Magnesium recovery from ferrochrome slag: kinetics and possible use in a circular economy

The ever-increasing demand for ferrochrome alloys has resulted in a substantial accumulation of ferrochrome slag by-products in many mining areas. On the other hand, the ferrochrome slag has been identified as one waste material that is rich in magnesium (Mg) and has not been effectively exploited. Beneficiating of ferrochrome slag (FCS) waste material is envisaged as a means of achieving sustainable recovery of Mg. Previous studies have used sulphuric acid as a lixiviant for leaching FCS at moderate temperatures to recover Mg. In this study, the recovery of Mg from ferrochrome slag was investigated using hydrochloric acid (HCl) as the lixiviant at low temperatures. Previous studies have shown that various metal oxides have been proven to be more amenable to leaching using HCl. This study examined the effects of acid content, leaching temperature, and reaction time on the recovery of Mg from FCS. Kinetic and thermodynamic analysis of the leaching process were also investigated as these are critical factors for maximum extraction of the Mg. The results showed that the highest recovery of Mg of 88.2% was obtained from FCS using 5 M HCl with a solid to liquid ratio of 1:10, mixing intensity of 250 rpm, reaction time and temperature of 150 min and 70 °C, respectively. The shrinking core model (SCM) was used in kinetic analysis to find the experimental data's best fit. A linear relationship was obtained with the coefficient of determination for the chemical reaction model (Kc) of >0.9 which indicates a good fit. The activation energy obtained for the diffusion and chemical reaction models were 95.44 and 41.45 kJ/mol, respectively, demonstrating that the rate-limiting phase is the one involving the chemical reaction

Recovering phosphorus as struvite from anaerobic digestate of pig manure with ferrochrome slag as a magnesium source

The circular economy initiative has driven the agriculture and agro-based industry to beneficiate from waste,thus closing the material loop towards enhancing economic and environmental performance. In this study, the aim was to recover phosphorus from anaerobic digestate of piggery wastewater (ADPW) using ferrochrome slag (FCSL) as the magnesium source to improve the environmental and economic sustainability of struvite precipitation. This was achieved by leaching 100 g L−1 of ferrochrome slag with 5 M HCl where 14.02 g L−1 of magnesium ions were extracted, and this acid-leachate of ferrochrome slag also contained 2650 mg L−1 of total iron. To simultaneously remove both high concentrations of organic matters in ADPW and iron in FCSL which are known to be detrimental to struvite precipitation, hydrogen peroxide (H2O2) at an H2O2/Fe molar ratio of 0.75 and pH 4.0 was added to the mixture of ADPW and FCSL. After the Fenton reaction, removal efficiencies of chemical oxygen demand (COD) and total iron reached 95.06% and 94.00%, respectively. Then COD and an iron-reduced mixture of ADPW and FCSL were added with a satisfying Mg:N:P molar ratio of 1.2:1:1.15 at pH 9.5 to produce struvite in 1 h. From 1 L of ADPW (2.6 g NH3–N), 0.5 L of FCSL (5.34 g Mg2+), and 6.62 g of PO43− P, were consumed to produce 45.57 g of struvite precipitate. Additionally, the economic feasibility of ferrochrome slag was assessed by estimating the chemical costs of FCSL against that of magnesium chloride which is commercially used. It was observed that using FCSL was cheaper as compared to using commercial MgCl2. Response surface methodology coupled with the central composite design was applied as a statistical tool to determine the effects of the key parameters (N:P; Mg:PO4; pH) on phosphorus recovery. Second-order polynomial equations were determined to correlate the parameters. ANOVA was applied and showed that p values for all the investigated parameters were less than 0.05 showing that they had a statistically significant effect on the phosphorus recovery. The study confirmed that it was possible to recover phosphorus as struvite from anaerobic digestate of pig manure with ferrochrome slag as a magnesium source

Characterization, kinetics and thermodynamic evaluation of struvite produced using ferrochrome slag as a magnesium source

There is limited data on studies that have focused on the kinetics, thermodynamics, and characterization of struvite crystallization from alternative magnesium sources. This study focused on thermal analysis of struvite (produced using ferrochrome slag as a magnesium source) and the results indicated that the residual quantities of struvite were lower than the theoretical mass loss of struvite of 51.42%. When using ferrochrome slag (FCS) as the magnesium source, 47.9%, 47.4%, and 46.9% losses in mass were observed for heating rates of 5°C/min; 10°C/min and 15°C/min respectively. The mean activation energies for struvite produced using FCS were deduced using isoconversional kinetic methods and ranged from 49.81to 56.20 kJ/mol which is very similar to the activation energies deduced using MgCl2. The study also focused on the surface morphology, and particle size of the final product at different pH and N:P ratios. The final particle size distribution of the product was significantly influenced by the solution pH. To improve the crystal growth kinetics for both MgCl2 and FCS, a high ratio of N:P molar ratios should be adopted. The product's highest median particle size was obtained using FCS as the magnesium source at a low pH. Median particle size increased with decrease in pH, at a pH of 7.5 the recorded median particle size was 96 µm whilst, the lowest was 31 µm at a pH of 9.5. The highest percent of fines (<10 µm) was recorded at a pH of 9.5 using FCS as magnesium source in the metastable region of struvite precipitation whereas at a pH of 7.5 no fines (<10 µm) were recorded. SEM images confirmed that the struvite underwent morphological changes when prepared with FCS in comparison to that produced using MgCl2. The surface morphology of the finished product demonstrated the presence of irregular shaped particles, due to presence of impurities. The kinetic data showed that struvite precipitation was limited by the chemical reaction step. Model fitting was used to determine the reaction control mechanism and the average activation energies obtained by four model free methods were FWO (56.2), KAS (51.67) Starink (49.61) and Tang (49.81) kJ/mol, indicating that the FWO method was the least accurate method. The thermodynamic data indicated that the thermal degradation of struvite crystals has a high degree of disorder, and the process is endothermic, irreversible, and non-spontaneous