Strategies to optimize phosphate removal from industrial anaerobic effluents by magnesium ammonium phosphate (MAP) production

BACKGROUND: Owing to more stringent phosphate discharge requirements and the increasing prices of fertilizers, beneficial recovery and reuse of phosphate from industrial anaerobic effluents is becoming an important issue. Phosphate recovery by struvite or magnesium ammonium phosphate (MAP) permits its recycling in the fertilizer industry because struvite is a valuable slow release fertilizer. Two different approaches to MAP crystallization depending on initial levels of phosphate in the wastewaters were tested and compared. RESULTS: For low‐phosphate‐containing anaerobic effluents (<30 mg PO₄^3?‐P L^?1), a novel approach using ureolytic induced MAP formation with MgO addition appeared to be suitable. The residual phosphate concentrations in the effluent ranged from 5 to 7 mg PO₄^3?‐P L^?1 and the separated matter contained residual amounts of Mg(OH)₂. High‐phosphate‐containing anaerobic effluents (100 to 120 mg PO₄^3?‐P L^?1) were treated efficiently using air stripping combined with MgCl₂ and NaOH reagents, yielding residual phosphate levels of 8 to 15 mg PO₄^3?‐P L^?1 and spherical pure MAP crystals of 0.5 to 2 mm. CONCLUSION: Results show that depending on the initial phosphate concentrations in the wastewaters and the ammonium and magnesium levels, the strategy selected for struvite crystallization is a determinative factor in achieving a cost effective technology. Copyright © 2008 Society of Chemical Industry     

Continuous reaction crystallization of struvite from diluted aqueous solution of phosphate(V) ions in the presence of magnesium ions excess

Continuous reaction crystallization of struvite MgNH₄PO₄·6H₂O from diluted aqueous solution containing phosphate(V) ions of concentration 0.20 wt% PO₄³⁻ was investigated experimentally. The tests were carried out in a continuous DT MSMPR type crystallizer in temperature 298 K assuming 20% excess of magnesium ions at the inlet point in respect to struvite synthesis reaction stoichiometry. Influence of pH (8.5–10) and mean residence time of suspension in a crystallizer (900–3600 s) on the product crystals size distribution, their size-homogeneity and process kinetics were identified. Crystals of mean size from ca. 19 to ca. 73 μm, of diverse size-homogeneity (CV 60–87%) were produced. Struvite particles of the largest sizes and acceptable homogeneity were produced at pH 8.5 for prolonged mean residence time 3600 s. Under these conditions struvite nucleation rate did not exceed 5.3 × 10⁷ l/(s m³) according to SIG MSMPR model predictions. Crystal linear growth rate within the investigated process parameter values varied from 3.62 × 10⁻⁹ to 1.68 × 10⁻⁸ m/s. Magnesium ions excess in a process environment influenced yield of continuous reaction crystallization of struvite advantageously – contrary to product crystals quality. Concentration of phosphate(V) ions in mother solution decreased from inlet 0.20 wt% to 0.9 × 10⁻³ – 9.2 × 10⁻³ wt% (9–92 mg/kg) depending on pH and mean residence time of suspension in a crystallizer, what can be regarded as a very good result of their recovering from solution.     

A polymer electrolyte membrane for high temperature fuel cells to fit vehicle applications

Poly(tetrafluoroethylene) PTFE/PBI composite membranes doped with H₃PO₄ were fabricated to improve the performance of high temperature polymer electrolyte membrane fuel cells (HT-PEMFC). The composite membranes were fabricated by immobilising polybenzimidazole (PBI) solution into a hydrophobic porous PTFE membrane. The mechanical strength of the membrane was good exhibiting a maximum load of 35.19 MPa. After doping with the phosphoric acid, the composite membrane had a larger proton conductivity than that of PBI doped with phosphoric acid. The PTFE/PBI membrane conductivity was greater than 0.3 S cm⁻¹ at a relative humidity 8.4% and temperature of 180 °C with a 300% H₃PO₄ doping level. Use of the membrane in a fuel cell with oxygen, at 1 bar overpressure gave a peak power density of 1.2 W cm⁻² at cell voltages >0.4 V and current densities of 3.0 A cm⁻². The PTFE/PBI/H₃PO₄ composite membrane did not exhibit significant degradation after 50 h of intermittent operation at 150 °C. These results indicate that the composite membrane is a promising material for vehicles driven by high temperature PEMFCs.     

Mass transportation in diethylmethylammonium trifluoromethanesulfonate for fuel cell applications

To use the protonic mesothermal fuel cell without humidification, mass transportation in diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), trifluoromethanesulfuric acid (TfOH)-added [dema][TfO], and phosphoric acid (H₃PO₄)-added [dema][TfO] was investigated by electrochemical measurements. The diffusion coefficient and the solubility of oxygen were ca. 10⁻⁵ cm² s⁻¹ and ca. 10⁻³ M (=mol dm⁻³), respectively. Those of hydrogen were a factor of 10 and one-tenth compared to oxygen, respectively. The permeability, which is a product of the diffusion coefficient and solubility, of oxygen and hydrogen were almost the same for the perfluoroethylenesulfuric acid membrane and the sulfuric acid solution; therefore, these values are suitable for fuel cell applications. On the other hand, a diffusion limiting current was observed for the hydrogen evolution reaction. The current corresponded to ca. 10⁻¹⁰ mol cm⁻¹ s⁻¹ of the permeability, and the diffusion limiting species was the hydrogen carrier species. The TfOH addition enhanced the diffusion limiting current of [dema][TfO], and the H₃PO₄ addition eliminated the diffusion limit. The hydrogen bonds of H₃PO₄ or water-added H₃PO₄ might significantly enhance the transport of the hydrogen carrier species. Therefore, [dema][TfO] based materials are candidates for non-humidified mesothermal fuel cell electrolytes.     

Synthesis and properties of imidazole-grafted hybrid inorganic-organic polymer membranes

Imidazole rings were grafted on alkoxysilane with a simple nucleophilic substitute reaction to form hybrid inorganic-organic polymers with imidazole rings. Proton exchange membranes (PEM) based on these hybrid inorganic-organic polymers and H₃PO₄ exhibit high proton conductivity and high thermal stability in an atmosphere of low relative humidity. The grafted imidazole rings improved the proton conductivity of the membranes in the high temperature range. It is found that the proton conductivities increase with H₃PO₄ content and temperature, reaching 3.2 × 10⁻³ S/cm at 110 °C in a dry atmosphere for a membrane with 1 mole of imidazole ring and 7 moles of H₃PO₄. The proton conductivity increases with relative humidity (RH) as well, reaching 4.3 × 10⁻² S/cm at 110 °C when the RH is increased to about 20%. Thermogravimetric analysis (TGA) indicates that these membranes are thermally stable up to 250 °C in dry air, implying that they have a good potential to be used as the membranes for high-temperature PEM fuel cells.     

Modification of titanium oxide layer by calcium and phosphorus

The aim of the study was to investigate the possibility of calcium and phosphorus ion implantation into an oxide film applied onto titanium during anodic passivation. The corrosion resistance of modified titanium in Tyrode's physiological solution has been identified. Anodic oxidation was carried out in two solutions. The first contained 20 g dm⁻³ NaH₂PO₂ in 4.3 M H₃PO₄ (K1), whereas the other, 20 g dm⁻³ Ca(H₂PO₂)₂ in 4.3 M H₃PO₄ (K2). Voltage of 100 and 150 V was applied. It has been found out that it is possible to incorporate Ca and P into the emerging passive layer. The application of the voltage of 150 V makes it very porous. It has been also demonstrated that titanium so modified presents higher resistance to corrosion in the investigated environment than titanium not modified in Tyrode's solution.     

Mechanochemical synthesis of kaolin-KH2PO4 and kaolin-NH4H2PO4 complexes for application as slow release fertilizer

A milling process to reduce kaolin to amorphous phase in the presence of KH₂PO₄ or NH₄H₂PO₄ and allow mechanochemical (MC) reaction for incorporation of KH₂PO₄ and NH₄H₂PO₄ into the kaolin structure was investigated in this work. Mixtures of kaolin and KH₂PO₄ and NH₄H₂PO₄ in separate systems were prepared by milling in a planetary ball mill. Tests with kaolin contents ranging from 25 to 75 wt.% and mill rotational speeds from 200 to 700 rpm were performed to evaluate incorporation of KH₂PO₄ and NH₄H₂PO₄ and release of K⁺, NH₄⁺ and PO₄³⁻ ions into solution. Analyses by XRD, DTA and ion chromatography indicated that the MC process was successfully applied to incorporate both KH₂PO₄ and NH₄H₂PO₄ into the amorphous kaolin structure. Release of K⁺ and PO₄³⁻ ions from the system (kaolin-KH₂PO₄) when dispersed in water for 24 h reached only up to 10%. Under similar conditions for the system (kaolin-NH₄H₂PO₄), release of NH₄⁺ and PO₄³⁻ ions reached between 25 and 40%. These results indicated that the MC process can be developed to allow amorphous kaolin to act as a carrier of K⁺, NH₄⁺ and PO₄³⁻ nutrients to be released slowly for use as fertilizer.     

Microwave solid-state synthesis and electrochemical properties of carbon-free Li3V2(PO4)3 as cathode materials for lithium batteries

Monoclinic Li₃V₂(PO₄)₃ can be rapidly synthesized at 750 °C for 5 min (MW5m) by using microwave solid-state synthesis method. The refined cell parameters and atomic coordination of the sample MW5m show some deviations compared with those of the sample synthesized in conventional solid-state synthesis method, especially the coordinate of Li atoms. Compared with the electrochemical properties of the carbon-coating sample Li₃V₂(PO₄)₃, the carbon-free sample MW5m presents well electrochemical properties. In the cut-off voltage of 3.0-4.3 V, MW5m sample presents a specific charge capacity of 132 mAh g⁻¹, almost equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹), and specific discharge capacity of 126.4 mAh g⁻¹. In the cut-off voltage of 3.0-4.8 V, MW5m shows an initial specific discharge capacity of 183.4 mAh g⁻¹ at 0.1 C, near the theoretical discharge capacity. In the cycle performance, the capacity fade of Li₃V₂(PO₄)₃ is dependent on the cut-off voltage and the preparation method, more capacity lost at relatively higher charge/discharge voltage. The reasons for the excellent electrochemical properties of Li₃V₂(PO₄)₃ rapidly synthesized in microwave field are discussed in detail.     

Crystal structure and electrochemical performance of Li3V2(PO4)3 synthesized by optimized microwave solid-state synthesis route

To investigate the crystal structure and electrochemical performance of samples synthesized under different microwave solid-state synthesis condition, a series of Li₃V₂(PO₄)₃ samples has been synthesized at five different temperatures for 3-5 min and at 750 °C for various time. The as-synthesized Li₃V₂(PO₄)₃ samples are characterized and studied by ICP-AES analysis, X-ray diffraction (XRD), Rietveld analysis, scanning and transmission electron microcopy (SEM and TEM). At relatively lower temperature (650 °C) and very short reaction time (3 min), pure phase of Li₃V₂(PO₄)₃ could be synthesized in microwave irradiation field. The crystal structure and Li atomic fractional coordinate present a significant deviation upon the change of microwave irradiation temperature and time. Relatively, the diffusion ability of lithium cations and the electrochemical performance are affected. Under the proper reaction temperature and time, the carbon-free samples MW750C5m and MW850C3m show the best specific discharge capacity 126.4 and 132 mAh g⁻¹ at the voltage range of 3.0-4.3 V, near the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). At the voltage range of 3-4.8 V, the sample MW750C5m presents the best initial specific charge capacity of 197 mAh g⁻¹, equivalent to the reversible cycling of three lithium ions per Li₃V₂(PO₄)₃ formula unit (197 mAh g⁻¹). The initial discharge capacity, the samples MW750C5m and MW850C3m present high specific discharge capacity 183.4 and 175.7 mAh g⁻¹, respectively. The relationship among microwave irradiation condition, crystal structure, lithium atomic fractional coordinates and the electrochemical performance have been discussed in detail.     

Process intensification of continuous starch hydrolysis with a Couette–Taylor flow reactor

Starch gelatinization and enzymatic hydrolysis was carried out in a continuous Couette–Taylor flow reactor with a water jacket. The degree of gelatinization and the concentration of reducing sugars produced via enzymatic saccharification were evaluated by varying operational variables: rotation speed of an inner cylinder, initial concentration of starch and reaction temperature. At the initial concentration of the starch suspension, 50 kg m⁻³, starch saccharification proceeded sufficiently even at low rotation speed of the inner cylinder and saccharification temperature. At the higher initial concentration, 100 and 150 kg m⁻³, a higher rotation speed of the inner cylinder and temperature of the saccharification section were required to obtain sufficient starch saccharification. Even in the case of C₀ = 100 and 150 kg m⁻³, the more reducing sugar was obtained by choosing an adequate rotation speed of the inner cylinder and a reaction temperature.     

Yellowish green-emitting KSrPO4:Tb phosphors with various doping concentrations prepared by using microwave assisted sintering

KSr_1−xPO₄:xTb³⁺ phosphors with various concentrations (x = 0.05, 0.06, 0.07, 0.08) of Tb³⁺ ions were synthesized in succession by using microwave assisted sintering. The sintering condition was set at 1200 °C for 1 h in air. The microstructural and luminescent characteristics of KSrPO₄:Tb³⁺ phosphors were investigated and are discussed here. The XRD result shows that the prepared KSr_1−xPO₄:xTb³⁺ phosphors would have an impure phase as the Tb³⁺ ion increases to more than x = 0.06. The photoluminescence measurement shows that the series of the emission-state ⁵D₄ → ⁷F₆, ⁵D₄ → ⁷F₄, and ⁵D₄ → ⁷F₃, corresponding to the typical 4f → 4f intra-configuration forbidden transitions of Tb³⁺, are appeared and the major emission peak is around at 542 nm. Moreover, the maximum photoluminescence intensity is appeared when the molar concentration of Tb³⁺ is 0.06. The decay time value of the KSr_1−xPO₄:xTb³⁺ phosphors with x = 0.06 is about 0.27 ms.     

The treatment of sulfate-rich wastewater using an anaerobic sequencing batch biofilm pilot-scale reactor

This paper presents the results from 92 cycles of an anaerobic sequencing batch biofilm reactor containing biomass immobilized on inert support (mineral coal) applied for the treatment of an industrial wastewater containing high sulfate concentration. The pilot-scale reactor, with a total volume of 1.2 m³, was operated at sulfate loading rates ranging from 0.15 to 1.90 kgSO₄²⁻/cycle (48 h — cycle) corresponding to sulfate concentrations of 0.25 to 3.0 gSO₄²⁻ l^− 1. Domestic sewage and ethanol were utilized as electron donors for sulfate reduction. Influent sulfate concentrations were increased in order to evaluate the minimum COD/sulfate ratio at which high reactor performance could be maintained. The mean sulfate removal efficiency remained between the range of 88 to 92% at several sulfate concentrations. Temporal profiles along the 48 h cycles were carried out under stable operation at sulfate concentrations of 1.0, 2.0 and 3.0 gSO₄²⁻ l^− 1. Sulfate removal reached 99% for cycle times of 15, 25, and 30 h, and the effluents sulfate concentrations were lower than 8 mgSO₄²⁻ l^− 1. The results demonstrate the potential applicability of the anaerobic configuration for the biological treatment of sulfate-rich wastewaters.     

Rapid preparation and electrochemical behavior of carbon-coated Li3V2(PO4)3 from wet coordination

An improved solid-state coordination method namely wet coordination has been developed to synthesize carbon-coated monoclinic Li₃V₂(PO₄)₃ rapidly at a low temperature of 600 °C in 1 h. The structure of the sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and energy dispersive analysis of X-rays (EDAX). The diffusion coefficient of the lithium ions was measured by cyclic voltammetry (CV). The electrochemical behavior of the sample exhibits a high initial discharge capacity of 130 mAh g⁻¹, which is very close to its theoretical capacity of 132 mAh g⁻¹ under 95 mA g⁻¹ (0.67 C) in the range of 3.3-4.3 V (vs. Li/Li⁺). These results suggest that wet coordination is a promising method for large-scale production of carbon-coated Li₃V₂(PO₄)₃.     

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

Co-doped Li₃V_2−xCo_x(PO₄)₃/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li₃V_2−xCo_x(PO₄)₃/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li₃V_2−xCo_x(PO₄)₃. XPS studies also revealed that V⁴⁺ and V³⁺ ions were present in the Co²⁺-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li₃V_2−xCo_x(PO₄)₃/C compounds showed that the voltage peaks associated with the extraction of three Li⁺ ions shifted to higher voltages with an increase in Co content, and when the Co²⁺-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li₃V₂(PO₄)₃ phase. For the Li₃V_1.85Co_0.15(PO₄)₃/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li₃V₂(PO₄)₃) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co²⁺into V sites should be favorable for the structural stability of Li₃V_2−xCo_x(PO₄)₃/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li⁺ extraction/insertion, thus resulting in the improvement of cell cycling ability.     

Improving the rate performance of LiFePO4 by Fe-site doping

LiFePO₄ doped by bivalent cation in Fe-sites show improved rate performance and cyclic stability. Under 10 C rate at room temperature, the capacities of LiFe_0.9M_0.1PO₄ (M = Ni, Co, Mg) maintain at 81.7, 90.4 and 88.7 mAh/g, respectively, in comparison with 53.7 mAh/g for undoped LiFePO₄ and 54.8 mAh/g for carbon-coated LiFePO₄ (LiFePO₄/C). The capacity retention is 95% after 100 cycles for doped samples while this value is only 70% for LiFePO₄ and LiFePO₄/C. Such a significant improvement in electrochemical performance should be partially related to the enhanced electronic conductivities (from 2.2 × 10⁻⁹ to <2.5 × 10⁻⁷ S cm⁻¹) and probably the mobility of Li⁺ ions in the doped samples.     

Formation of porous anodic titanium oxide films in hot phosphate/glycerol electrolyte

The present study reveals the formation of porous anodic films on titanium at an increased growth rate in hot phosphate/glycerol electrolyte by reducing the water content. A porous titanium oxide film of 12 μm thickness, with a relatively low content of phosphorus species, is developed after anodizing at 5 V for 3.6 ks in 0.6 mol dm⁻³ K₂HPO₄ + 0.2 mol dm⁻³ K₃PO₄/glycerol electrolyte containing only 0.04% water at 433 K. The growth efficiency is reduced by increasing the formation voltage to 20 V, due to formation of crystalline oxide, which induces gas generation during anodizing. The film formed at 20 V consists of two layers, with an increased concentration of phosphorus species in the inner layer. The outer layer, comprising approximately 25% of the film thickness, is developed at low formation voltages, of less than 10 V, during the initial anodizing at a constant current density of 250 A m⁻². The pore diameter is not significantly dependent upon the formation voltage, being ∼10 nm.     

Development of blue ceramic dyes from cobalt phosphates

In this study the development of blue ceramic dyes from compositions based on phosphate structures have been investigated. The replacement of cobalt by copper or iron to minimize the Co content have been considered. MFeO(PO₄) (M = Co, Cu) solid solutions have been obtained with Co_1−xCu_xFeOPO₄ (0 ≤ x ≤ 1) compositions prepared from gels and fired at 1000 °C/2 h. Co_1−xCu_xFeOPO₄ compositions are not indicated to minimize the Co content in ceramic dyes because they decompose in glazed samples and pinhole defect is obtained. From FeCoOPO₄–2FePO₄ compositions, Co₃Fe₄(PO₄)₆ structure introduces the Co²⁺ ions into glassy matrix and suitable blue materials are obtained. In the conditions of this study, optimal cobalt amount is about 10 wt% Co from Co_1−xFe_1+xO_1−x(PO₄)_1+x (x ≈ 0.6) compositions.     

Synthesis of organosiloxane-based inorganic/organic hybrid membranes with chemically bound phosphonic acid for proton-conductors

Proton conductive inorganic-organic hybrid membranes were synthesized from 3-glycidoxypropyltrimethoxysilane (GPTMS) and phosphonoacetic acid (PA) with various ratios by a sol-gel process. Self-standing, homogeneous, highly transparent membranes were synthesized. TG-DTA analyses indicated that these membranes were thermally stable up to 200 °C. The results of FT-IR and ¹³C NMR revealed that phosphonic acid groups of PA were chemically bound to organosiloxane network as a result of reaction between PA and GPTMS. The leach out of phosphonic acid groups from GPTMS-PA to water was reduced compared with phosphoric acid groups from GPTMS-H₃PO_4. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The conductivity of GPTMS/PA with a 1/1.05 ratio at 130 °C was 8.7 × 10⁻² S cm⁻¹ at 100% relative humidity (RH).     

Effects of neodymium aliovalent substitution on the structure and electrochemical performance of LiFePO4

LiFe_1−xNd_xPO₄/C (x = 0-0.08) cathode material was synthesized using a solid-state reaction. The synthesis conditions were optimized by thermal analysis of the precursor and magnetic properties of LiFePO₄/C. The structure and electrochemical performances of the material were studied using XRD, FE-SEM, EDS, electrochemical impedance spectroscopy and galvanostatic charge-discharge. The results show that a small amount of aliovalent Nd³⁺ ion-dopant substitution on Fe²⁺ ions can effectively reduce the particle size of LiFePO₄/C. Cell parameters of LiFe_1−xNd_xPO₄ (x = 0.04-0.08) were calculated, and the results showed that LiFe_1−xNd_xPO₄/C had the same olivine structure as LiFePO₄. LiFe_0.4Nd_0.6PO₄/C delivers the discharge capacity of 165.2 mAh g⁻¹ at rate of 0.2 C and the capacity retention rate is 92.8% after 100 cycles. Charge-transfer resistance decreases with the addition of glucose and Nd³⁺ ions. Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) was synthesized and PZS nanorods were used as a carbon source to coat LiFePO₄. All of the results show that aliovalent doping substitution of Fe in LiFePO₄ is well tolerated.     

Uncommon potential hysteresis in the Li/Li2xVO(H2−xPO4)2 (0 ≤ x ≤ 2) system

Physical and electrochemical investigations of vanadium phosphates, Li_2xVO(H_2−xPO₄)₂ (0 < x < 2), have been undertaken. H⁺/Li⁺ ionic exchange from VO(H₂PO₄)₂ to Li₂VO(HPO₄)₂ leads to grain decrepitation. Further ionic exchange toward formation of Li₄VO(PO₄)₂ lowers the symmetry. As inferred from potentiodynamic cycling correlated to ex situ and in situ X-ray diffraction (XRD), the system Li/Li₄VO(PO₄)₂ shows several phase transformations that are associated with thermodynamical potential hysteresis that span from roughly 15 mV to more than 1.8 V. Small hysteresis are associated with topotactic reactions and with V^V/V^IV and V^III/V^II redox couples. Large potential hysteresis values (>1 V) were observed when oxidation of V^III to V^IV is involved.