Graduation Year

2018

Document Type

Thesis

Degree

M.S.E.V.

Degree Name

MS in Environmental Engr. (M.S.E.V.)

Degree Granting Department

Civil and Environmental Engineering

Major Professor

Sarina Ergas, Ph.D.

Committee Member

Jeffrey Cunningham, Ph.D.

Committee Member

Maya Trotz, Ph.D.

Keywords

ANOVA, cost analysis, eutrophication, MINTEQ, sidestream

Abstract

Water resources in Florida have been severely degraded by eutrophic conditions, resulting toxic algae blooms, which negatively affect health and tourism. Eutrophication, or excessive amount of phosphorus (P) and nitrogen (N) in water, overstimulates the production of aquatic plants, depletes dissolved oxygen, and deteriorates the aquatic environment. However, phosphorus is a non-renewable resource essential for all living organisms. In fact, more than half of the total demand for P globally is to supply the food industry, which has concerningly accelerated the depletion rates of phosphate reserves.

In many wastewater treatment plants (WWTPs), the enhanced biological phosphorus removal (EBPR) approach has been employed to achieve high phosphorus removals from wastewater through phosphate-accumulating organisms (PAOs). However, during either anaerobic or aerobic digestion of EBPR sludge, stored polyphosphates are released and carried into the sidestream, which is typically returned to the headworks of the main treatment facility, thereby recycling phosphorus back into the system. This treatment train is highly inefficient because nutrients rather are recirculated rather than recovered.

Struvite (MgNH4PO4•6H2O) is precipitated in oversaturated aqueous solutions with equal molar concentrations of magnesium, ammonium, and phosphate. The controlled crystallization of struvite may be applied to remove phosphorus and some ammonium from sidestreams, which is the liquid portion of the digester effluent. Struvite can be employed as a sustainable slow-release fertilizer due to its low solubility in water. This offers the opportunity of marketing the struvite produced under controlled conditions and creating a revenue for the utility.

The specific research objectives of this thesis are (1) to investigate different possible operating conditions under which anaerobically digested sludge from EBPR facilities might be treated through struvite precipitation; (2) to quantify the removal of N and P from sidestreams from anaerobically digested EBPR sludge via struvite precipitation and assess the composition of the precipitate obtained; and (3) to generate a cost analysis to assess the trade-offs between the capital and operation and maintenance (O&M) costs of struvite production and the benefits such as reduced chemical use and production of a slow-release fertilizer.

The main parameters affecting struvite precipitation are the Mg2+ to PO43- molar ratio, pH, temperature, mixing speed, hydraulic retention time (HRT), and the seed quantity added to promote nucleation. Different operating conditions within these parameters were batch-tested as part of this study using sidestream from the pilot-scale anaerobic digester (AD) fed from Falkenburg Advanced Wastewater Treatment Plant (FAWWTP) EBPR sludge. Additionally, the effect of temperature and pH were investigated using Visual MINTEQ simulations. Analysis of Variance (ANOVA) was employed to investigate the variance within the removals from the centrate obtained for phosphate, ammonium, magnesium, and calcium. The chemical composition of the solids collected after employing the selected operating conditions was analyzed by powder X-ray diffraction (PXRD).

The results for the batch tests performed as part of this thesis were quantified in terms of the removals of phosphate, ammonium, magnesium, and calcium from the centrate. The greatest amount of phosphate removal was achieved by operating the struvite reactor at 4.0 mmol of Mg2+ per mmole of PO43-. The other molar ratios tested were 1.0, 2.0, and 3.0. Visual inspection of the data showed significant variability in removals of ammonium, calcium, and magnesium, which are likely to be correlated with the highly variable influent concentrations into the struvite reactor. In this case, ANOVA will require larger data sets to accurately analyze variance in the results. The statistical results given by ANOVA for the pH suggests that the main species to contribute with struvite being precipitated are statistically stable within the tested pH values of 8.5, 9.0, and 9.5. The results obtained by the simulation using Visual MINTEQ indicated that maximum saturation as function of pH takes place at a pH between 9.5 and 10.0. The ANOVA for the mixing speed showed that significant amounts of ammonium were removed at higher mixing speeds. This is likely due ammonium being volatilized, which is enhanced by turbulence. Magnesium and phosphate showed lower removals at higher mixing speeds, suggesting that too high mixing speeds will promote struvite seed dissolution. ANOVA identified NH4+ and Ca2+ as the species significantly impacted by modifying the HRT from 8 to 20 minutes. This suggests that prolonged HRT promotes inorganic nitrogen species to volatilize. It is likely that at higher HRT, tricalcium phosphates (TCP) or other favored calcium species coprecipitated together with struvite. Regarding the added struvite seed for nucleation, the greatest removals of ammonium, magnesium, and, phosphate were observed when 1g/L of struvite seed was added. The results also indicated that adding 5 and 10 g/L was an excessive amount of seed, which ended up contributing significantly to more nutrients into the centrate rather than precipitating them. The results also suggested that the struvite crystals formed in the sidestream by secondary nucleation, since removals close to zero were reached after adding no seed. The optimum temperature identified by the simulation in Visual MINTEQ was 21°C.

Operating the struvite reactor under the optimal conditions identified in the batch tests, resulted in an average of 99% total P (TP) and 17% total N (TN) removals. The precipitate molar composition for [Mg2+:NH4+:PO43-] was equal to [2:2:1] based on the concentrations that disappeared from the aqueous solution, suggesting that other minerals coprecipitated with struvite. Visual MINTEQ predicted that together with struvite, CaHPO4 and CaHPO4•2H2O will also precipitate under the tested conditions. However, given the obtained ratio it is likely that other unpredicted species by Visual MINTEQ, such as magnesium carbonates or magnesium hydroxide coprecipitated with struvite. PXRD analysis also revealed that the sample was likely contaminated struvite, although the specific contaminants were not identified.

A cost analysis was performed to distinguish the economic feasibility of incorporating a struvite harvesting system to treat the anaerobically digested sidestream from the Biosolids Management Facility (BMF) within the Northwest Regional Water Reclamation Facility (NWRWRF). Three different scenarios were evaluated; in Scenario (1) Ostara® Nutrient Recovery Technologies Inc. (Ostara®) evaluated the production of struvite from anaerobically digested EBPR sidestream using a fluidized reactor. In Scenario (2), Ostara® evaluated the production of struvite in a fluidized bed reactor by employing Waste Activated Sludge Stripping to Remove Internal Phosphorus (WASSTRIP™) in a mixture of post-anaerobic digestion centrate and pre-digester thickener liquor. Scenario (3) was addressed by Schwing Bioset Inc. (SBI) for a continuously-stirred reactor followed by a struvite harvesting system.

Scenario (2) offers the highest TP and TN recoveries through WASSTRIP™ release due to the additional mass of phosphorus that is sent to the phosphorus recovery process. Therefore, although Scenario (2) has the highest total capital costs ($5M) it also has the shortest payback period (18 years). Scenarios (1) and Scenario (3) have similar payback periods (22-23 years) but very different total capital costs. The annual savings by producing struvite in Scenario (3) is $40K, which is about 30% less than producing struvite in Scenario (1). This is probably because the only savings considered under Scenario (3) were the lower alum usage and the fertilizer revenue; however, the savings by producing class A biosolids, were not accounted for. Consequently, the reduced total capital cost of $960K and the annual payment amount per interest period close to $80K, positioned Scenario (3) as the more feasible one, considering 20 years as the expected life of the asset at a 5% interest rate.

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