Thermal decomposition of magnesium ammonium phosphate and adsorption properties of its pyrolysis products toward ammonia nitrogen

High-purity magnesium ammonium phosphate （MAP） was precipitated by controlling pH value of the reaction system of 9.0-9.5. The thermal decomposition behavior of MAP and the adsorption properties of its pyrolysis products toward ammonia-nitrogen were also studied by XRD, SEM, TGA-DTA and FT-IR methods. The results indicated that high-purity MAP was obtained at pH value of 9.0-9.5. Upon heating to 100-120℃ for 120 min, MAP was thermally decomposed, losing water and ammonia concomitantly with a reduction in grain size and crystallinity. The capacity of pyrolysis products for ammonia nitrogen adsorption reached 72.5 mg/g, with a removal rate of up to 95% from an 800 mg/L solution. The characteristic diffraction peaks corresponding to MAP mainly appeared in their XRD patterns after adsorption of ammonia nitrogen. The pyrolysis products of MAP at 100-120 ℃ could be recycling-used as the chemical treatment regents of ammonia nitrogen in the practical application.

Temperature-programmed pyrolysis of magnesium ammonium phosphate and removal of ammonia-nitrogen by its pyrolysate

In order to achieve the dual goals of complete deamination of magnesium ammonium phosphate（MAP） and ensure the pyrolysate＇s good removal properties towards ammonia-nitrogen, a temperature-programmed method for the pyrolysis of MAP was studied, as well as the thermodynamic and kinetic processes involved in the removal reaction system between MAP pyrolysate and aqueous ammonium. It was found that the pyrolysis method and pyrolysis final temperature had significant effects on the MAP pyrolysate＇s removal properties towards aqueous ammonium, and the following conditions were deemed to be more appropriate： pyrolysis final temperature and heating rate at 180 ℃ and 5 ℃/min, respectively, and a pH level of 9.5 for the removal reaction system. The resultant ammonium removal capacity by the MAP pyrolysate was 95.62 mg/g. After 120 min, the removal rate with an initial concentration of 1000 mg/L was 82%. The kinetic and thermodynamic results indicated that the removal of aqueous ammonium by MAP pyrolysate was the exchange process between H^＋ and NH4^＋ via MAP precipitation. The kinetics complied with the Lagergren quasi second-order model with an equilibrium time of 120 min, while the isothermal curves complied with the Freundlich model.

Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate

Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is （28.795 ± 0.182） kJ/mol （298.15 K）, and the standard molar enthalpy of formation of the title complex is （-2185.43 ± 13.80） kJ/mol （298.15 K）. Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction： an nth-order reaction （Fn） with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction （F2） with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1.

Thermodynamic study on phosphorus removal from tungstate solution via magnesium salt precipitation method

The thermodynamic equilibrium diagrams of Mg2＋- 3-4PO - ＋4NH -H2O system at 298 K were established based on the thermodynamic calculation. From the diagram, the thermodynamic conditions for removing phosphorus from the tungstate solution by magnesium salt precipitation were obtained. The results show that when the concentration of total magnesium increases from 0.01 mol/L to 1.0 mol/L, the optimal pH for the phosphorus removal by magnesium phosphate decreases from 9.8 to 8.8. The residual concentration of total phosphorus almost keeps the level of 4.0×10-6 mol/L in the system. MgHPO4, Mg3（PO4）2 and the mixture of Mg3（PO4）2 and Mg（OH）2 are stabilized in these system, respectively. However, increasing the total concentration of magnesium has little effect on phosphorus removal by magnesium ammonium phosphate, while it is helpful for phosphorus removal by increasing the total ammonia concentration. The calculated results demonstrate that the residual concentration of total phosphorus can decrease to 5.0×10-7 mol/L as the total concentration of ammonia reaches 5.0 mol/L and the optimal pH value is 9-10. Finally, verification experiments were conducted with home-made ammonium tungstate solution containing 50 g/L WO3 and 13 g/L P. The results show that when the dosage of MgCl2 is 1.1 times of the theoretical amount, the optimum pH for removing phosphorus is 9.5, which matches with the results of the theoretical calculation exactly.

Formation of Struvite Crystals in a Simulated Food Waste Aerobic Composting Process

Bench-scale treatments with three mixtures of Mg and P salts, including K3PO4＋MgSO4, K2HPO4＋MgSO4, and KH2PO4＋MgSO4 as additives in a simulated food waste aerobic composting process, were conducted to test the magnesium ammonium phosphate（MAP） formation, and the compost products were analyzed by X-ray diffraction（XRD）, Scanning electron microscopy（SEM）, and Energy dispersive X-ray spectroscopy（EDS） analyses. The comparison results between XRD, SEM, and EDS analyses of MAPs in the dried compost and synthesized MAPs confirm the formation of MAP crystals in the simulated food waste aerobic composting process. The analysis of the compost also indicates that the addition of all the three mixtures of Mg and P salts in the aerobic composting process can increase nitrogen conservation and decrease nitrogen loss because of the formation of MAPs. The mechanism of MAP formation was verified as the reaction of ammonium（NH4＋） with magnesium（Mg^2＋） and phosphate[HnPO4^（3-n） , n=0, 1, and 2）.

Modeling assessment for ammonium nitrogen recovery from wastewater by chemical precipitation

Chemical precipitation to form magnesium ammonium phosphate（MAP） is an effective technology for recovering ammonium nitrogen（NH4＋-N）.In the present research,we investigated the thermodynamic modeling of the PHREEQC program for NH4＋-N recovery to evaluate the effect of reaction factors on MAP precipitation.The case study of NH4＋-N recovery from coking wastewater was conducted to provide a comparison.Response surface methodology（RSM） was applied to assist in understanding the relative significance of reaction factors and the interactive effects of solution conditions.Thermodynamic modeling indicated that the saturation index（SI） of MAP followed a polynomial function of pH.The SI of MAP increased logarithmically with the Mg2＋/NH4＋ molar ratio（Mg/N） and the initial NH4＋-N concentration（CN）,respectively,while it decreased with an increase in Ca2＋/NH4＋ and CO32？/NH4＋ molar ratios（Ca/N and CO32？/N）,respectively.The trends for NH4＋-N removal at different pH and Mg/N levels were similar to the thermodynamic modeling predictions.The RSM analysis indicated that the factors including pH,Mg/N,CN,Ca/N,（Mg/N）×（CO32？/N）,（pH）2,（Mg/N）2,and（CN）2 were significant.Response surface plots were useful for understanding the interaction effects on NH4＋-N recovery.

Optimization of process parameters for mature landfill leachate pretreatment using MAP precipitation

Chemical precipitation is a useful technology as a pretreatment to treat mature landfill leachate with high concentrations of ammonium-nitrogen （NH＋-N） and refractory organic compounds. Orthogonal experiments and factorial experiments were carried out to determine the optimal conditions enhancing the magnesium ammonium phosphate （MAP） precipitation process, and the experi- mental results demonstrated that the removal rate of NH＋ -N was more than 85% when MgO and NaHEPO4.2H20 were applied as external sources of magnesium and phosphorous under the optimal conditions that molar ratio n（Mg）：n（N）：n（P） = 1.4：1：0.8, reaction time 60 min, original pH of leachate and settling time 30 min. In the precipitation process, pH could be maintained at the optimal range of 8-9.5 because MgO could release hydroxide ions to consume hydrogen ions. Calcium ions and carbonate ions existed in the leachate could affect the precipitation process, which resulted in the decrease of NH＋-N removal efficiency. The residues of MAP sediments decomposed by heating under alkaline condi- tions can be reused as the sources of phosphorous and magnesium for the removal of high concentrations of NH4＋ -N, and up to 90% of ammonium could be released under molar ratio of n[OH]：n[MAP] = 2.5： 1, heating temperature 90℃ and heating time 2h.