A novel method for the stabilization of soluble contaminants in electrolytic manganese residue: Using low-cost phosphogypsum leachate and magnesia/calcium oxide.

Electrolytic manganese residue (EMR) contains a large amount of NH4+-N and Mn2+ and can negatively impact the environment. A stabilization treatment of soluble contaminants in the EMR is necessary for its reuse and safe stacking. This study presents experimental results for the stabilization of NH4+-N and Mn2+ in the EMR using phosphogypsum leachate as a low-cost phosphate source and MgO/CaO (PLMC) process. The results demonstrated that the stabilization efficiency of NH4+-N and Mn2+ was 93.65% and 99.99%, respectively, under the following conditions: a phosphogypsum leachate dose of 1.5 mL g-1, an added MgO dose of 0.036 g g-1, an added CaO dose of 0.1 g g-1 and a reaction time of 2 h. The stabilization effect of the PLMC process was higher and more cost effective than that of using Na3PO4·12H2O and MgO/CaO. The concentration of NH4+-N and Mn2+ in the leaching liquor decreased to 80 mg L-1 and 0.5 mg L-1, respectively, after the stabilization under the optimum conditions. The stabilization characteristics indicated that NH4+-N was stabilized to form NH4MgPO4·6H2O (struvite) and that Mn2+ was stabilized to form Mn5(PO4)2(OH)4, Mn3(PO4)2·3H2O and Mn(OH)2. PO43--P, F-, and heavy metal ions of the phosphogypsum leachate were removed from the leaching liquor and stabilized in the treated EMR.

Development of phosphorus recovery reactor for enlargement of struvite crystals using seawater as the magnesium source.

Struvite crystallization is an interesting method for the recovery of phosphorus (P) from wastewater. However, the struvite crystals obtained are small, which makes them difficult to separate from wastewater. A continuous reactor for enlarging struvite crystals was developed. Batch-scale experiments were conducted to investigate the optimum factors for the enlargement of struvite crystals. The results of pH experiments showed that P recovery efficiency increased with an increase of pH values (7.6 to 10), while the size of struvite crystals decreased. The results of the Mg:P ratios found that the maximum P recovery efficiency occurred at the maximum ratio of Mg:P. The sizes of struvite crystals were not significantly different. For the variation of temperature values, the results showed that P recovery efficiency and crystal sizes decreased when temperature values increased. Therefore, the optimized conditions for P recovery efficiency and enlargement of struvite crystals for the continuous reactor were pH 8.5 and an Mg:P ratio of 1.2:1 at 30 °C (room temperature). The treated swine wastewater and seawater were continuously fed in at the bottom of the reactor. After 30 days, the size of struvite crystals had increased from 125 µm to 0.83 mm (seven times).

Phosphorous in the environment: characteristics with distribution and effects, removal mechanisms, treatment technologies, and factors affecting recovery as minerals in natural and engineered systems.

Phosphorus (P), an essential element for living cells, is present in different soluble and adsorbed chemical forms found in soil, sediment, and water. Most species are generally immobile and easily adsorbed onto soil particles. However, P is a major concern owing to its serious environmental effects (e.g., eutrophication, scale formation) when found in excess in natural or engineered environments. Commercial chemicals, fertilizers, sewage effluent, animal manure, and agricultural waste are the major sources of P pollution. But there is limited P resources worldwide. Therefore, the fate, effects, and transport of P in association with its removal, treatment, and recycling in natural and engineered systems are important. P removal and recycling technologies utilize different types of physical, biological, and chemical processes. Moreover, P minerals (struvite, vivianite, etc.) can precipitate and form scales in drinking water and wastewater systems. Hence, P minerals (e.g., struvite, vivianite etc.) are problems when left uncontrolled and unmonitored although their recovery is beneficial (e.g., slow release fertilizers, sustainable P sources, soil enhancers). Sources like wastewater, human waste, waste nutrient solution, etc. can be used for P recycling. This review paper extensively summarizes the importance and distribution of P in different environmental compartments, the effects of P in natural and engineered systems, P removal mechanisms through treatment, and recycling technologies specially focusing on various types of phosphate mineral precipitation. In particular, the factors controlling mineral (e.g., struvite and vivianite) precipitation in natural and engineered systems are also discussed.

Comparative study of heavy metal residues in struvite products recovered from swine wastewater using fluidised bed and stirred reactors.

Struvite (MgNH4PO4·6H2O) crystallisation is a promising approach for phosphorus recovery from swine wastewater. Currently, intensive pig feeding has made heavy metals (HMs) extensive in swine wastewater; therefore, significant amounts of HMs have been detected in struvite recovery products. In this study, the HM residues in the struvite products recovered from stirred and fluidised bed reactors were investigated. The results showed that Zn, Mn, and Cu were the most abundant elements in swine wastewater (1,175.3 ± 178.0, 745.4 ± 51.5, and 209.3 ± 54.4 µg L-1, respectively). The HMs, especially Zn (97.0%) and Cu (96.8%), were mainly distributed in the total suspended solids (TSS) of the swine wastewater. Redundancy analysis revealed that the HMs in the struvite products harvested from the fluidised bed reactor were mainly attributable to the aggregation of dissolved matters, because most TSS were elutriated through fluidisation. In contrast, the HMs in the struvite products harvested from the stirred reactor mainly originated from the TSS, which complexed with the HMs, and co-precipitated and settled with the struvite products. Furthermore, chemical fractionation of the HM species confirmed that the presence of HMs in the struvite products was mainly attributable to metal precipitation and organic aggregation.

Crystallization and demineralization phenomena in washed-rind cheese.

This report documents an observational study of a high-moisture washed-rind cheese. Three batches of cheese were sampled on a weekly basis for 6 wk and again at wk 10. Center, under-rind, rind, and smear samples were tested for pH, moisture, and selected mineral elements. Powder x-ray diffractometry and petrographic microscopy were applied to identify and image the crystal phases. The pH of the rind increased by over 2 pH units by wk 10. The pH of the under-rind increased but remained below the rind pH, whereas the center pH decreased for most of aging and only began to rise after wk 5. Diffractograms of smear material revealed the presence of 4 crystal phases: brushite, calcite, ikaite, and struvite. The phases nucleated in succession over the course of aging, with calcite and ikaite appearing around the same time. A very small amount of brushite appeared sporadically in center and under-rind samples, but otherwise no other crystallization was observed beneath the rind. Micrographs revealed that crystals in the smear grew to over 250 µm in length by wk 10, and at least 2 different crystal phases, probably ikaite and struvite, could be differentiated by their different optical properties. The surface crystallization was accompanied by a mineral diffusion phenomenon that resulted, on average, in a 217, 95.7, and 149% increase in calcium, phosphorus, and magnesium, respectively, in the rind by wk 10. The diffusion phenomenon caused calcium, phosphorus, and magnesium to decrease, on average, by 55.0, 21.5, and 36.3%, respectively, in the center by wk 10. The present study represents the first observation of crystallization and demineralization phenomena in washed-rind cheese.

A novel treatment processes of struvite with pretreated magnesite as a source of low-cost magnesium.

By crystallization process, phosphorus can be recycled from wastewater. However, the reagent cost limits the application of struvite precipitation. Magnesite, as a low-cost magnesium source, can result in a cost savings, while the poor dissolution offset of low-cost reagent. In this study, most of the pyrolysate of magnesite was dissolved by changing the process of reagent addition; the solubility of the pyrolysate was increased at acid wastewater. The removal rate of phosphate by the pyrolysate was higher than that of magnesite, the phosphate removal rate was from 70.2 to 88.2% at 600 °C, 0.5 h to 1200 °C, 3 h. Phosphate removal rate was achieved optimal when calcination temperature was 700 °C at 2 h. By adding the pyrolysate to acid wastewater (pH ≤ 2) before NH4Cl, phosphate removal rate was closed to that of MgCl2 as magnesium source, while magnesite was priced at similar levels to lime.

Nutrient removal and energy production from aqueous phase of bio-oil generated via hydrothermal liquefaction of algae.

Removal of nutrients (phosphorus and nitrogen) as struvite from bio-oil aqueous phase generated via hydrothermal liquefaction of algae was evaluated in this study. Effect of process parameters such as pH, temperature and reaction time on struvite formation was studied. More than 99% of phosphorus and 40-100% ammonium nitrogen were removed under all experimental conditions. X-ray diffraction analysis confirmed the formation of struvite, and the struvite recovered from bio-oil aqueous phase can be used as a slow-release fertilizer. Biogas production from struvite recovered bio-oil aqueous phase showed 3.5 times higher CH4 yield (182±39mL/g COD) as compared to non-struvite recovered aqueous phase. The results from this study indicate that both struvite and methane can be produced from bio-oil aqueous phase.

Prospect of recovering phosphorus in magnesium slag-packed wetland filter.

Phosphorus recovery from wastewater not only reduces the unbearable impacts of excessive nutrient discharge on environmental systems but also favor the reuse of phosphorus resource. Based on the mechanism as well as technical analysis for major phosphorus recovery techniques including struvite precipitation and wetland substrate adsorption, a novel magnesium slag-packed wetland filter and corresponding operational procedures are proposed, which aim to reduce the dependence of using magnesium-containing chemical reagent as magnesium sources for struvite precipitation, and improve the accumulation and recovery performance for struvite precipitation within porous wetland substrate. Results from preliminary experiments indicated that magnesium slag particles with approximately 2 mm in diameter can recover 43.20-72.39% phosphorus from 1-25 mol/L PO43- solution, and the presence of 5-50 mol/L NH4+ contributed to 11.71-29.11% enhancement of phosphorus recovery mainly due to struvite precipitation. The detected generation of struvite via XRD spectrum analysis partly demonstrated the potential of phosphorus recovery in magnesium slag-packed wetland filter. The proposed phosphorus recovery technology is free of secondary pollution and solid waste generation; phosphorus-saturated (mainly due to struvite precipitation and adsorption) magnesium slag particles can be potentially used as phosphorus fertilizer and thus partly solved the traditional shortages of disposing phosphorus-saturated substrate due to low phosphorus contents.

Effect of different struvite crystallization methods on gaseous emission and the comprehensive comparison during the composting.

This study compared 4 different struvite crystallization process (SCP) during the composting of pig feces. Four combinations of magnesium and phosphate salts (H3PO4+MgO (PMO), KH2PO4+MgSO4 (KPM), Ca(H2PO4)2+MgSO4 (CaPM), H3PO4+MgSO4 (PMS)) were assessed and were also compared to a control group (CK) without additives. The magnesium and phosphate salts were all supplemented at a level equivalent to 15% of the initial nitrogen content on a molar basis. The SCP significantly reduced NH3 emission by 50.7-81.8%, but not the N2O. Although PMS group had the lowest NH3 emission rate, the PMO treatment had the highest struvite content in the end product. The addition of sulphate decreased CH4 emission by 60.8-74.6%. The CaPM treatment significantly decreased NH3 (59.2%) and CH4 (64.9%) emission and yielded compost that was completely matured. Due to its effective performance and low cost, the CaPM was suggested to be used in practice.

Phosphorus recovery as struvite from farm, municipal and industrial waste: Feedstock suitability, methods and pre-treatments.

Global population growth requires intensification of agriculture, for which a sustainable supply of phosphorus (P) is essential. Since natural P reserves are diminishing, recovering P from wastes and residues is an increasingly attractive prospect, particularly as technical and economic potential in the area is growing. In addition to providing phosphorus for agricultural use, precipitation of P from waste residues and effluents lessens their nutrient loading prior to disposal. This paper critically reviews published methods for P recovery from waste streams (municipal, farm and industrial) with emphasis on struvite (MgNH4PO4·6H2O) crystallisation, including pre-treatments to maximise recovery. Based on compositional parameters of a range of wastes, a Feedstock Suitability Index (FSI) was developed as a guide to inform researchers and operators of the relative potential for struvite production from each waste.