ANAEROBIC DIGESTION SYSTEM AND PROCESS FOR POULTRY LITTER TREATMENT WITH WATER RECIRCULATION
20250313965 ยท 2025-10-09
Assignee
Inventors
Cpc classification
C12M43/00
CHEMISTRY; METALLURGY
C02F11/04
CHEMISTRY; METALLURGY
C25B9/00
CHEMISTRY; METALLURGY
C25B1/18
CHEMISTRY; METALLURGY
International classification
C25B1/18
CHEMISTRY; METALLURGY
C12M1/107
CHEMISTRY; METALLURGY
C02F11/04
CHEMISTRY; METALLURGY
C25B9/00
CHEMISTRY; METALLURGY
Abstract
The invention relates to a system and process for digesting poultry litter. In general, in a first aspect, a poultry litter digester includes an anaerobic digestion reactor configured to digest poultry litter to produce an effluent and a biogas, and an electrolytic reactor having at least one magnesium anode, where the electrolytic reactor is configured to precipitate struvite from the effluent.
Claims
1. A poultry litter digester comprising: an anaerobic digestion reactor configured to digest poultry litter to produce an effluent and a biogas; and an electrolytic reactor comprising at least one magnesium anode, wherein the electrolytic reactor is configured to precipitate struvite from the effluent.
2. The poultry litter digester of claim 1, wherein the effluent comprises Mg.sup.2+, NH.sub.4.sup.+, and PO.sub.4.sup.3.
3. The poultry litter digester of claim 1, wherein the biogas comprises methane.
4. The poultry litter digester of claim 1, wherein the anaerobic digestion reactor is an anaerobic sequencing batch reactor, a plug flow reactor, an induced blanket reactor, an up flow anaerobic sludge blanket, a continuous stirred tank reactor, or an anaerobic filter.
5. The poultry litter digester of claim 4, wherein the anaerobic digestion reactor is an anaerobic sequencing batch reactor.
6. The poultry litter digester of claim 5, wherein the anaerobic sequencing batch reactor is a liquid anaerobic sequencing batch reactor that is configured to perform micro-aeration.
7. The poultry litter digester of claim 1, wherein the electrolytic reactor is a column air-lift electrolytic reactor or a dual-chamber reactor.
8. The poultry litter digester of claim 7, wherein the electrolytic reactor is a column air-lift electrolytic reactor.
9. The poultry litter digester of claim 1, wherein the electrolytic reactor is further configured to produce a rejected water as the struvite is precipitated.
10. The poultry litter digester of claim 9, further comprising: a water reclamation system configured to convert the rejected water from the electrolytic reactor into reclaimed water; and at least one pump configured to transfer the reclaimed water to the anaerobic digestion reactor.
11. The poultry litter digester of claim 10, wherein the water reclamation system is a forward osmosis reactor.
12. A method for digesting poultry litter comprising the steps of: preparing a substrate solution from poultry litter and a carbon-rich source; introducing the substrate solution into an anaerobic digestion reactor; performing anaerobic co-digestion on the substrate solution within the anaerobic digestion reactor to recover an effluent and a biogas; and routing the effluent to an electrolytic reactor, wherein the electrolytic reactor is configured to precipitate struvite from the effluent.
13. The method of claim 12, wherein the step of performing anaerobic co-digestion on the substrate solution further comprises a step of introducing air or oxygen to the anaerobic digestion reactor.
14. The method of claim 13, wherein the air or oxygen is introduced to the anaerobic digestion reactor at an air supply rate of 25 mL per L of reactor working volume per day.
15. The method of claim 12, wherein the electrolytic reactor is further configured to produce a rejected water as the struvite is precipitated.
16. The method of claim 15, further comprising the steps of: recycling the rejected water into a reclaimed water; and pumping the reclaimed water to the anaerobic digestion reactor.
17. The method of claim 12, further comprising the step of drying the struvite.
18. A poultry litter digester comprising: an anaerobic digestion reactor configured to digest poultry litter to produce an effluent and a biogas; an electrolytic reactor comprising at least one magnesium anode, wherein the electrolytic reactor is configured to precipitate struvite from the effluent while producing a rejected water; and a water reclamation system configured to convert the rejected water from the electrolytic reactor into reclaimed water.
19. The poultry litter digester of claim 18, wherein the anaerobic digestion reactor is configured to perform micro-aeration.
20. The poultry litter digester of claim 18, wherein the anaerobic digestion reactor is an anaerobic sequencing batch reactor, and the electrolytic reactor is a column air-lift electrolytic reactor.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0029] The above and other objects and advantages of this invention may be more clearly seen when viewed in conjunction with the accompanying drawing wherein:
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DETAILED DESCRIPTION
[0049] While this invention is susceptible to embodiment in many different forms, there are shown in the drawings and will herein be described hereinafter in detail some specific embodiments of the invention. It should be understood, however, that the present disclosure is to be considered an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments so described.
[0050] A poultry litter digester 100 is disclosed for converting poultry litter into a slow-release phosphorous fertilizer (e.g., magnesium ammonium phosphate (MgNH.sub.4PO.sub.4.Math.6H.sub.2O), also known as struvite and biogas. As used herein, the term poultry litter includes chicken feces and may also include bedding material such as straw, sawdust, wood shavings, shredded paper, and peanut or rice hulls.
[0051] In one embodiment, as depicted in
[0052] The anaerobic digestion reactor 102 digests poultry litter with one or more external carbon-rich streams, such as agricultural straw waste, to achieve a balanced carbon-to-nitrogen ratio (C/N). By employing anaerobic co-digestion, the anaerobic digestion reactor 102 solves several common problems associated with traditional anaerobic digestion. For example, anaerobic co-digestion offers enhanced digestibility, improved process stability, and a better digestate product with a higher nutrient value versus traditional designs.
[0053] Depending on the operating conditions, various anaerobic digestion reactors 102 will be suitable for use in the poultry litter digester 100, including but not limited to anaerobic sequencing batch reactors (ASBR), plug flow reactors (PFR), induced blanket reactors (IBR), upflow anaerobic sludge blankets (UASB), continuous stirred tank reactors (CSTR), and anaerobic filters (AF). The anaerobic digestion reactor 102 may facilitate anaerobic digestion using micro-aeration, i.e., dosing with small quantities of air or oxygen. In various embodiments, air or oxygen is introduced to the anaerobic digestion reactor 102 via a single injection, intermittently (pulse-mode), or continuously. Dosing can also be carried out at different stages of the digestion process (pretreatment, during digestion, or post digestion).
[0054] In one embodiment, as depicted in
[0055] The anaerobic digestion reactor 102 is optionally wrapped with a temperature-control element, such as clear vinyl tubing running temperature-controlled water, to maintain a desirable anaerobic co-digestion temperature (e.g., 372 C.), which is optionally measured by a digital thermometer. In one embodiment, the water for the temperature-control element is heated in a tank using a bucket heater and fed to the tubing by a submersible water pump.
[0056] In the embodiment depicted in
[0057] Methane-containing biogas produced from the anaerobic co-digestion process is optionally collected through an outlet in the anaerobic digestion reactor 102, e.g., within a gas bag 156 and/or through a gas collection tube. This biogas produced can be used as heating and cooking fuel, supporting a poultry producer's own energy demands or producing a potential revenue stream. In producing biogas, the anaerobic digestion reactor 102 facilitates the breakdown of organic substances and turns magnesium and phosphorous into an effluent that is available for downstream processing by the electrolytic reactor 104. This breakdown is critical because magnesium and phosphorus in indigested wastes are largely bound to solid organic materials and are not available for further processing.
[0058] After anaerobic co-digestion, the resulting anaerobic digested poultry wastewater (ADPW) effluent is characterized by high levels of nutrients (nitrogen and phosphorus) and, in general, by increased ion concentrations of Mg.sup.2+, NH.sub.4.sup.+, and PO.sub.4.sup.3. Once biogas is captured, the effluent is routed from the anaerobic digestion reactor 102 to the electrolytic reactor 104, which is configured to recover phosphate (PO.sub.4.sup.3) and ammonia-nitrogen (NH.sub.3N) through electrochemical struvite precipitation. As previously noted, struvite precipitation presents a valuable opportunity to reclaim a fertilizer from poultry waste.
[0059] The electrolytic reactor 104 employs soluble magnesium electrodes 158, 160 to provide the Mg.sup.2+ ions needed to support struvite precipitation. More particularly, the electrolytic reactor 104 includes one or more lightly electrically charged magnesium plates 158, 160 that produce Mg.sup.2+ at anode 158 in electrolysis. The magnesium sacrificial anode 158 facilitates struvite precipitation without the need to add magnesium salts and NaOH to the effluent. The use of an electrolytic reactor 104 also prevents water electrolysis, so no hydrogen gas is produced. Mg.sup.2+ release may be controlled by adjusting the current density applied. In one embodiment, controlled Mg.sup.2+ release from the anodic magnesium plate 158 in the electrolytic process is automated. It will be appreciated that the magnesium consumption required from the electrolytic reactor 104 can be reduced where the effluent received from the anaerobic digestion reactor 102 already has increased Mg.sup.2+ content.
[0060] When the magnesium plates 158, 160 produce Mg.sup.2+ at anode in electrolysis, OH.sup. radicals are simultaneously generated at the cathode, which can increase the liquid pH. In this way, the two requirements for struvite formation, i.e., sufficient Mg.sup.2+ concentration and a raised pH in the liquid, can be easily met. The electrolytic reactor 104 separates the nitrogen and phosphorous nutrients from the effluent and drops the same into a settling tank as struvite, which is subsequently dried to form a powder. Depending on the amount of phosphate and ammonium present, approximately 1 gram of struvite precipitates from each one liter of effluent.
[0061] In one embodiment, as shown in
[0062] The depicted embodiment from
[0063] Turning to another embodiment, as shown in
[0064] The ALER system creates larger, more uniform struvite crystals than the dual-chamber reactor. More particularly, the ALER lacks mechanical contacts and, therefore, can suppress or reduce the secondary nucleation rate to grow crystals of large sizes. The ALER also provides a high surface-to-volume ratio which allows adequate mixing of reactants with a low shear force and high liquid-solid mass transfer rate due to increased liquid circulation rates. Further, the circulation flow within the ALER can keep struvite crystals suspended for a long time, allowing them to grow. The gas phase can also help with pH regulation by stripping CO.sub.2 from the solution, resulting in a slight pH increase which helps to resist pH drops caused by struvite formation. As a result, significantly less chemicals are needed to maintain the pH at the desired operating value. Column-shaped ALERs are also easy to scale up, and foam production between electrodes, which is often a significant problem when treating organic-rich wastewater in electrochemical reactors, can be minimized by controlling the up-flow velocity.
[0065] After processing, the precipitated struvite is collected in a settling tank (not shown) or within the electrolytic reactor 104, and the remaining effluent is removed. Although most of the nutrients are precipitated by the electrolytic reactor 104 and between 80% and 90% of the water from the effluent comes out from the electrolytic reactor 104 clear, a small amount of rejected water is created that also contains a small amount of nutrients. In some embodiments, the rejected water is disposed of or is reused in a separate context, e.g., as a road treatment for ice and snow prevention in the wintertime, without further processing at the poultry litter digester 100. In another embodiment, the poultry litter digester 100 recovers the rejected water and recycles it to a reclaimed water for reuse. The rejected water must be cleaned enough to dilute incoming poultry litter. To accomplish this recycling, the rejected water is routed to a water reclamation system 106 for further processing after struvite precipitation. The water reclamation system 106 performs water clarification on the rejected water. In one embodiment, the water reclamation system 106 is a forward osmosis reactor that is configured to remove the majority of minerals and other ions that are not removed by the electrolytic reactor 104. The forward osmosis reactor filters the rejected water through a semipermeable membrane and uses the natural energy of osmotic pressure to separate liquid from the solids in the solution. It will be appreciated that different membranes may be used for the forward osmosis reactor.
[0066] Once recycled, the reclaimed water can be recirculated to the anaerobic digestion reactor 102 to liquefy dry poultry litter for continuous digestion, thus minimizing the water input required for anaerobic co-digestion. In one embodiment, peristaltic pumps are used to transfer the reclaimed water back into the anaerobic digestion reactor 102. After recycling for some time, the rejected water has a reduced volume and minimal N and P content and can no longer be recycled to the anaerobic digestion reactor 102. This final rejected water is removed from the poultry litter digestion reactor and can be land applied locally without posing environmental pollution risks.
[0067] Turning to
EXAMPLES
[0068] The process and system for poultry litter digestion is further illustrated by the following Examples, which are provided for the purpose of demonstration rather than limitation.
Example 1Set Up
[0069] This Example was designed to evaluate anaerobic co-digestion of poultry litter with wheat straw in a daily-schedule-based operated ASBR system. Two identical anaerobic digestion reactors with a working volume of 16 L were built and set up for experimental runs. The reactor body was covered with hot water circulation and cotton insulation to maintain the temperature (35 C.2 C.). The reactor was operated in an ASBR mode with cycle time maintained at 24 h (one day). A full operation cycle included an effluent discharging period after the solids settling, an immediately followed substrate feeding period, and two solids settling (reaction) periods divided by two mixing periods (each for 10 min).
[0070] For the substrate, raw poultry litter and wheat straw were collected from a poultry farm and a grass farm, respectively. The poultry litter had a total carbon (TC) of 27.202.92%, total nitrogen (TN) of 3.370.65%, and a moisture content of 21.970.31%, while the wheat straw had a relatively higher TC of 43.470.15%, and a relatively lower TN of 0.760.03%, and a relatively lower moisture content of 9.230.11%. The desired C/N ratio and TS level could be reached by balancing the weight proportions of poultry litter, wheat straw, and water. Two types of inoculum sludge were collected from two local wastewater treatment plants.
[0071] The three key operation parameters including substrate C/N ratio, substrate TS (%), and HRT (d) were examined, each at five levels includingalpha (=1.682), 1 (high and low), and 0 (medium) as the coded values. The actual values of the high and low levels of each factor were 25 and 15, 8 and 4, and 21 and 11 for the C/N ratio, TS, and HRT, respectively. A total of 20 experimental runs were generated, including 6 replicates of the center values (0, 0, 0), 8 cube points (1, 1, 1), and 6 axial points (0, 0, 1.682; 0, 1.682, 0; and 1.682, 0, 0). Even with the reduced experimental points, CCD could still accurately determine the contour behavior of the fitting model. The coded values and the corresponding actual values of the levels of each variable in different runs in the two ASBR systems were described in Tables 1 and 2.
TABLE-US-00001 TABLE 1 Reactor 1. Methane production (mean values and standard deviation of biogas Substrate production rate and composition methane production rate Input variables (Code value) based on were provided based on 3- C/N HRT fresh 11 days' measurements) ratio TS (%) (d) weight (%, OLR (g BPR MPR (L Run (X1) (X2) (X3) PL:WS) VS/LR/d) (L/LR/d) CH4/LR/d) 1 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.60 0.30 0.03 0.05 2 20 (0) 6 (0) 24.4 (1.68) 2.91:4.13 1.61 0.39 0.20 0.02 0.03 3 15 (1) 4 (1) 21 (1) 2.79:2.02 1.19 0.29 0.14 0.02 0.02 4 15 (1) 4 (1) 11 (1) 2.78:2.02 2.28 0.70 0.37 0.03 0.06 5 20 (0) 6 (0) 7.6 (1.68) 2.90:4.12 5.20 1.18 0.72 0.09 0.14 6 15 (1) 8 (1) 21 (1) 5.57:4.04 2.33 0.46 0.21 0.02 0.02 7 25 (1) 4 (1) 11 (1) 1.39:3.22 2.53 0.70 0.4 0.04 0.07 8 25 (1) 8 (1) 21 (1) 2.78:6.45 2.67 0.57 0.26 0.03 0.04 9 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.61 0.30 0.01 0.02 10 11.6 (1.68) 6 (0) 16 (0) 5.50:1.88 2.16 0.41 0.19 0.02 0.03 11 20 (0) 2.6 (1.68) 16 (0) 1.28:1.81 0.94 0.28 0.16 0.02 0.01 12 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.56 0.29 0.01 0.03
TABLE-US-00002 TABLE 2 Reactor 2. Methane production (mean values and standard deviation of biogas Substrate production rate and composition methane production rate Input variables (Code value) based on were provided based on 3- C/N HRT fresh 11 days' measurements) ratio TS (%) (d) weight (%, OLR (g BPR MPR (L Run (X1) (X2) (X3) PL:WS) VS/LR/d) (L/LR/d) CH4/LR/d) 1 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.61 0.31 0.02 0.05 2 15 (1) 8 (1) 11 (1) 5.56:4.04 4.46 0.88 0.45 0.05 0.07 3 25 (1) 4 (1) 21 (1) 1.39:3.22 1.32 0.38 0.21 0.02 0.03 4 25 (1) 8 (1) 11 (1) 2.77:6.44 5.10 0.86 0.43 0.08 0.15 5 28.4 (1.68) 6 (0) 16 (0) 1.66:5.18 2.71 0.60 0.3 0.01 0.02 6 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.65 0.33 0.01 0.02 7 20 (0) 9.4 (1.68) 16 (0) 4.53:6.42 3.77 0.63 0.29 0.06 0.12 8 20 (0) 6 (0) 16 (0) 2.90:4.11 2.47 0.56 0.28 0.01 0.03
[0072] The selected inoculum sludge was analyzed in physio-chemical properties and was used to start up the anaerobic co-digestion process. Twenty (20) experimental runs were performed, and the feeding substrate compositions for each experimental run were calculated (see Table 1). The center values of the operation parameters were employed in the first 3-6 days of operation as the adaptation period in each experimental run and were also adopted when inhibitions occurred.
[0073] The TC and TN of the poultry litter and wheat straw were measured by combustion using Elementar varioMax CN Cube (Elementar, German). TS, moisture content, and volatile solids (VS) were analyzed by thermogravimetric analysis. For the effluent liquid samples, the concentration of chemical oxygen demand (COD), TN, ammonium nitrogen (NH.sub.4.sup.+N), nitrite nitrogen (NO.sub.2.sup.N), nitrate nitrogen (NO.sub.3.sup.N), phosphorus, and magnesium (Mg.sup.2+) were analyzed using a DR 3900 Hach Spectrophotometer and Hach vials (Hach Company, IA, US). All the data was measured in triplicates and mean values with standard deviations were obtained.
[0074] For the biogas analysis, the volumes of daily collected biogas were measured using a wet gas test meter (Model XMF-1, Shanghai Cixi Instrument Co., ltd, Chin). The compositions of biogas samples were analyzed using a Shimadzu Gas Chromatograph (GC 2014, Shimadzu Scientific Instruments, Inc., Maryland, CO, USA) equipped with a thermal conductivity detector (TCD).
[0075] The microbial community was analyzed for inoculum selection. Microbial community analysis DNA extractions were performed using the DNeasy PowerLyzer PowerSoil Kit (Qiagen, Germantown, MD). The raw reads were submitted to the NCBI (National Center for Biotechnology Information) Sequence Read Archive (SRA). The microbial inoculum was selected based on microbial community analysis.
Example 1Results
[0076] At the phylum level, inoculum (a) mainly contained the phylum of Bacteroidota (44%), followed by Firmicutes (22%) and Chloroflexi (13%). While in inoculum (b), the most abundant phylum was Chloroflexi (42%), followed by Actinobacteriota (11%), Cloacimonadota (11%), and Bacteroidota (10%). Compared to inoculum (a), inoculum (b) showed a more diverse microbial structure. In addition, the major phyla in inoculum (b) were found to be likely ubiquitous in most stable anaerobic digestion reactors. Chloroflexi is found responsible for the hydrolysis of both monosaccharides and polysaccharides as well as the production of acetic acid. Actinobacteriota is hydrolytic bacteria that can also decompose polysaccharides and proteins in AD systems. Cloacimonadota is found to be especially important in lipid-rich waste AD. At the genus level, Bacteroides dominated inoculum (a) with an abundance (31%), far exceeding the other genus (lower than 5%). However, the distribution of microorganisms in inoculum (b) was more even. SBR1031 and Longilinea were the two dominant genera (accounting for 16% and 13%, respectively). The abundance of methanogens genus was negligible (lower than 1%) in inoculum (a) but was 2% (Methanosaeta) in inoculum (b), making inoculum (b) a better choice than inoculum (a) for the anaerobic co-digestion process.
[0077] In reactor, the daily biogas production (DBP, L) in each run became stable (difference within 5%) after an adapting period of about 3-5 days (see
[0078] In summary, the anaerobic co-digestion process in the ASBRs showed continuous methane production with a BPR ranging from 0.28 to 1.18 (L/LR/d). The highest BPR was reached in Run 5 of Reactor 1 with C/N ratio=20, TS level=6%, and HRT=7.6 d, being (1.180.14) L/LR/d, where the MPR was (0.720.09) L CH4/LR/d. Furthermore, a modified second-order quadratic model (Equation 1) that best fitted the experimental data could be built for BPR using the response surface methodology. Analysis of variance (ANOVA) (see supplementary material) showed that the model was significant (p<0.0001) with a correlation coefficient (R.sub.2) of 0.9724. And it also showed that all the single factors had a significant (p<0.05) effect on the BPR.
[0079] Turning to the effects on effluent quality and, more particularly, the effects on COD, in Reactor 1, the effluent COD showed an obvious decreasing trend and tended to become relatively stable at the last 3-4 days (
[0080] When evaluating the effects on nitrogen, phosphorus, and magnesium, in the effluent of most runs, the concentrations of different nitrogen species were similar with NH4.sup.+-N in the range of 120-160 mg/L, NO3.sup.N in the range of 17-34 mg/L, and NO.sub.2.sup.N in the range of 0.7-1.2 mg/L, and TN in the range of 400-500 mg/L (see supplementary material). However, there are some exemptions. In Run 4 of Reactor 1, total organic nitrogen (TON) was lower although NH4+-N was higher (177.31.0 mg/L), compared to other runs probably due to its relatively lower C/N ratio (15). In Run 10 of Reactor 1, which had the lowest C/N ratio (11.6), the effluent showed relatively high nitrogen concentrations in different forms including TN (548.022.6 mg/L) and NH.sub.4.sup.+N (224.62.0 mg/L) (see supplementary material), indicating that a low C/N ratio could lead to high nitrogen concentration in the effluent. At a relatively lower C/N ratio, which meant a higher proportion of PL in the mixture substrate, the bacteria activities released relatively more nitrogen, which was mainly from the degradation of protein and lipid in poultry litter, by Actinobacteriota and Cloacimonadota, respectively. The effluent phosphorus concentrations in most runs were stable in the range of 440-500 mg/L (see supplementary material). However, several runs including Run 7 and 8 in Reactor 1 and Run 3 in Reactor 2 (all had a relatively high C/N ratio of 25) showed relatively higher effluent phosphorus (520-650 mg/L). The phosphorus concentration was trending down for Runs 4 and 7 in Reactor 2 with inhibitions. In all, it could be inferred that the effluent phosphorus level could be affected by many factors such as the C/N ratio, OLR, and process stability of the ASBR. The magnesium level in the effluent was generally in the range of 160 to 230 mg/L, except in Run 8 of Reactor 1 and Run 3, 4, and 5 of Reactor 2 which showed a higher range of 260 to 300 mg/L. The release of phosphorus and magnesium was related to the efficiency of bacterial activity that degraded the substrate solids, which was not only determined by the substrate characteristics but also affected by the process stability.
[0081] In conclusion, the inoculum with a diverse microbial structure that included 2% of methanogens (Methanosaeta) was chosen for the anaerobic co-digestion of poultry litter with wheat straw in the two ASBRs. The highest BPR (1.180.14 L/LR/d) and MPR (0.720.09 L CH4/LR/d) were obtained at C/N=20, TS=6%, and HRT=7.6 d. The modified quadratic model was significant (p<0.0001) for predicting BPR. Inhibitions due to COD accumulation were relieved by employing the center values of parameters (C/N=20, TS=6%, HRT=16 d). The concentration of nitrogen, phosphorus, and magnesium in the effluent was affected by the C/N ratio, TS, HRT, and process stability.
Example 2Set Up
[0082] Anaerobic digested poultry wastewater (ADPW) effluent from Example 1 was stored at 4 C. until use for nutrient recovery, i.e., for struvite (magnesium ammonium phosphate) precipitation using an electrolytic reactor. Table 3 shows the average values of the physicochemical properties of the ADPW samples used in this Example. All values in Table 3 are in mg/L except pH and conductivity.
TABLE-US-00003 TABLE 3 Physiochemical properties of ADPW effluent. Parameters (mg/L) Value (mean S.D.) pH 7.78 0.1 Conductivity (mS/m) 13.4 0.1 sCOD 5137 0.001 PO.sub.4.sup.3 1397 0.001 NH.sub.3N 941 0.001 Mg.sup.2+ 123.8 0.5 K.sup.+ 164 0.08 Zn.sup.2+ 0.2 0.001 Fe.sup.2+ 0.82 0.001 Cr.sup.2+ 0.02 0.001 Cu.sup.2+ 0.1 0.001 Ca.sup.2+ 64.58 0.08 Alkalinity (CaCO.sub.3) 2540 0.28
[0083] The first set of experiments was carried out with simulated poultry wastewater to study the effects of different air-flow rates on the amount of nutrient removal and particle size distribution (PSD) of precipitate generated. This was done to establish the optimal mixing characteristics of the electrolytic reactor. The chemical components of ADPW were used to prepare the simulated poultry wastewater matrix by combining deionized water with various analytical-grade salts, including ammonium chloride (NH.sub.4Cl, 99.8%), acetic acid glacial (C.sub.2H.sub.4O.sub.2, 99.85%), sodium phosphate monobasic dihydrate (NaH.sub.2PO.sub.4.Math.2H.sub.2O, 99.0%), calcium chloride (CaCl.sub.2, 97%), glucose (C.sub.6H.sub.12O.sub.6, 99.5%) and potassium sulfate (K.sub.2SO.sub.4, 99.0%). The solution was uniformly mixed using a magnetic stirrer, and the pH was adjusted using 1 M NaOH before each experiment. Trace elements (Zn, Cr, Cu, and Fe) with concentrations <0.2 mg/L were not added to the composition of the simulated wastewater because such small concentrations do not have a significant effect on struvite formation, especially when the concentration of PO.sub.4.sup.3 and NH.sub.3N are very high.
[0084] An air-lift electrolytic crystallizer was set up according to the schematic and geometric details shown in
[0085] To investigate the effect of the up-flow velocity on the PSD of struvite precipitates in the ALER, a total of eight (8) experiments were performed at different flow rates (1, 3, 6, 9 L/min) in duplicates for 4 hrs using simulated poultry wastewater solutions. The air-flow rate was controlled and adjusted using the mass flow controller, and all experiments were conducted in batch mode at room temperature. An applied current (0.5 A) was used with no pH adjustment. The superficial gas velocity (U.sub.sg) is the ratio of the gas volumetric flowrate (Q.sub.g) to the total cross-sectional area of the inner diameter of the riser (A.sub.r) according to Equation 2:
[0086] The optimal U.sub.sg for mixing was selected and used with the optimum applied current (0.5 A) for batch experiments using the actual ADPW. Experiments with the ADPW were also conducted in duplicate.
[0087] Thermodynamic chemical equilibrium was modeled for the relevant analytics. Struvite precipitation from aqueous solutions occurs when Mg, PO.sub.4.sup.3, and NH.sub.4.sup.+ ion concentrations exceed the struvite solubility product, and the process is mainly dependent on the degree of supersaturation inside the reactor. The degree of supersaturation for a system with multiple components is usually expressed in terms of the supersaturation index (SI), which is the logarithmic ratio between the ion activity product [IAP] and solubility product (K.sub.sp). Calculation of the activity coefficients by the model was done using the Davies approximation of the Debye-Huckle equation (see Equations 3 and 4):
[0090] The efficiency of PO.sub.4.sup.3 and NH.sub.3N recovery as struvite from the ADPW sample was also calculated after each batch experiment using the following Equation 7:
[0093] In terms of the reaction kinetics of struvite precipitation, during each experiment, 7 mL samples were collected at 20 min intervals from the reactor and analyzed to determine the changes in COD, PO.sub.4.sup.3, and NH.sub.3N concentrations. PO.sub.4.sup.3 was measured using a HACH TNT 843 (0.15-4.5 mg/L) and TNT 846 kits (5-90 mg/L), respectively. NH.sub.3N was measured using HACH TNT 831 (1-12 mg/L) and HACH TNT 833 (47-130 mg/L). While the COD was analyzed using HACH TNT 823 kit (250-15000 mg/L). All HACH kits were analyzed using a DR 3900 spectrophotometer (Loveland, CO, USA) according to the manufacturer's instructions. The rate of PO.sub.4.sup.3 and NH.sub.3N disappearance or removal from solution over time was evaluated according to a first-order kinetic model as shown in Equations 9:
[0095] The space-time yield (Y.sub.ST) was also calculated to give an overall index of a reactor's performance. As shown in Equation 11, it is the amount of product (m.sub.p) produced per unit of time (t) and reactor volume (V.sub.r).
[0096] At the end of each experiment, all precipitates in the reactor were collected by vacuum filtration using a glass filter (WHEATON) and air-dried at room temperature for 48 h to characterize the recovered products. After weighing using a balance, the elemental composition of the sample was determined by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (Zeiss Supra 35, Zeiss, Oberkochen, Germany) analysis. Recovered precipitates were also subjected to X-ray diffraction (XRD) analysis (Siemens D5000, Princeton, NJ, USA) for phase identification and quantification. The functional groups present in the precipitates and the nature of the bonds in the precipitates were analyzed using Fourier transform infrared spectroscopy (FT-IR) (Nicolet iSTM20 Spectrometer, Fisher Scientific, PA, USA).
[0097] The PSD of recovered precipitates was obtained by automatic image processing and analysis of crystals using a revolutionary artificial intelligence (AI) technology. For each run, 20 mg of struvite was placed in a vial, and 5 drops of Milli-Q water were added. The vial was then mixed until the crystals were well-dispersed. Three drops of the sample were placed on a glass slide, followed by a coverslip. The specimens were observed under a microscope at 10 magnification. Images of struvite crystals were captured by an optical microscope (Olympus AX70 Fluorescence Motorized Microscope) connected to a 14 MP HD digital color camera (AmScope MU1403, United Scope, CA, United States). The size distribution (Feret diameter) and statistics were determined using MIPAR image analysis software (Columbus, Ohio, United States) which uses a powerful deep learning technology to effectively recognize particle boundaries and generates size distribution data based on various features of interest. A total of 100 images were captured per sample, and over 5000 crystals were analyzed per sample.
Example 2Results
[0098] First, the effect of up-flow velocity on particle size distribution was observed during struvite precipitation. The effectiveness of struvite precipitation depends on the crystallizer type and its mode of operation, which is often evaluated from two key aspects: nutrient recovery efficiency and product quality (purity and PSD). In a supersaturated solution, precipitation usually begins with the birth of new particles or nuclei from the liquid phase (nucleation). Once generated, the fate of the nuclei is primarily determined by the thermodynamic and hydrodynamic conditions inside the reaction vessel. Hydrodynamics and mixing promote crystal nucleation and growth by enhancing contact between PO.sub.4.sup.3, NH.sub.4.sup.+, and Mg.sup.2+ ions; mass transfer of ions from solution to the crystal phase; and settling behavior of generated crystals. Therefore, adequate mixing is essential for effective process operation. In the air-lift crystallizers particles become fully suspended when the up-flow velocity becomes strong enough to counteract the downward pull of gravity. Consequently, only larger particles with a settling velocity equal to or higher than the upward air velocity can settle at the bottom of the reactor.
[0099] The results indicate that the electrolytic reactor's superficial gas velocity (U.sub.sg) is strongly related to the mean particle size of recovered precipitates. The data showed a slight shift of particle size classes to the right, indicating that the mean size of struvite crystals increased with a corresponding increase in U.sub.sg. The mean particle size grew from 42.51 m to 79.93 m (88.03%) when the U.sub.sg was raised from 11.94 m/h to 35.81 m/h. At high U.sub.sg, the mean particle size increased from 102 m at 71.6 m/h to 174.9 m at 107.42 m/h (71.47%). Overall, the mean particle size increased by 311.43% when the U.sub.sg was raised from 11.94 m/h to 107.42 m/h. D50 and D90 values also increased from 40.7 to 134.5 m and 47.3 to 269.1 m, respectively, with increasing U.sub.sg. At the same time, D10 values changed from 36.4 to 65.2 m at low U.sub.sg (11.94 to 35.81 m/h) and then dropped marginally to 60 and 55.8 m at 71.61 and 107.42 m m/h, respectively. However, adjustment of aeration intensity did not improve the nutrient removal efficiency. In general, an increase in U.sub.sg will often result in an increase in nucleation rates of struvite crystals due to enhanced molecular mixing between reactants. Additionally, high U.sub.sg promotes the suspension of particles and also increases interparticle collisions, leading to the formation of bigger particles (aggregates) with higher sedimentation velocity. However, very high U.sub.sg beyond a specific threshold value or optimum will enhance foam formation and cause breakage of crystal aggregates. On the contrary, low U.sub.sg and, therefore, slower dissipation of reactants leads to locally higher supersaturation which favors nucleation over crystal growth. This would explain the smaller crystal sizes achieved at low U.sub.sg.
[0100] Nutrient recovery efficiency from the ADPW was also investigated. The changes in PO.sub.4.sup.3 and NH.sub.3N removal efficiency and COD concentration changes after 4 hrs of treatment under constant current and air-flow rate are presented in
[0101] Predicted metal oxides in the system from chemical equilibrium modeling were Mg(OH).sub.2, Fe(OH).sub.2, and Zn(OH).sub.2. These hydroxides can provide active surfaces for the adsorption of wastewater pollutants and promote flocculation of dispersed particles, which can then be removed during downstream processing steps by filtration or centrifugation. It has also been suggested that foreign substances (colloidal impurities) can facilitate nucleation by reducing the Gibbs free energy needed to produce a crystal nucleus or serve as nuclei for the growth of struvite crystals. The total amount of precipitate recovered at the end of the process was 23.72 g, and the space-time yield was 0.988 kg/m.sup.3 h. The efficiency of PO.sub.4.sup.3 removal increased steadily from 30.12% after 30 mins to 89.5% after 120 mins of treatment and then almost plateaued. There was little change in PO.sub.4.sup.3 removal observed between 150 mins (91.8%) and 240 mins (99.9%) even though the pH was already over 8.9 after 150 mins of treatment. This event was unexpected since it is generally known that at high pH values, the concentration of PO.sub.4.sup.3 ions increases, increasing its potential for recovery. Because the ratio of PO.sub.4.sup.3:NH.sub.3N in this Example was 1.5:1, the reduction in PO.sub.4.sup.3 removal efficiency after 150 mins of treatment was most likely due to passivation or the formation of a non-conducting oxide on the anode surface which limited electron transfer and corrosion of the Mg alloy. This is a significant issue in electrochemical crystallizers because as the passivation layer thickens, the overpotential required for Mg dissolution increases by several orders of magnitude, thereby limiting the overall efficiency of the process. It is also inconvenient since electrode plates must be manually cleaned, acid-washed, or replaced to remove the protective film on the surface of the AZ91 allow, which takes time. The passive film on Mg alloys usually consists of a chemisorbed oxygen film or compact three-dimensional inner layer of magnesium MgO and a porous outer layer of Mg(OH).sub.2/MgNH.sub.4PO.sub.4/MgCO.sub.3. MgO is generated directly through the interaction of the AZ91 alloy with the surrounding electrolyte according to the following mechanism in Equation 12:
[0103] Kinetic modeling was performed for the observed struvite precipitation. The formation of struvite generally proceeds through the following stoichiometric Equation 14:
[0105] It is important to note that since Mg is the limiting reactant, and its dissolution rate depends on the amount of electric current supplied to the system, increasing the current density can speed up the removal of nutrients. The higher the current density, the more Mg.sup.2+ ions are liberated from the sacrificial anode, increasing the rate of struvite formation with a corresponding decrease in treatment time. However, increasing the current density will also lead to an increase in operating costs.
[0106] Variation of electrolyte pH and conductivity with treatment time were also observed. The pH value of a wastewater sample has a significant impact on the overall NRE, purity, and growth of struvite crystals inside a reactor since it regulates the solubility and availability or effective concentrations of Mg.sup.2+, NH.sub.4.sup.+, and PO.sub.4.sup.3, including other constituent ions in the wastewater matrix.
[0107] 2H.sub.2O+2e.sup..fwdarw.2H.sub.2+2OH.sup. (Equation 16) Many studies have reported that struvite precipitation is possible over a broad range of (4-12). However, a pH range of 8.0-9.5 is recommended to obtain high-purity struvite. In this Example, the initial and final pH values were well within the appropriate pH range to obtain high-purity struvite; hence pH adjustment was unnecessary. This implies that the operating cost can be reduced significantly when the process is scaled-up, considering that calculations from a full-scale pilot plant with a processing capacity of 400 m.sup.3/d revealed that the addition of sodium hydroxide for pH regulation was responsible for up to 97% of the overall chemical cost. On the other hand, the electrical conductivity (EC) of the ADPW decreased along with treatment time from its initial value of 13.45 to 10.24 mS/m (23.9%) after 4 hrs. This observation can be attributed to a decrease in total dissolved solids (TDS) and precipitation of minerals as the experiment progressed.
[0108] Turning to modeling of thermodynamic chemical equilibrium for the ALER process, for designers and operators, predicting the behavior of nutrient recovery systems or the potential for nutrient recovery from a wastewater sample of known chemical composition under specified operating conditions is essential for anticipating potential mineral formation and unwanted process design failures. The SI is an important parameter that controls crystal nucleation, growth, and aggregation; hence it can be used to assess or predict the likelihood of mineral precipitation and its purity. It is related to the change in the Gibbs free energy (G), which is the thermodynamic driving force for crystal formation and crystal growth, as shown in Equation 17:
[0110] The identification of crystalline phases, elemental composition, and morphology of the precipitates recovered after a 4-hr treatment period were determined using XRD, FTIR, and SEM-EDX, respectively. The XRD spectrum shown in
[0111] In nutrient recovery processes, the final PSD is another key indicator of product quality. Since larger crystals are desired (3.5 to 5 mm), it is necessary to have dedicated crystal growth compartments in the crystallizer design.
TABLE-US-00004 TABLE 4 Comparison of literature on electrochemical nutrient recovery from different wastewater substrates Type of substrate Mean Reactor treated + Crystal design and initial nutrient Mg Current size volume concentrations Anode density pH HRT NRE Mixing (m) DCE (1 L) AD Swine AZ91D 22.2 8.5 1 93% 80 NR with wastewater A/m.sup.2 hr PO.sub.4P rpm AEM/CEM [PO.sub.4.sup.3 = 52.8 removal mg/L: NH.sub.4.sup.+ = 7.8523 mg/L] Jar (1.5 L) Swine Mg plate 2 7.8 45 85% 150 NR wastewater mA/cm.sup.2 mins PO.sub.4.sup.3 rpm [PO.sub.4.sup.3 = 103 and mg/L: NH.sub.3 90% N = 426 mg NH.sub.3N L.sup.1] removal SCR (1 L) Fermented AZ91HP 45 7.5-9.3 3 98% NR waste A/m.sup.2 hrs PO.sub.4.sup.P activated removal sludge [PO.sub.4.sup.P = 0.056 g/L: NH.sub.3N = 0.114 g/L] SCR (0.5 AD chicken AZ31B 20 8.6-8.9 1.5 70.46% 300 NR L) manure slurry Mg rod A/cm.sup.2 hrs PO.sub.4.sup.P rpm [PO.sub.4P = removal 521.50 mg/L: NH.sub.3N = 3994.05 mg/L] CFE (50 L) Swine Mg plate 4 V on 7.28 15 99.5% 20 15-20 wastewater 0.04 m.sup.2 mins PO.sub.4.sup.P rpm m [PO.sub.4P removal 136.3 mg/L: NH.sub.3N = 0.41 g/L] Example 2 AD poultry AZ91D 12.4 7.8-9.2 4 99.9% 9 142.95 [PO.sub.4P = A/m.sup.2 hrs PO.sub.4.sup.P L/min m 1397 mg/L: and NH.sub.3N = 97.3% 941 mg/L] NH.sub.3N removal
[0112] Operating cost and energy efficiency of the ALER process were evaluated. Large-scale implementation of electrochemical nutrient recovery via struvite precipitation from any type of wastewater depends primarily on its operating cost, including the market price of struvite and other competing fertilizer products. While a complete economic assessment is beyond the scope of this Example, a simplified economic expression can be written if the energy required for mixing is neglected and only the two main components of electrochemical reactor design are considered, as shown in Equation 18:
[0116] The current efficiency of the ALER was 520.59% which suggested that the actual dissolving rate of the Mg alloy was far greater than its theoretical value. In addition to electrolytic dissolution, chemical dissolution also contributes to the amount of metal ions released from a sacrificial anode. For instance, high PO.sub.4.sup.3 concentration can enhance the corrosion rate of Mg electrodes. Therefore, it is plausible that the high PO.sub.4.sup.3 concentration in the ADPW caused the AZ91 anode to corrode more quickly, hence the high current efficiency. Considering that only a fraction of the applied current goes towards the desired reaction, the depletion time or lifetime (D.sub.t) of the sacrificial AZ91D electrode can be estimated as follows with Equations 24 and 25, assuming that 100% of the electrode is utilized before discarding:
Example 3Set Up and Results
[0118] Another round of anaerobic co-digestion testing was performed using the same set up as Example 2, with a total working volume of 6 L run under constant current density (12 A/m.sup.2) and air flow rate (1 L/min). Oxalic acid was used as the extraction acid in place of NaOH to lower the liquid pH to 2.5. The liquid properties before and after treatment are shown in Table 5.
TABLE-US-00005 TABLE 5 Acid pre-treated ASBR effluent quality before and after electrolytic treatment. Before After Reduction Components (mg/L) (mg/L) (%) pH 7.78 8.5 Electrical conductivity (mS/cm) 13.4 9.2 31.3 Total suspended solids (TSS) 446.7 52.3 88.3 Total nitrogen (TN) 1405.4 172 87.8 Total phosphorus (TP) 1397 Not detected 100 NH.sub.3N 941 45 95.2 NO.sub.2N Not detected Not detected NO.sub.3N Not detected 1.4 COD 5137 4539 11.6 Mg.sup.2+ 195 58 70.2
[0119] As indicated in Table 5, for nutrient recovery, TP was completely removed with some NH.sub.3N and Mg.sup.2+ remaining. In other words, with the assistance of oxalic acid, the ALER was able to convert all P in the liquid to struvite. It was observed that the solution pH rose quickly to >8 once the electrolytic process started (producing OH) without needing any chemicals.
[0120] In the chemical formula of struvite, MgNH.sub.4PO.sub.4.Math.6H.sub.2O, the molar ratio of the three constituents is 1:1:1. Since nitrogen was not limiting, an appropriate amount of Mg.sup.2+ equivalent to 0.045 mol of PO.sub.4.sup.3 (1397 mg/L of TP=4281 mg/L of PO.sub.4.sup.3) was needed. Apparently, the existing amount of Mg.sup.2+ in the ASBR effluent was not enough (0.195 g/24.3 g/mol=0.008 mol<0.045 mol PO.sub.4.sup.3), and the deficiency of Mg.sup.2+ was then met by the release of Mg.sup.2+ from the magnesium anode of ALER. In theory, no Mg.sup.2+ should be left in the effluent, but there was still a small amount of Mg.sup.2+ (58 mg/L) unused (see Table 5). This observation indicates that the ALER was not optimized, causing over-release of Mg.sup.2+ from the magnesium anode. Since the amount of Mg.sup.2+ ions needed in the liquid could be controlled by adjusting the current density applied, to avoid wasting the Mg anode, optimization of the running parameters for the ALER is necessary.
Example 4Set Up and Results
[0121] Additional testing was performed to verify the effect of micro-aeration (air injection) on anaerobic co-digestion of poultry litter with wheat straw. Two glass containers 180, each having a total volume of 648 mL (500 mL working volume), were set up for batch operation as shown in
[0122] For purposes of the instant disclosure, the term at least followed by a number is used herein to denote the start of a range beginning with that number (which may be a range having an upper limit or no upper limit, depending on the variable being defined). For example, at least 1 means 1 or more than 1. The term at most followed by a number is used herein to denote the end of a range ending with that number (which may be a range having 1 or 0 as its lower limit, or a range having no lower limit, depending upon the variable being defined). For example, at most 4 means 4 or less than 4, and at most 40% means 40% or less than 40%. Terms of approximation (e.g., about, substantially, approximately, etc.) should be interpreted according to their ordinary and customary meanings as used in the associated art unless indicated otherwise. Absent a specific definition and absent ordinary and customary usage in the associated art, such terms should be interpreted to be 10% of the base value.
[0123] When, in this document, a range is given as (a first number) to (a second number) or (a first number)-(a second number), this means a range whose lower limit is the first number and whose upper limit is the second number. For example, 25 to 100 should be interpreted as a range whose lower limit is 25 and whose upper limit is 100. Additionally, it should be noted that where a range is given, every possible subrange or interval within that range is also specifically intended unless the context indicates the contrary. For example, if the specification indicates a range of 25 to 100, such range is also intended to include subranges such as 26-100, 27-100, etc., 25-99, 25-98, etc., as well as any other possible combination of lower and upper values within the stated range, e.g., 33-47, 60-97, 41-45, 28-96, etc. Note that integer range values have been used in this paragraph for purposes of illustration only, and decimal and fractional values (e.g., 46.7-91.3) should also be understood to be intended as possible subrange endpoints unless specifically excluded.
[0124] It should be understood that the exemplary embodiments described above should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within these embodiments should typically be considered as available for other similar features or aspects in other embodiments.
[0125] While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope of the inventive concept as defined by the following claims.