 K, increases surface area and pore volume, whereas at 733 K a small decrease in both parameters appears at higher H₃PO₄ concentrations. Whole apricot stones produce activated carbon of inferior porous characteristics. Development of the extensive pore structure was described in light of the effect of H₃PO₄ on the lignocellulosic mataerial during carbonisation.     

Oxochloromolybdenum(V)tetraphenylporphyrin complex-containing polymer as a phosphate ion exchanger

Summary Oxochloro(5,10,15,20-tetraphenylporphyrinate)molybdenum (V) was physically entrapped into poly (styrene) by lyophilizing a benzene solution including both complex and polymer. The functional ability of the obtained complex-containing resin to adsorb H₂PO₄ ^– from an aqueous solution was investigated in the presence of various anions. It was found that the selectivity of the resin for H₂PO₄ ^– is superior to those of conventional anion exchangers.     

Study on removal of Fe3+ from sodium dihydrogen phosphate by emulsification solvent extraction

Wet-process phosphoric acid (WPA) is gradually paid attention to in recent years. However, there are some undesirable impurities (Fe³⁺, Al³⁺, Mg²⁺) in WPA, which will degrade the quality of sodium dihydrogen phosphate (NaH₂PO₄) products. To get the superior grade NaH₂PO₄, the WPA should be purified. Enhancing the pH of the solution, often to 4, can remove most of the metal ions, but there is still some Fe³⁺ which has great effect on the NaH₂PO₄ crystal products, seem to be irregular long strips. Therefore, before the neutralized NaH₂PO₄ solution is concentrated, the Fe³⁺ must be removed.The emulsification extraction of Fe³⁺ from sodium dihydrogen phosphate (NaH₂PO₄) solution by di(2-ethylhexyl)phosphoric acid (D2EHPA) is investigated. The good extraction efficiency of Fe³⁺ with D2EHPA from NaH₂PO₄ solution by emulsification extraction is verified. Meanwhile, to study the advantages of the emulsification extraction process, the major influencing factors, such as the D2EHPA volume fraction, the phase volume ratio, the initial pH of NaH₂PO₄ solution, the stirring time and agitation speed on the extraction efficiencies of Fe³⁺, are studied, and the optimal process conditions are obtained. The results of extraction experiments from practical NaH₂PO₄ solution show that superior grade NaH₂PO₄ can be obtained by three stages of extraction under appropriate condition.     

Activated carbon from sugar cane bagasse by carbonization in the presence of inorganic acids

Dried ground bagasse, impregnated with 50% inorganic acids and carbonized at 500°C, showed the sequence H₃PO₄ > H₂SO₄ > HCl > HNO₃, with respect to the efficiency of activation. Treatment with phosphoric acid of various concentrations (30–50 wt%) was followed by carbonization at 300–500°C for 3 h. Pore structure parameters were determined from the low-temperature adsorption of nitrogen, by applying the BET and α_s methods. Activated carbons obtained at low temperatures are essentially microporous with a low degree of mesoporosity. At higher temperatures products of higher surface area and total pore volume with developed mesoporosity and low microporosity are formed. An increase in the period of carbonization leads to a small decrease in both surface area and pore volume. Activated carbons with surface areas > 1000 m² g^?1 and mean pore dimensions around 2·0 nm, suitable for various purposes, are thus obtained.     

Electrolyte effects on oxygen reduction kinetics at platinum: A rotating ring-disc electrode analysis

A comparative study of the electrode kinetics of oxygen reduction of platinum in perchloric, phosphoric, sulfuric, trifluoromethanesulfonic acids (all at pH = 0) and in potassium hydroxide (pH = 14) was made at 25°C using rotatating ring-disc electrode techniques. The platinum electrode was first characterised in these electrolytes using the cyclic voltammetric method. The results showed that in the potential region from 0.8 to 0.6 V/rhe, the kinetics of oxygen reduction in these electrolytes decreases in the order KOH > H₂SO₄ ～ CF₃SO₃H > H₃PO₄ > HClO₄. This order of activity is reflected in the effects of the electrolytes, in respect to specific adsorption of anions, on the platinum oxide formation reaction. The role of anion adsorption is also apparent in the dependence of the rate constant for oxygen reduction to water or to hydrogen peroxide and of hydrogen peroxide reduction to water on potential. The superior behavior of oxygen reduction in KOH is due to minimal adsorption of the OH^? ion. The more complex adsorption behavior of the oxyanions in the investigated acid electrolytes than that of simple anions like the halide ions presents difficulties in drawing detailed correlations between oxygen reduction kinetics and adsorption behavior of oxyanions of platinum.     

Extraction of Uranium from “Abu-Tartur” Phosphate Aqueous Leachate Solution

Abstract

Uranium was effectively extracted from a synthetic aqueous monocalcium phosphate/phosphoric acid mixture (MCP/H₃PO₄) by tri-n-octylamine dissolved in different solvents and the presence of low concentrations of some counteranions (oxalate, citrate, chloroacetate) in the aqueous phase. The extraction efficiency was markedly enhanced by the salting out action of the concentration of calcium ions in the MCP/H₃PO₄ solution.     

Preparation of ordered porous carbon from tea by chemical activation and its use in Cr(VI) adsorption

Ordered porous carbon was prepared from a new carbon precursor??the tea leaves, the most widely used beverage worldwide by a chemical activation process. We obtained well developed spherical interlinked meso and micro pores with uniform pore morphology and high surface area from green, black and waste tea by NaOH as well as H₃PO₄ activation process. The carbon obtained from green tea by H₃PO₄ activation had the highest BET surface area of 1,285?m²g^?1 with total pore volume of 0.6243?mL?g^?1. The as prepared porous carbon showed high adsorption efficiency of Cr(VI) adsorption from aqueous solution.     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

Removal of cadmium from phosphoric acid solution by solvent-impregnated resins (sirs) - sorption kinetics and equilibria studies

Cyanex-302 (bis [2,4,4-trimethylpentyl] monothiophosphinic acid) was impregnated into macroporous Diaion HP-10 and HP-1MG polymeric resin matrices and used as an extractant to recover cadmium from concentrated phosphoric acid. The optimum conditions for batchwise extraction of cadmium were established, and equilibrium data in the concentration range 0-200 mg/L Cd were obtained in 40% H 3 PO 4 solution. A Langmuir adsorption isotherm gave the best fit of the adsorption equilibrium data. A preliminary kinetic study was carried out in order to elucidate the rate-controllingmechanism. The uptake of trace cadmium onto Cyanex 302 containing solvent-impregnated resins from 40% phosphoric acid appears to be particle diffusion controlled.     

Effect of pH on Fumaric Acid Adsorption onto IRA900 Ion Exchange Resin

The effects of pH on fumaric acid adsorption onto IRA900 ion exchange resin were studied. The optimum pH with the highest adsorption capacity depended on the fumarate concentration: the optimum pH was > 4.0 for fumarate concentrations < 5.0 g/L and < 3.0 for higher concentrations. Such different adsorption behaviors of IRA900 resins at different pHs were attributed to the different ion forms of fumarate present in solution at different pHs. Modeling results showed that the two-site-occupancy adsorption reaction between FA^2? and resin active sites contributed to the high adsorption capacity at pH 5, whereas the intraparticle diffusion resulting from the hydrophobic interaction between H₂FA and the hydrophobic resin backbone of IRA900 increased significantly and led to a higher adsorption capacity at pH 3.     

Adsorption of cadmium and zinc from aqueous solution on natural and activated bentonite

The adsorption of cadmium and zinc ions on natural bentonite heat-treated at 110°C or at 200°C and on bentonite acid-treated with H₂SO₄ (concentrations: 0·5 mol dm^?3 and 2·5 mol dm^?3), from aqueous solution at 30°C has been studied. The adsorption isotherms corresponding to cadmium and zinc may be classified respectively as H and L types of the Giles classification which suggests the samples have respectively a high and a medium affinity for cadmium and zinc ions. The experimental data points have been fitted to the Langmuir equation in order to calcualte the adsorption capacities (X_m) and the apparent equilibrium constants (K_a) of the samples; X_m and K_a values range respectively for 4·11 mg g^?1 and 1·90 dm³ g^?1 for the sample acid-treated with 2·5 mol dm^?3 H₂SO₄ [(B)-A(2·5)] up to 16·50 mg g^?1 and 30·67 dm³ g^?1 for the natural sample heat-treated at 200°C [B-N-200], for the adsorption process of cadmium, and from 2·39 mg g^?1 and 0·07 dm³ g^?1, also for B-A(2·5), up to 4·54 mg g^?1 and 0·45 dm³ g^?1 [B-N-200], for the adsorption process of zinc. X_m and K_a values for the heat-treated natural samples were higher than those corresponding to the acid-treated ones. The removal efficiency (R) has also been calculated for every sample; R values ranging respectively from 65·9% and 8·2% [B-A(2·5)] up to 100% and 19·9% [B-N-200], for adsorption of cadmium and zinc.     

Solid–liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99

BACKGROUND: In this work, the solid‐liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99, an equivalent of di‐2‐ethylhexyl phosphoric acid, has been investigated. The parameters studied include equilibration time, acid concentration, amount of resin, metal concentration, kinetics, temperature, loading, elution, regeneration and recycling. RESULTS: FT‐IR results confirm the physical interaction of the extractant with the resin. The extraction of terbium with TOPS 99 impregnated Amberlite XAD 4 resin was acid dependent and transfer of metal follows a cation exchange mechanism. The loading capacity of TOPS 99‐impregnated resin for terbium was calculated to be 23.8 mg g^?1 resin. Controlling mechanism of the adsorption was found to be a chemical reaction following pseudo‐second‐order kinetics. The endothermic nature of extraction was confirmed by temperature studies. Among the various eluants studied, H₂SO₄ was the best. Regeneration and recycling of the resin indicated the resin can be used for continuous cycles. CONCLUSIONS: Terbium was successfully extracted from phosphoric acid using TOPS 99 extractant impregnated into Amberlite XAD4 with a maximum loading of 23.8 mg g^?1 resin and fully recovered with 1 mol L^?1sulfuric acid. The resin was subjected to seven cycles of extraction and elution without any loss of performance. Further studies showed that terbium could be separated from lutetium. Copyright © 2010 Society of Chemical Industry     

水热一步法合成SO42-/Zr-PHTS及其催化性能

在低酸度硫酸体系中,以P123(EO₂₀PO₇₀EO₂₀)为模板剂水热法一步合成硫酸化锆掺杂PHTS固体酸催化剂(SO₄^2-/Zr-PHTS),利用XRD、TEM、N₂吸附-脱附以及NH₃-TPD、Py-FTIR等手段对其进行表征。结果表明,SO₄^2-/Zr-PHTS具有有序的六方相介孔结构,具有以L酸为主的弱、中强度的酸性中心;随着硅锆摩尔比的增加,其酸量逐渐减少,比表面积逐渐增加,孔容、孔径无显著变化。SO₄^2-/Zr-PHTS在催化四氢呋喃聚合中表现出良好的反应性能,推测固体酸的表面酸性和孔结构决定着催化四氢呋喃聚合的反应性能。