Development of novel fertilizer manufacturing processes using human urine

57 Figure 5-5: Experimental and simulation of the conductivity as a function of added NaHCO3 (A), and the change in conductivity per mmol L-1 of added NaHCO3 (B). 171 Figure D-3: Comparison of the normalized flux for synthetic and real urine stabilized with citric acid (A), stabilized with Ca(OH)2 and pretreated with air bubble (B), comparison of the normalized flux for synthetic urine stabilized with citric acid and synthetic urine stabilized with Ca(OH)2 and pretreated with air bubbles (C), and comparison of the absolute flux for both real and synthetic urine stabilized with citric acid or stabilized with Ca(OH)2 and pretreated with air bubbles (D).

Introduction

Furthermore, the raw material for urea production, NH3, is produced using the Haber-Bosch process, which is responsible for 1.2% of global anthropogenic CO2 emissions (Nørskov et al., 2016). The development of viable source separation methods such as waterless urinals (Flanagan and Randall, 2018) and no-mix toilets with dual plumbing (Gundlach et al., 2021) are helping to advance the field of source separation and urine reuse.

Literature review

URINE CHEMISTRY

The formation of NH3 and H2CO3 results in an increase in pH to about 9 (Udert et al., 2003a). The increase in the concentration of buffer compounds, ammonia and bicarbonate ions, also increases the alkalinity of the solution (Udert et al., 2006).

URINE STABILIZATION

In addition, urine stabilization with Ca(OH)2 results in the precipitation of calcium phosphate (>98% P recovery (Flanagan and Randall, 2018)) which has been shown to be an effective fertilizer (Meyer et al., 2018) . An additional benefit of baseline stabilization is the possibility of pathogen inactivation (Senecal et al., 2018).

Table 1: Summary of methods used to stabilize fresh unhydrolyzed urine.

URINE COLLECTION

2021b) used the Blue Diversion Autarky toilet (Enssle and Udert, 2016) which has a treatment capacity of 10 users per day. These systems use unmixed toilets (like the save!), the urine is diverted to a collection tank pre-dosed with Ca(OH)2 for stabilization, and then the water is evaporated from the urine to form a dry toilet to produce. fertilizer.

CONCENTRATION METHODS

Evaporation of hydrolysed urine results in low nitrogen recovery (10%) (Bethune et al., 2014) due to the volatilization of ammonia gas. Ek et al., 2006) recovered 80% of the water from acidified and hydrolysed urine, but the urine was diluted.

Figure 2-2: Various potential urine volume reduction methods, including variations within each method

MICROPOLLUTANTS

Storage at pH 4 for one year did not result in a significant decrease in PhAC (Gajurel et al., 2007). Although the high energy requirements of plasma (two orders of magnitude more than UV/H2O2) may reduce its desirability (Rodriguez et al., 2022).

FERTILIZER QUALITY

Drugs and hormones: Storage at a pH of 10 for one year showed no significant reduction of four PhACs (Gajurel et al., 2007). Salts can be washed out during rainfall and irrigation (Guizani et al., 2016), but fertilizer application will need to be monitored in dry areas and soils with poor drainage.

URINE PRE-TREATMENT

Salinity can affect soil structure and plant growth (Friedler et al., 2013) and therefore can affect the effectiveness of using an RO brine stream as a liquid fertilizer. To ensure optimal plant growth, application rates may need to be varied based on crop sensitivity to salinity (Mnkeni et al., 2008), and irrigation and soil drainage should be considered (Guizani et al., 2016).

PROPOSED TREATMENT OPTIONS

These methods can potentially be used as a pre-treatment step before the RO concentration process of stabilized urine.

Figure 2-5: Proposed integrated treatment process options to concentrate urine stabilized with Ca(OH) 2 or citric acid, including ore-treatment, membrane separation, and eutectic freeze crystallization

RESEARCH OUTLINE

Conduct a high-level economic analysis evaluating overall energy requirements and product value in the specialty and bulk fertilizer markets considering nutrient recovery and dewatering of various process configurations.

SCOPE AND KNOWLEDGE CONTRIBUTION

Rejection of nitrogen species in real fresh and hydrolyzed human urine by reverse osmosis and nanofiltration. Field testing of a pilot-scale system for alkaline dehydration of source-separated human urine: a case study in Finland.

Theory

REVERSE OSMOSIS AND NANOFILTRATION

It is defined as the occurrence of increased solute concentration at the membrane surface relative to the bulk solution (Bergman, 2007). Cm = the solute concentration at the membrane surface (g L-1) Cp = the solute concentration in the permeate (g L-1).

FREEZE CRYSTALLIZATION

As the solution cools further and more ice forms, the liquid becomes more concentrated, and this process is known as freezing concentration. If the solution is cooled further and enough ice forms, the solution will reach CE.

Figure 3-1: Temperature profile of a liquid as it is cooled from point 1 and when ice crystallization begins at point 2 (A), and a binary phase diagram for a water and salt X solution where the orange line depicts how the concentration of salt X increase

General methods

URINE COLLECTION AND STABILIZATION
THERMODYNAMIC MODELING
ANALYTICAL METHODS
ray diffraction

Scanning electron microscopy (SEM) (FEI Nova SEM 230, FEI, USA) was used to analyze the CaCO3. The SEM was equipped with an Oxford X-Max dispersive X-ray spectroscopy (EDS) detector (Oxford Instruments, England) which was used to characterize deposits on the membrane surface using elemental analysis. The ICDD database (PDF4+, released 2020) was used to compare the diffraction patterns with the reference data files.

Table 6: Recipe for fresh synthetic urine in g L -1 , pH = 5.7.

Chemical addition pre-treatment

INTRODUCTION

There are two common obstacles to the implementation of RO technology: brine management and disposal (Bond and Veerapaneni, 2007), and membrane scaling (Greenlee et al., 2009). Stabilization with Ca(OH)2 is also beneficial as it leads to the precipitation of another scale compound, calcium phosphate (Flanagan and Randall, 2018), which can also be recycled and used as fertilizer (Meyer et al., 2018). However, their effectiveness is limited with increasing CaCO3 saturation indices and precipitation can still occur (Greenlee et al., 2010).

MATERIALS AND METHODS

To determine whether conductivity can be used as a proxy for calcium concentration, the 1 M NaHCO3. To determine the amount of NaHCO3 needed for the single dose, five different urine compositions were collected plus one synthetic urine composition. After it was confirmed that the model accurately reflected the experimental results, it was used to determine whether three other carbonate-forming compounds (KHCO3, NH4HCO3 and MgCO3) could be used as alternative compounds for NaHCO3.

RESULTS AND DISCUSSION

Each sample was stabilized with Ca(OH)2 and the calcium concentrations of the solutions were measured. To increase the sample size, the calcium concentration of three additional stabilized urine compositions from this work and literature (Flanagan and Randall, 2018; Randall et al., 2016) were also evaluated. The single dose was then calculated as the mean plus one standard deviation, which was rounded to 40 mmol NaHCO3 L-1.

CONCLUSIONS

The concentration of Ca(OH)2-stabilized urine using reverse osmosis without pretreatment is likely to cause significant membrane scaling that would make the process economically unfeasible. However, the addition of a bicarbonate salt (NaHCO3 or NH4HCO3) has been proven to be a quick, simple and cost-effective method of reducing the scale potential of Ca(OH)2-stabilized urine. The effect of antiscaling agent addition on calcium carbonate precipitation for a simplified synthetic brackish water reverse osmosis concentrate.

Aeration pre-treatment

INTRODUCTION
MATERIALS AND METHODS
RESULTS
DISCUSSION
CONCLUSIONS

For air bubbling, when the pH of the solution reached 8.6 ± 0.1, the reaction was considered complete and the air supply was turned off. At pH values below 3.5 and above 8.6, the metabolism of the urease-producing bacterium Helicobacter pylori is irreversibly inhibited (Rektorschek et al., 1998), this phenomenon can potentially inhibit the activity of urease-producing bacteria present in urine, also after We observe a decrease in pH. The rate of CO2 dissolution was found to be the key process controlling the pH of the solution, and ultimately the calcium is removed as solid CaCO3.

Table 9: Experimental conditions for different CO 2 bubbling experiments.

Concentration using reverse Osmosis

INTRODUCTION
RESULTS AND DISCUSSION
CONCLUSIONS

In the first study, Ek et al. 2006) removed 80% of the water from hydrolyzed urine using a high-pressure seawater reverse osmosis (SWRO) membrane. Synthetic urine was used to determine the effect of the stabilization method and pretreatment on the key operating parameters (volume reduction factor, flux, rejection, scaling/fouling). Visual inspection of the membranes showed the formation of visible brown fouling of the membrane for acidified urine.

Table 10 summarizes the type of urine, pre-treatment, and operating conditions used for each experiment

Hybrid nanofiltration process

INTRODUCTION
CONCLUSIONS

The recovery and purity of urea in the permeate will also be affected by the extent of the volume reduction factor (VRF) (amount of water removed as permeate). For the synthetic urine experiments, 77.6% of the urea in the permeate was recovered, at an 80% water removal. Urine pretreatment with stiff NF recovered 48% of the urea in the permeate (75% water removal).

Table 11: Characteristics of salicylic acid, paracetamol, stavudine, lamivudine, tenofovir, chlorpheniramine maleate

Eutectic freeze crystallization

INTRODUCTION
CONCLUSIONS

Part of the ice (40 g) was washed separately with deionized water (40 g) precooled to 4°C. After the liquid temperature reached -13.2°C, the stirrer was turned off to allow the ice and salt to separate by gravity. A detailed overview of the assumptions used for the mass balance can be found in Appendix G (Table G-2).

Figure 9-1: Mass % of ice formed, and mass of salt formed when freezing urine that has been pre- pre-concentrated (70% water removal) using RO

Economic analysis

INTRODUCTION

The main difference in operating costs would be the energy requirements of the various processes. The gross value of the fertilizer produced is a function of the fertilizer selling price and the volume produced. Compare the value of the fertilizer produced using the different treatment configurations in the context of the niche fertilizer market.

Figure 10-1:Summary of tested and preferred treatment process options.

METHODS

A summary of the assumptions and values from the literature used for these calculations is available in Table G-2. A sensitivity analysis was performed comparing gross fertilizer sales as a function of niche fertilizer market size. For the AD system, the transport costs were calculated based on the average N content of the fertilizers produced in the four studies.

Figure 10-2: Process diagram for a potential urine source-separation, transport, and treatment system, where the red line indicates the boundaries for the system investigated in this analysis, adapted from (Chipako and Randall

RESULTS AND DISCUSSION

However, this was not considered in the analysis as the main focus was on the N content of the UBF. The gross value of UBF produced is a function of the size of the fertilizer market, its selling price, and the amount of fertilizer produced by each treatment method. The gross value of the fertilizer produced is determined by the amount of fertilizer produced and is reached when all the fertilizer produced from the 7 500 L of urine input is sold at the selling price of the niche fertilizer.

Figure 10-3: Energy required to treat 1 m 3 urine (A) and the energy required per kg-N recovered (B) for urine treated with different concentration technologies and varying water recoveries

CONCLUSIONS

A design of experiments to determine phosphorus removal and crystal properties in struvite precipitation from source-separated urine using different Mg sources. A comparative study of reverse osmosis and freeze concentration for the removal of valeric acid from wastewater. Alkaline dehydration of source-separated fresh human urine: Preliminary insights into the use of different dehydration temperature and media.

Conclusions and future work

CONCLUSIONS

In Chapter 7, urine pretreated with air bubbles and addition of bicarbonate salt was concentrated by RO, and the performance of the pretreatment methods was compared with the no-pretreatment process. The permeate from the tight NF membrane (75% water removal) contained 48% urea, and the permeate from the loose NF membrane contained 78% urea. Further concentration of the permeate using loose NF membranes (up to 80% total water removal) would increase the total urea recovery to 52%.

FUTURE WORK

An estimate of CAPEX and OPEX for different treatment methods as well as for different treatment volumes (eg 100 L per day versus 1000 L per day) should be determined. A detailed fertilizer market analysis is required to better understand the market size, consumer demands, and a realistic selling price.

Energy calculations

Converting this based on 5.86 g N L-1 of urine (Maurer et al., 2003) to determine the energy required to produce the equivalent amount of urea present in urine. 2003) reported that N treatment at a WWTP using denitrification requires 45 MJ kg-N-1. Converting this based on the equation above would require 73.25 kWh to treat the N in 1 m3 of urine.

Real urine composition

Experimental Setup

Urine compositions

Simulation Improvements

Analysis of precipitates

It was therefore assumed that the 15-19% potassium removal observed was due to experimental errors in the analysis process.

Figure C-2: Removal of magnesium, sulfate, chloride, and potassium for air flowrates varying between 1.5 and 9 L min -1

Model Fit

Correction of the dissociation constants of the inorganic carbon system improved the NSE coefficient from 0.972 to 0.985 and the inclusion of creatinine improved the NSE coefficient from 0.848 to 0.985.