Crystallization kinetics and growth of struvite crystals by seawater versus magnesium chloride as magnesium source: towards enhancing sustainability and economics of struvite crystallization.

The recycling of nutrients from wastewater and their recovery in the form of valuable products is an effective strategy to accelerate the circular economy concept. Phosphorus recovery from wastewater by struvite crystallization (MgNH4PO4·6H2O) is one of the most applied techniques to compensate for the increasing demand and to slow down the depletion rate of phosphate rocks. Using low-cost magnesium sources, such as seawater, improves the financial sustainability of struvite production. In this study, the potential of seawater for struvite crystallization versus the commonly used magnesium source, MgCl2, was tested by crystal growth and kinetic experiments. The impact of ammonium concentration, magnesium concentration and pH on the growth kinetics of struvite in synthetic and real reject water were studied. The results showed that simultaneous precipitation of calcium phosphate was insignificant when using seawater, while presence of struvite seeds diminished it further. Among the supersaturation regulators, pH had the most significant effect on the struvite growth with both MgCl2 and seawater, while high N:P molar ratios further improved the struvite crystal growth by seawater. The N:P molar ratios higher than 6 and Mg:P molar ratios higher than 0.2 are recommended to improve the crystal growth kinetics. It was concluded that seawater is a promising alternative magnesium source and the control of supersaturation regulators (i.e., Mg:P, N:P and pH) is an effective strategy to control the reaction kinetics and product properties.

Struvite crystallization by using raw seawater: Improving economics and environmental footprint while maintaining phosphorus recovery and product quality.

Seawater, as an alternative magnesium source, has the potential to improve the overall economics and environmental footprint of struvite production compared to the use of pure magnesium salts. However, the dilution effect and the presence of other ions in seawater can reduce the phosphorus recovery potential and the simultaneous precipitation of other compounds may reduce the quality of the produced struvite. This work presents a comparative study of seawater and MgCl2 by performing a series of thermodynamic equilibrium modeling and crystallization experiments. The results revealed that acceptable phosphorus recovery (80-90%) is achievable by using seawater as the magnesium source for struvite precipitation. Further, the simultaneous precipitation of calcium phosphates was successfully controlled and minimized by optimum selection of reaction pH and seawater volume (i.e. Mg:P and Mg:Ca molar ratios). The increase of temperature from 20 °C to 30 °C reduced the phosphorus recovery by 15-20% while it increased the particle size by 30-35%. The presence of suspended solids in reject water did not have significant effects on phosphorus recovery but it made the struvite separation difficult as the obtained struvite was mixed with suspended solids. The experimental results and economic evaluation showed that the use of seawater can reduce the chemical costs (30-50%) and the CO2-footprint (8-40%) of struvite production. It was concluded that seawater is a potential alternative to pure magnesium sources in struvite production, while studies in larger scale and continuous mode are needed for further verification before full-scale applications.

Self-optimizing attainable regions of the anaerobic treatment process: Modeling performance targets under kinetic uncertainty.

Despite the advantage of model-based design, anaerobic digesters are seldom designed using biokinetic models due to lack of reliable kinetic coefficients and/or systematic approaches for incorporating kinetic models into digester design. This study presents a systematic framework, which couples practical identifiability, uncertainty quantification and attainable region (AR) concepts for defining process performance targets, especially when reliable kinetic coefficients are unavailable. Within the framework, we introduce the concept of self-optimizing ARs, which define performance targets that results in near optimal operation in spite of variations in kinetic coefficients. Using the case of modified Hill model, only 3 out of the 6 model parameters (unidentifiable set) are responsible for the model prediction uncertainty. The uncertainty bands (mean, 10th percentile and 90th percentile) on the model states has been computed using the Monte Carlo Simulation procedure and attainable regions for the different levels of uncertainty has been constructed and the boundaries interpreted into digester structures. The self-optimizing attainable regions have been defined as the intersection region of the attainable regions corresponding to the mean, 10th percentile and 90th percentile. Incorporating uncertainty significantly reduces performance targets of the process but increases self-optimality in defining performance targets. Unlike the attainable region, which represents the limits of achievability for defined kinetics, the self-optimizing attainable region represents the set of all possible states attainable by the system even in cases of kinetic uncertainty. In summary, the concept of self-optimizing ARs provides a systematic way of defining process performance targets and making economic decisions under conditions of uncertainty.

Simulation of two-dimensional attainable regions and its application to model digester structures for maximum stability of anaerobic treatment process.

Unlike high-rate anaerobic digesters that employ some mechanism to retain microbial sludge mass, low-rate systems use sufficiently long hydraulic retention times to ensure process stability, which becomes economically unattractive for treating large quantities of waste. This study presents the use of attainable region to develop a new strategy to enhance the stability of low-rate digesters. By considering three digestion cases, diary manure only (batch 1) or diary manure with granular (batch 2) or lagoon (batch) sludge as innoculum, the following findings were obtained. (1) For a given concentration of volatile acids in an anaerobic digester, higher concentrations of methanogenic archae can be attained using a digester structure (combination of different digesters) as opposed to single digester. (2) For a given digested substrate, a change in the source of inoculum results in a change in the limits of achievability by the system (attainable limits for batches 1, 2 and 3 were 46.486(g/L)2, 5.562(g/L)2 and 0.551(g/L)2, which resulted in performance improvements of 118.604%,175.627% and 200.436% respectively), and hence optimal digester structure. The evidence from this study suggests that the technique can be used to simultaneously improve process stability, define performance targets and propose digester structures required to achieve a given target.

Enhancing efficiency and economics of phosphorus recovery process by customizing the product based on sidestream characteristics - an alternative phosphorus recovery strategy.

The enhanced biological phosphorus removal process makes the phosphorus recovery feasible from the dewatering streams of biological sludge. The physicochemical properties of these sidestreams, as an input to a crystallizer, are different before and after anaerobic digestion. In this study, phosphorus recovery by calcium phosphate is proposed for pre-digestion sidestreams and by struvite precipitation for post-digestion sidestreams. The thermodynamic modeling followed by experimental tests was performed to evaluate the recovery efficiency and product properties of struvite and calcium phosphates. The variations in phosphorus recovery potential, reaction kinetics and particle size distribution emphasize the importance of the adjustment of initial supersaturation and pH of the reaction. The optimum pH, considering the economics and recovery efficiency, for both calcium phosphate and struvite precipitation was found to be pH = 8.5, whereas further increase of pH will not improve the overall efficiency of the process. In the case of calcium phosphate precipitation, it was shown that possible phase transformations should be considered and controlled as they affect both process efficiency and product properties. The economic evaluation indicated that the optimized operational condition should be determined for the phosphorus recovery process and that chemical costs for the production of calcium phosphates is lower than for struvite.

A study on the reactivity characteristics of dissolved effluent organic matter (EfOM) from municipal wastewater treatment plant during ozonation.

The reactivity of dissolved effluent organic matter (EfOM) in the process of ozonation was examined. Under different ozone dosages (0.42 ± 0.09, 0.98 ± 0.11 and 2.24 ± 0.17 mgO3/mg DOC), the EfOM before and after ozonation could be classified into four fractions according to their hydrophobicities. By ozonation, the hydrophobic fractions, especially hydrophobic acid (HOA) and hydrophobic neutral (HON), were found to undergo a process of transformation into hydrophilic fractions (HI), of which the HOA were first transformed into HON, and then the majority of the HON fraction was later converted to HI by further ozonation. It was noticeable that after ozonation, the fluorescence intensity in the humic-like and protein-like regions decreased as indicated by the excitation and emission matrix (EEM) spectra for the hydrophobic fractions. By coupling the EEM spectra with the molecular size analysis using high performance size exclusion chromatography (HPSEC), the difference between the characteristic distributions of the humic-like and protein-like fluorophores were further revealed. It could thus be extrapolated that ozone might have preferentially reacted with the protein-like hydrophobic fraction with molecular weight (MW) less than 100 kDa. Moreover, by X-ray photoelectron spectroscopy (XPS) analysis, it was identified that with increasing ozone dosage (from 0 to 2.24 ± 0.17 mgO3/mg DOC), the aromaticity of HON decreased dramatically, while aliphatics and ketones increased especially at the low ozone dose (0.42 ± 0.09 mgO3/mg DOC). Of the EfOM fractions, the HON fraction would have a higher content of electron enriched aromatics which could preferentially react with ozone rather than the HOA fraction.