Phosphorus recovery from phosphate tailings through a two-stage leaching-precipitation process: Toward the harmless and reduction treatment of P-bearing wastes.

To achieve highly efficient extraction of phosphorus (P) and comprehensive utilization of phosphate tailings, a two-stage leaching-precipitation method was proposed. Phosphate tailings primarily consisted of dolomite, fluorapatite, and quartz. During the first-stage leaching, the large majority of dolomite was selectively dissolved and the leaching efficiency of Mg reached 93.1 % at pH 2.0 and 60 °C. The subsequent second-stage leaching of fluorapatite was performed and the P leaching efficiency was 98.8 % at pH 1.5 and 20 °C, while the quartz remained in the residue. Through two-stage leaching, a stepwise leaching of dolomite and fluorapatite was achieved. After chemical precipitation, calcium phosphate with a high purity of 97.9 % was obtained; and the total recovery efficiency of P exceeded 98 %. The obtained calcium phosphate can be a raw material in the phosphorus chemical industry, while the Mg-rich leachate and the final quartz-rich residue have the potential for Mg extraction and the production of mortars or geopolymers, respectively. The two-stage leaching-precipitation process could significantly reduce the leaching costs, and enhance the reaction rates. It is expected to realize a volume reduction and efficient resource utilization of the phosphate tailings by using this sustainable and promising solution.

Evaluating the opportunities for mainstream P-recovery in anaerobic/anoxic/aerobic systems.

Mainstream P-recovery can help wastewater treatment plants (WWTPs) to effectively maintain good enhanced biological phosphorus removal (EBPR) while helping to recover P. In this study, a pilot-scale anaerobic-anoxic-aerobic (A2O) process was operated for simultaneous COD/N/P removal and P-recovery under different operational conditions. The operation with conventional extraction of waste activated sludge (WAS) from the aerobic reactor was compared to the mainstream P-recovery strategy of WAS extraction from the anaerobic reactor. Successful nutrient removal was obtained for both scenarios, but the anaerobic WAS extraction results improved polyphosphate accumulating organisms (PAOs) activity by increasing almost 27 % P concentration in the anaerobic reactor. WAS fermentation was also evaluated, showing that anaerobic WAS required only 3 days to reach a high P concentration, while the aerobic WAS fermentation required up to 7 days. The fermentation process increased the amount of soluble P available for precipitation from 24.4 % up to 51.6 % in the fermented anaerobic WAS scenario. Results obtained by precipitation modelling of these streams showed the limitations for struvite precipitation due to Ca2+ interference and Mg2+ and NH4+ as limiting species. The optimum precipitation scenario showed that P-recovery could reach up to 51 % of the input P, being 90 % struvite.

Leaching of phosphorus from phosphate tailings and extraction of calcium phosphates: Toward comprehensive utilization of tailing resources.

Phosphate tailing is an extremely fine by-product during phosphate ore flotation. Due to the large quantities and relatively higher P2O5 content, the phosphate tailings have been considered as a potential P resource, compared to other P-bearing wastes. Besides, phosphate tailings also contain a large amount of available components, such as Ca, Mg, and Si. To explore a low-cost and efficient process for the utilization of phosphate tailings, the hydrochloric acid leaching-precipitation method was employed to recover phosphorus. The P in phosphate tailings can be selectively dissolved into leaching liquor, followed by the precipitation of calcium phosphates from the leaching liquor through pH adjustment. The results showed that P was predominantly concentrated in fluorapatite and its dissolution ratio increased with the decrease in pH. At pH 1.0, the P dissolution efficiency from phosphate tailings reached 96.3%, along with the majority of Mg and Ca. However, Si was hardly dissolved. It demonstrated that almost all the fluorapatite and dolomite were dissolved while the quartz was difficult to dissolve. Dolomite was more preferentially dissolved than fluorapatite. Increasing temperature contributed to the dissolution of dolomite while suppressing fluorapatite dissolution. The residue containing 87.9% SiO2 (quartz) and only 0.25% P2O5 has the potential as a building material. As the pH increased to 7.0, the collected precipitate consisted of 34.18% P2O5 and 56.10% CaO, which can serve as a source of a slow-released phosphate fertilizer. The highly efficient utilization of phosphate tailings was achieved via this process.

A novel calcium peroxide/attapulgite-Fe(II) process for high concentration phosphate removal and recovery: Efficiency and mechanism.

Phosphorus (P) has been overused in livestock farming, which inevitably results in high-concentration P-containing wastewater. Managing total phosphorus discharge is important to prevent eutrophication in aquatic environments, thus it is critical to develop new technologies for the removal and recovery of high-concentration phosphate. In this study, a novel calcium peroxide/attapulgite (CP/ATP) composite was developed and coupled with Fe(II) for high-concentration phosphate removal and recovery. The results demonstrated that the optimal dosage of the CP/ATP-Fe(II) process was CP/ATP = 0.25 g/L and Fe(II) = 2 mM. The pH effect on phosphate removal was minimal, while phosphate removal efficiency rose by 16.7% with the temperature increased from 10 °C to 25 °C. The co-existing ions exhibited little effect on phosphate removal, and the CP/ATP-Fe(II) process showed effective phosphate removal from the real piggery wastewater. The P content of the precipitates after phosphate removal by this process was as high as 25.82%, indicating its good potential for P recycling. A significant synergistic effect existed in CP/ATP and Fe(II) for phosphate removal, and the SEM-EDS, XRD, Raman and XPS characterization exhibited that the phosphate removal mainly relied on the in-situ-formed Fe(III) and the participation of calcium (Ca) species. Co-precipitation was the predominant mechanism for phosphate removal, and the proportions of Fe(III)-P, Ca-P and Ca-Fe(III)-P in the precipitates were 51.5%, 31.2% and 17.3%, respectively. This study provides a highly efficient process for phosphate removal and recovery from wastewater, and insights into interactions among phosphorus, iron and calcium.

Phosphorus recovery from high solid content liquid fraction of digestate using seawater bittern as the magnesium source.

Phosphorus recovery from digestate is considered a challenge because the possible discharge can lead to eutrophication. This study focuses on phosphorus recovery as struvite from the liquid fraction of swine manure digestate at a high total solids concentration, by using a lab-scale crystallizer operated in continuous mode (7 L·d-1). A by-product of salt production (seawater bittern, SWB) was assessed as Mg source for the formation of struvite instead of a chemical dosage (MgCl2) within a circular economy approach. Different Mg/P (1.8:1; 2:1; 3:1) ratios and different TS contents (TS 3.5 and 4.5 %) were studied. The maximum P recovery of 85 % and N recovery of 52 % was obtained at 4.5 % of TS and Mg/P ratio of 2:1, corresponding to an overall P and N recovery on the raw digestate of 70 % and 46 %, respectively. The presence of struvite was confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM-EDS). Dried samples were then used as fertilizer in agronomic pot tests using Brassica rapa chinensis. Struvite obtained, showed comparable fertilizing properties in comparison with conventional fertilizers in terms of P (Mineral 5.6 ± 0.4; Poultry 5.7 ± 0.2; Struvite 5.9 ± 0.1 g kg-1), N and total biomass content such as chlorophylls ratio. The growth tests confirmed the possible use of struvite recovered as competitive alternative to conventional chemical phosphate fertilizers. The results showed that it can be possible to promote sustainable P recovery from high solids digestates by the combination of crystallizer reactor and Mg-salt byproducts.

Exploring the stability of an A-stage-EBPR system for simultaneous biological removal of organic matter and phosphorus.

This work evaluates the performance and stability of a continuous anaerobic/aerobic A-stage system with integrated enhanced biological phosphorus removal (A-stage-EBPR) under different operational conditions. Dissolved oxygen (DO) in the aerobic reactor was tested in the 0.2-2 mgDO/L range using real wastewater amended with propionic acid, obtaining almost full simultaneous COD and P removal without nitrification in the range 0.5-1 mgDO/L, but failing at 0.2 mgDO/L. Anaerobic purge was tested to evaluate a possible mainstream P-recovery strategy, generating a P-enriched stream containing 22% of influent P. COD and N mass balances indicated that about 43% of the influent COD could be redirected to the anaerobic digestion for methane production and 66% of influent NH4+-N was discharged in the effluent for the following N-removal B-stage. Finally, when the system was switched to glutamate as sole carbon source, successful EBPR activity and COD removal were maintained for two months, but after this period settleability problems appeared with biomass loss. Microbial community analysis indicated that Propionivibrio, Thiothrix and Lewinella were the most abundant species when propionic acid was the carbon source and Propionivibrio was the most favoured with glutamate. Thiothrix, Hydrogenophaga, Dechloromonas and Desulfobacter appeared as the dominant polyphosphate-accumulating organisms (PAOs) under different operation stages.

Nitrogen and phosphorous recycling from human urine by household electrochemical fixed bed in sparsely populated regions.

Decentralized treatment of human urine in sparsely populated regions could avoid the problem of sewage collection in traditionally centralized treatment schemes and simultaneously utilize the recovered N/P fertilizer in-situ to nurture gardens. Herein, an integrated electrochemical fixed bed packed with divided magnesite and carbon zones was constructed for the pretreatment of human urine, followed by the recovery of 95.0% NH4+ and 85.8% PO43- via struvite precipitation and NH3 volatilization as well as the on-site employment of the produced struvite as fertilizer. In the process, the acid/base zones created by electrochemical water splitting dissolved the magnesite filler as the Mg2+ source of struvite, further creating an ideal pH environment for struvite precipitation and NH3 volatilization in the effluent. Without the need to control solution pH by chemical addition, the system can resist impacts from changes in water quality by adjustment of the current density and flow rate, indicating its great potential for automatic operation. Life cycle assessment indicated that the on-site employment of produced struvite avoids the long-distance fertilizer transportation required for fertilization, thus reducing carbon emission by a hundred million tons per year if the household facility is driven by clean electricity.

Variation in Phosphorus Speciation of Sewage Sludge throughout Three Wastewater Treatment Plants: Determined by Sequential Extraction Combined with Microscopy, NMR Spectroscopy, and Powder X-ray Diffraction.

The variation in phosphorus (P) speciation of sewage sludge throughout three wastewater treatment plants (WWTPs) was obtained by combining sequential P extraction with optical and scanning electron microscopy (SEM), chemical analyses, powder X-ray diffraction (PXRD), and 27Al and 31P nuclear magnetic resonance (NMR) spectroscopy. The WWTPs combine chemical P removal (CPR) and enhanced biological P removal (EBPR) and were compared to understand the effect of iron (Fe) dosing with and without codosing of aluminum (Al) and thermal hydrolysis on the P speciation. 31P NMR showed comparable inorganic orthophosphate (ortho-P, 53-60% of total P) and organophosphate (organic-P, 37-45%) in primary sludge, whereas polyphosphate (poly-P, 23-44%) from poly-P accumulating organisms (PAOs) was mainly observed in the secondary sludge. Inorganic ortho-P (90-98%) dominated after anaerobic digestion, which degraded poly-P and most organic-P. The inorganic ortho-P was mainly Fe bound P (Fe-P), especially after anaerobic digestion (71%). Codosing of Fe and Al led to two comparable fractions: Fe-P (38%) and P sorbed on amorphous Al (hydr)oxides (38%). Vivianite was identified in all samples by microscopy and chemical extraction but was PXRD amorphous in 12 out of 17 samples. Thus, vivianite may be more common in sewage sludge than previously known.

Synthesis and characterization of struvite derived from poultry manure as a mineral fertilizer.

Animal manure is an important source of nutrients for crop production, but environmental issues can restrict its direct use. Thermochemical processing these manures may be an alternative to concentrate nutrients and reduce the final volume for agriculture application. We aimed here to evaluate the viability of extracting nutrients from chicken manure using a thermochemical process which reduces the volume of transported nutrients, targeting phosphorus (P) recovery as precipitated struvite, without add external source of P. The extraction of nutrients from poultry manure was performed in water, followed by a thermochemical treatment of the solid phase by incineration and acidulation of the resulting ash. Struvite was produced from the acidified ash extract after supplementation with Mg and regulating the pH (~8.5) by KOH addition. The recovery efficiency of P from the poultry manure and incorporation into struvite was 90%. The final product was a multi-nutrient fertilizer with high macronutrient levels (P, K, Mg and S) and low micronutrient content when compared to fresh manure, as well as lower levels of heavy metals, potentially harmful for the environment. The precipitated product obtained here is composed of struvite-NH4 and struvite-K, alongside appreciable quantities of potassium sulphate and hydroxyapatite carbonate. Overall, we conclude that poultry manure represents a viable source of P and N for struvite production resulting in a nutrient-rich, pathogen-free inorganic fertiliser suitable for widespread use in agriculture.

Use of calcined sepiolite in removing phosphate from water and returning phosphate to soil as phosphorus fertilizer.

We investigated the application of cheap but efficient sepiolite for the removal of phosphate and the use of phosphate-adsorbed sepiolite for rice cultivation. Sepiolite was calcined under different temperatures to improve its phosphate adsorption capacity; the sepiolite calcined at 950 °C (950-SPL) was found to have highest adsorption capacity. As the calcination temperature increased, the amount of Ca eluted from sepiolite also increased, resulting in the formation of Ca-P precipitates. Phosphate adsorption on 950-SPL reached equilibrium within 12 h. Both the Langmuir and Freudlich models were not well-fitted to the equilibrium adsorption model because phosphate at initial concentration was fully removed by 950-SPL. The maximum adsorption capacity of 950-SPL with respect to phosphate was 172.34 mg/g. The phosphate adsorption of 950-SPL was endothermic and spontaneous. Phosphate adsorption at pH 3 was two times higher than at pH 11. The presence of bicarbonate significantly influenced the decrease of phosphate by 950-SPL. A breakthrough of column packed with 950-SPL/sand was not observed during >200 h. The phosphate fraction in 950-SPL was mainly composed of apatite-P and residual fraction. A toxicity test using Daphnia magna showed that the toxic units of 950-SPL corresponded to no acute toxicity. Tiller number, shoot height, shoot dry weight and total dry weight were significantly higher in P-adsorbed 950-SPL application than control. It can be concluded that calcined sepiolite can be effective in the removal of phosphate and that the sepiolite after phosphate adsorption can be used as a P fertilizer in soil.

A novel approach of synchronously recovering phosphorus as vivianite and volatile fatty acids during waste activated sludge and food waste co-fermentation: Performance and mechanisms.

This research proposed an innovative approach to synchronously enhance the recovery of phosphorus (P) as vivianite and volatile fatty acids (VFAs) during waste activated sludge (WAS) and food waste (FW) co-fermentation. A high performance was achieved under 30% FW addition and pH uncontrolled, which gained 83.09% of TP recovery as high-purity vivianite (93.90%), together with efficient VFAs production (7671 mg COD/L). The FW supplement could enhance VFAs production and subsequently lower pH to contribute to the release of Fe2+ and PO43-. Also, it could dampen disrupting effects of strong acidic pH on microbial cells (lowering LDH release). Moreover, the flexible pH variation caused by biological acidification could maintain relatively higher microbial activities (increasing enzymes' activities), which was advantageous to the biological effects involved in Fe2+ and PO43 release and VFAs generation. Therefore, this research provide a promising and economic alternative to dispose of WAS and FW simultaneously for valuable resource recovery.

Phosphorus recovery as vivianite from waste activated sludge via optimizing iron source and pH value during anaerobic fermentation.

This study presented an innovative method for phosphorus (P) recovery as vivianite from waste activated sludge (WAS) via optimizing iron dosing and pH value during anaerobic fermentation (AF). The optimal conditions for vivianite formation were in the pH range of 6.0-9.0 with initial PO43- >5 mg/L and Fe/P molar ratio of 1.5. Notably, FeCl3 showed advantages over ZVI for the simultaneous release of Fe2+ and PO43- during WAS fermentation, especially in acidic conditions. The FeCl3 dosing at pH 3.0 could contribute to 78.81% Fe2+ release and 85.69% of total PO43- release from WAS. They were ultimately recovered in the form of high-purity vivianite (93.67%). Clostridiaceae (40.25%) was the predominant bacteria in FeCl3-pH3 reactors, which played key roles in inducing dissimilatory iron reduction for Fe2+ formation. Therefore, P recovery as vivianite from WAS fermentation might be a promising and highly valuable approach to relieve the P crisis.

An overview of technologies to recover phosphorus as struvite from wastewater: advantages and shortcomings.

Phosphorus (P) is a significant limiting nutrient which is essential for all forms of lives. However, phosphate rock reserves are depleting rapidly due to population growth. At the same time, several countries have imposed legislative regulations on P-release into surface waters due to eutrophication. Nutrient recovery from wastewater can facilitate a sustainable, cost-effective and environment-friendly source of phosphorus. Although P-recovery as struvite from wastewater has been widely studied for a long time, there still exists a lot of challenges for widespread full-scale implementation. This paper presents a comprehensive analysis of the current state of the technologies for phosphorus recovery in the form of struvite. Fluidized bed reactors (FBRs) are widely used compared to continuously stirred reactors for P-recovery as struvite because of different solid and liquid retention time. Commercially available technologies were reported to accomplish about 80% P-removal efficiencies with a reasonable P-recovery for the most of the cases. The struvite production rate of various technologies varies from 0.89 to 13.7 kg/kg influent P. Nevertheless, these technologies are associated with several shortcomings such as high operational costs, high energy consumption, and large footprint. Increasing efforts focusing on the development of sustainable and commercially feasible technologies are expected in this sector as P-recovery is considered to be the future of wastewater engineering.

Acidogenic phosphorus recovery from the wastewater sludge of the membrane bioreactor systems with different iron-dosing modes.

A novel acidogenic phosphorus recovery (APR) process was developed in combination with Fe(III)-based chemical phosphorus removal and a membrane bioreactor (MBR) for enhanced wastewater treatment and effective P recovery. Two different system configurations were evaluated: Fe-dosing MBR (Fe-MBR), with the Fe-dosing into the MBR, and Fe-enhanced primary sedimentation followed by the MBR (FeP-MBR). The results show that both systems performed well for enhanced nutrient (N and P) removals and P recovery, with approximately 50% of the total P recovered from the municipal wastewater in the form of vivianite. Compared to the Fe-MBR system, FeP-MBR achieved more efficient P recovery under low food-waste loading conditions, maintained a higher ratio of biomass in activated sludge and experienced a slower rate of membrane fouling. Important functional bacteria were identified, including Prevotella and Selenomonas, which are active in hydrolysis and acidogenesis of sludge, and Aeromonas and Sulfurospirillum, which are involved in dissimilatory iron reduction.

Impact of supersaturation ratio on phosphorus recovery from synthetic anaerobic digester supernatant through a struvite crystallization fluidized bed reactor.

Over the past few decades, several technologies have been developed to recover phosphorus (P) as struvite from wastewater. Although these technologies have achieved reasonable P-removal efficiencies, these technologies are associated with several shortcomings such as high capital and operating costs, longer crystallization time and production of low-quality product. This study focussed on the development of an efficient technology by designing a new fluidized bed reactor (FBR) and determining its optimum operating conditions. The supersaturation ratio is the most important process parameter for struvite recovery. This study exerted effort to establish a range of supersaturation ratios in order to achieve optimum P-removal and recovery with a lesser amount of fine crystals produced. Bench-scale FBR used in this study was able to accomplish 90% P-removal with 18% P-recovery. P-removal efficiency was observed to be increasing with an increase in the initial supersaturation ratio up to a value of 6.5. On the other hand, an increase in the supersaturation ratio resulted in a lower P-recovery efficiency with an increase in fines production. The supersaturation ratio from 5.5 to 6.0 was found to be optimum for efficient operation of the reactor.

An integrated membrane bioreactor system with iron-dosing and side-stream co-fermentation for enhanced nutrient removal and recovery: System performance and microbial community analysis.

An integrated membrane bioreactor (MBR) system was developed for enhanced nutrient (N and P) removal and effective P recovery in wastewater treatment. The system consisted of an iron-dosing MBR and side-stream fermentation for P removal and recovery and side-stream denitrification for N removal. Around 98.1% of the total phosphorus (TP) in wastewater was removed by ferric iron-induced precipitation and membrane filtration in the aerobic MBR, and nearly 53.4% of the TP could be recovered via anaerobic fermentation from the MBR sludge. In addition, the fermenter that allowed acidogenic co-fermentation with food waste provided sufficient soluble organics for biological denitrification, and an overall 91.8% total N removal was achieved through the side-stream denitrification. High-throughput sequencing was applied to analyse the microbial communities in the integrated system, and important functional bacteria were identified for nitrification, denitrification, acidogenic fermentation and dissimilatory iron reduction through the different components of the system.

Effect of various types of thermochemical processing of sewage sludges on phosphorus speciation, solubility, and fertilization performance.

Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950°C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400°C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers.

Roles of extracellular polymeric substances in enhanced biological phosphorus removal process.

Enhanced biological phosphorus removal (EBPR) process is known to mainly rely on the ability of phosphorus-accumulating organisms to take up, transform and store excess amount of phosphorus (P) inside the cells. However, recent studies have revealed considerable accumulation of P also in the extracellular polymeric substances (EPS) of sludge, implying a non-negligible role of EPS in P removal by EBPR sludge. However, the contribution of EPS to P uptake and the forms of accumulated extracellular P vary substantially in different studies, and the underlying mechanism of P transformation and transportation in EPS remains poorly understood. This review provides a new recognition into the P removal process in EBPR system by incorporating the role of EPS. It overviews on the characteristics of P accumulation in EPS, explores the mechanism of P transformation and transportation in EBPR sludge and EPS, summarizes the main influential factors for the P-accumulation properties of EPS, and discusses the remaining knowledge gaps and needed future efforts that may lead to better understanding and use of such an EPS role for maximizing P recovery from wastewater.